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Organic solid-state lasers: a materials view

and future development
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Cite this: DOI: 10.1039/d0cs00037j

Yi Jiang,a Yuan-Yuan Liu,a Xu Liu,a He Lin,a Kun Gao,a Wen-Yong Lai *ab and
Wei Huang ab

Lasing applications have spread over various aspects of human life. To meet the developing trends of
the laser industry towards being miniature, portable, and highly integrated, new laser technologies are in
urgent demand. Organic semiconductors are promising gain medium candidates for novel laser devices,
due to their convenient processing techniques, ease of spectral and chemical tuning, low refractive
indexes, mechanical flexibilities, and low thresholds, etc. organic solid-state lasers (OSSLs) open up a
new horizon of simple, low-cost, time-saving, versatile and environmental-friendly manufacturing
technologies for new and desirable laser structures (micro-, asymmetric, flexible, etc.) to unleash the full
potential of semiconductor lasers for future electronics. Besides the development of optical feedback
structures, the design and synthesis of robust organic gain media is critical as a vigorous aspect of
Received 27th March 2020 OSSLs. Herein, we provide a comprehensive review of recent advances in organic gain materials, mainly
DOI: 10.1039/d0cs00037j focused on organic semiconductors for OSSLs. The significant breakthroughs toward electrical pumping
of OSSLs are emphasized. Opportunities, challenges and future research directions for the design of
[Link]/chem-soc-rev organic gain media are also discussed.

a
Key Laboratory for Organic Electronics and Information Displays (KLOEID), Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications,
9 Wenyuan Road, Nanjing 210023, China. E-mail: iamwylai@[Link]
b
Frontiers Science Center for Flexible Electronics, Xi’an Institute of Flexible Electronics (IFE) and Xi’an Institute of Biomedical Materials & Engineering,
Northwestern Polytechnical University, 127 West Youyi Road, Xi’an 710072, China

Dr Yi Jiang received his BS degree Dr Wen-Yong Lai is a full

from College of Chemical Engi- professor at Nanjing University
neering and Materials Science of of Posts and Telecommuni-
Tianjin University of Science and cations. He received his PhD
Technology in 2012. Since 2013, from Fudan University in 2007.
he has been a PhD student in He then joined the Key Labora-
Nanjing University of Posts & tory for Organic Electronics &
Telecommunications under the Information Displays, Institute
supervision of Prof. Wen-Yong of Advanced Materials (IAM),
Lai. In 2017, he joined in Prof. Nanjing University of Posts &
Donal D. C. Bradley’s group in Telecommunications. His research
Department of Physics at mainly focuses on the design,
Yi Jiang University of Oxford as a visiting Wen-Yong Lai synthesis, and application of
PhD student. He then spent two organic & polymer optoelectronic
months as a visiting PhD student at Hong Kong Baptist University materials for organic/flexible electronics. He is also interested in the
working on the research of non-linear optics supervised by Prof. Kok exploration of novel materials and processes for printed electronics.
Wai Cheah. After got his PhD degree in 2018, he went on to work in
Hong Kong Baptist University as a postdoctoral fellow. His current
research mainly focuses on organic gain media, organic functional
materials, optoelectronic/laser devices, and non-linear optics.

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1. Introduction conjugated polymers were reported by Friend and Heeger

in 1996 by using poly(p-phenylenevinylene) (PPV) and PPV
Since the first discovery of laser oscillation nearly sixty years derivatives as organic gain media.17,18 Since then, a number
ago,1 lasing applications have spread over various areas, including of reports on organic semiconductors based OSSLs have
scientific researches, pharmaceutical industries, telecommunica- emerged. A majority of organic semiconductors are demon-
tions, etc. The development of materials plays a crucial role in strated with high optical gain, enabling their uses as optical
advancing novel laser techniques. amplifiers and laser media. The development milestones of
Organic semiconductors have attracted immense attention organic gain media are summarized in Fig. 1.12–14,16–23
in recent years owing to their large-area and low-cost manu- A number of excellent book chapters and review articles
facturing by solution processing, and tunable optoelectronic focusing on various aspects of OSSLs have been published
properties by the convenient molecular design, which make recently, covering topics including organic crystal lasers,24–28
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them potential materials for numerous applications such as light-emitting diode (LED) pumped lasers,29,30 innovative laser
organic light-emitting diodes (OLEDs),2–5 organic solar cells fabrication techniques and applications,31–33 the prospect of
(OSCs),6–8 organic thin-film transistors (OTFTs)9,10 and organic electrically-driven lasers,34 etc. Although several reviews on
solid-state lasers (OSSLs).11,12 A variety of organic semiconductors OSSLs have been constructed by Samuel,35 Forget,36 and
have been explored, which significantly promote the rapid Gather,37 it should be noted that there is no review or book
progress of organic electronics. Particularly, extensive studies have chapter by far to make a comprehensive introduction focusing
been carried out to promote OLEDs into commercial applications on organic gain media. Consequently, a review that provides a
as flat-panel displays and solid-state lighting emitters. OSSLs, clear panorama of organic gain media is highly desirable to
especially organic semiconductor lasers (OSLs), the likely succes- build up a comprehensive overview and for those who may be
sor to OLEDs, as another important class of organic light emitters, interested in the field to get a quick understanding and
have been a young and challenging research topic. A large amount appreciation of this exciting research direction. In this review,
of organic light emitters have been explored as gain media. Due to first, the architectures of organic lasers are briefly described,
their facile processabilities, organic semiconductors are compa- which require a definite selection of organic gain media. Next, a
tible with various optical resonators, and in many cases, the comprehensive overview of organic gain media is presented
optical resonators can be integrated directly with organic gain with the latest researches on organic lasers and gain media.
media, leading to the versatile and relatively low-cost laser devices. The emphatic illustration is placed on the different types of
OSSLs can date back to 1967, when rhodamine 6G doped in organic gain media as well as the discussion of the develop-
polymethylmethacrylate (PMMA) was reported as an organic ment and challenges of OSSLs. The last chapter highlights the
gain medium.13 Whereafter OSLs based on anthracene in strategies and efforts to overcome the challenges accompanied
doped and non-doped single crystals were reported.14,15 with the electrically pumped OSSLs. A major goal of this review
In 1987, Tang and Van Slyke at Kodak reported the first thin- is to provide illustrative accounts on recent researches and
film OLED using tris(8-quinolinolato) aluminum(III) (Alq3) as systematize our knowledge in this field, building up the basic
the emissive layer.16 The significant advancements of OLEDs relationships between organic gain media and light amplified
have revolutionized our understanding on the structure design behaviors. The fundamental principles, extracted from diverse
and functions of organic materials, leading to remarkable research topics, are vital for the rational molecular design of
progress in the development of OSLs. The first OSLs based on organic gain media for electrically pumped OSSL applications.

Dr Wei Huang received his PhD 2. Organic semiconductor laser

from Peking University in 1992. architectures
In 2001, he was appointed as
a chair professor at Fudan 2.1 The building blocks of lasers
University, where he founded Like any other lasers, organic lasers are comprised of three
and chaired the Institute of principal building blocks, a pumping source, an optical feed-
Advanced Materials (IAM). After back structure, and a gain medium. The organic gain medium,
that he became the vice president a p-conjugated organic molecule in most cases, is the basic
of Nanjing University of Posts & characteristic of an organic laser. To fully explore the potentials
Telecommunications, and then of organic lasers, such as facile processing, mechanical
president of Nanjing Tech flexibility and biocompatibility, organic molecules are widely
University. Now he is the deputy investigated as optical gain media for organic lasers. Indeed,
Wei Huang president of Northwestern Poly- the gain media with specific shapes can act as optical feedback
technical University. He was structures by themselves. As far as we are concerned, for the
elected as Academician of Chinese Academy of Sciences in 2011. purpose of laser operation, light trapped within the feedback
His research interest includes organic/plastic materials and structure needs to be amplified, which is required to depress
devices, nanomaterials and nanotechnology, etc. any loss involved in the whole process. As shown in Fig. 2,

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Fig. 1 The development milestones of organic gain media. Soffer and McFarland firstly demonstrated the organic dye for solid-state laser in 1967.13 The
first organic crystal laser using anthracene as gain media was reported by Karl in 1972.14 Tang and VanSlyke demonstrated the first OLED using Alq3 as the
emitter in 1987.16 In 1996, the groups of Friend and Heeger reported the solid-state conjugated polymer lasers by using PPV and PPV derivatives as gain
media, respectively.17,18 In 2008, a polymer laser pumped by LED was proposed by Samuel’s group using a fluorene co-polymer as the emitter.19 Lai and
co-workers in 2009 reported a deep-blue laser with very low lasing threshold and high slope efficiency using monodisperse starburst macromolecular
semiconductors as gain media.12 In 2011, the first observation of lasing behavior in a living system with green fluorescent protein (GFP) was reported by
Gather and co-workers.20 Most recently, Adachi’s group reported the quasi continuous-wave (CW) lasers based on 4,4 0 -bis[(N-carbazole)styryl]biphenyl
(BSBCz) emitters, and near-infrared (NIR) thermally activated delayed fluorescent (TADF) emitters (boron difluoride curcuminoid derivatives) as gain
media.21,22 An electrically pumped organic laser based on BSBCz as gain medium has been demonstrated by Adachi in 2019.23

A fraction of the spontaneous emission from organic semi-

conductors could be reflected back and forth between the
mirrors. With the interactions of excitons in organic gain media
in their excited states, light can initiate stimulated emission
and thus be amplified. If the light amplification exceeds the
optical losses that usually resulted from cavity defect and
absorption of gain medium itself, a continuous photon avalanche
will occur.

2.2 Quasi four-level laser structure of organic semiconductors

In order to realize efficient lasing output from an integrated
Fig. 2 The principal building blocks of a laser: a pumping source, an optical optical feedback structure, the construction of multiple level
feedback structure (formed by two curved mirrors), and a gain medium. lasing system is necessary to achieve efficient population
inversion. Organic gain media are generally advantageous due
to their inherent quasi four-level lasing systems. As depicted
a classical laser design consists of two mirrors for optical in Fig. 3, organic materials are usually rich in energy levels,
feedback with organic gain media filling the space inside. so many stimulated radiative channels are formed under the

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Fig. 3 Energy level diagram of an organic semiconductor, showing singlet excitons, triplet excitons and charges.

coupling of electronic vibration. Actually, most organic emitters In most reports, fluorescent emitters are used as organic
are featuring with quasi four-level systems. In the case of gain media, while triplet emitters with phosphorescence or
optical pumping, the excitons are excited from the electronic TADF are rarely reported.22,40–43 Theoretically, population
ground state (S0, level 1) to the first electronic excited state inversion could also be realized for triplet emitters by con-
(S1, level 2) followed by a rapid vibrational relaxation process to structing quasi four-level lasing system. However, for most
the lowest vibrational level of S1 (level 3). Due to the short triplet emitters (phosphorescence or TADF emitters), the
lifetime from level 2 to level 3 (less than a picosecond), the cross-section of the excited-state absorption (sex, T1 - Tn) is
population inversion usually occurs from level 3 to one of much larger than the maximum cross-section of stimulated
the higher vibrational levels of S0 (level 4). It is very fast for emission (sem, T1 - S0). As a result, no stimulated emission
vibrational relaxation back to level 1, which prevents the occurs during the pumping process.44
construction of any significant exciton population in level 4.
Considering the inevitable optical loss in the gain media and 2.3 Amplified spontaneous emission (ASE)
integrated optical devices, the inherent four-level system of ASE characterization is a simple and effective methodology to
organic emitters is thus much more favorable to ensure the compare the gain characteristics of different materials without
initial sufficient optical gain for generating efficient lasing cavity effects. When the population inversion is established
output. in the quasi four-level system, the stimulated emission ampli-
There are various unfavorable losses, such as cavity scat- fication occurs in the gain medium without optical feedback
tering, ground-state self-absorption, charge absorption, triplet structure. A photon avalanche called ASE will occur through
excited state absorption and so on. These losses can introduce further stimulated emission. ASE characterizations can be used
absorption in the lasing/amplification wavelength region, thus to quantify the available gain excluding an optical feedback
reducing the lasing output energy and/or preventing the lasing structure. Besides, ASE intensity is collected from the edge of
output. As shown in Fig. 3, the singlet excitons may flip their the sample as a function of stripe length, which is referred to
spins to the lowest triplet excitation state (T1) through inter- the variable stripe length (VSL) method. After firstly reported
system crossing (ISC), generally lower in energy, where they can in nitrogen laser by Shaklee,45 VSL method has been widely
accumulate because of the much longer triplet-state lifetime used to evaluate the gain characteristics of organic gain
compared with that of S1. Unfortunately, the triplet–triplet media.11,46–55 The typical gains of organic gain media recorded
absorption band is very broad and overlaps the singlet fluores- with VSL method are in the range of 100–102 cm1.
cence emission band.38 The long lived triplet excitons can lead Actually, the gain could be evaluated by changing the lasing
to optical losses for light amplification due to triplet–triplet (or amplification) output or changing the stimulated emission-
absorption and the reduction of S1 population via singlet– induced signals under different conditions.56–62 Another general
triplet annihilation (STA). Charge absorption is another impor- method to study gains in organic gain media is by transient
tant absorption process potentially detrimental to lasing absorption measurement. The gain calculated from transient
(see Fig. 3). As the absorption overlaps with the stimulated absorption measurement is from the changes in transmission
emission and the long lifetimes allow significant population due to the formation of stimulated emission during the short-
build-up, the absorption from charge excited states could pulse (typically 100 fs) lasing excitation. Transient absorption
prejudice the stimulated emission and gain.32,39 The influences gives more insight into the factors controlling the gain and
of charge absorption and triplet excitons under electrically- provides the gain dynamics. Very high gain is confirmed in this
driven conditions will be discussed further in Section 4. process. For example, the gain coefficients of methyl-substituted

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ladder-type poly(paraphenylene) (MeLPPP) and poly(9,9-dioctyl-

fluorene) (PFO) were calculated to be 2  103 cm1 and 1.2 
104 cm1, respectively, through the transient femtosecond pump/
probe experiments.59,60 However, the gain lifetimes are usually
short (within picosecond time scale). This means that a high
pump rate is needed to maintain a population inversion, which
may lead to exciton annihilation.
It is worth mentioning that ASE and some other effects
are mistakenly interpreted as lasing characteristics, which
Fig. 4 (a) Schematic representation of the excitation direction and Fabry–
complicates the unambiguous identification of organic lasing. Perot cavity direction in the crystal. Reproduced with permission from
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Careful consideration should be given to the evaluation of ref. 68. Copyright 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
lasing rather than ASE, especially in the case of electrical (b) Fluorescence microscopy image of the as-prepared 1,4-bis(2-methyl-
pumping conditions.63 Generally speaking, the threshold and styryl)benzene (o-MDSB) microcrystals. Reproduced with permission from
ref. 66. Copyright 2014 American Chemical Society. (c) Fluorescence
the linewidth narrowing of ASE are less pronounced as compared
microscopy image of the single crystal N,N 0 -bis(1-ethylpropyl)-2,5,8,11-
with lasing. In general, the line width of ASE is a few nanometers, tetrakis(p-methyl-phenyl)-perylenediimide (mp-PDI-1). Reproduced with
while that of single-mode lasing is less than 1 nm.63 permission from ref. 69. Copyright 2015 American Chemical Society.
(d) Fluorescence microscopy image of the single crystal (2Z,2 0 Z)-3,3 0 -
(1,4-phenylene)bis(2-(4-butoxyphenyl)acrylonitrile) (b-DBDCS). Repro-
2.4 Optical feedback structures duced with permission from ref. 68. Copyright 2014 Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim. (e) Fluorescence microscopy image of the
The design and manufacturing of optical feedback structures single crystal of 5,5 0 -bis(4 0 -methoxybiphenyl-4-yl)-2,2 0 -bithiophene
has been developing constantly since lasing was first demon- (BP2T-OMe). Reproduced with permission from ref. 64. Copyright 2012
strated in 1960s. These designs have been widely used for Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
constructing organic lasers. Due to the facile solution-
processibility and the availability of simple device fabrication
process of organic gain media, various optical resonator of l. Recently, similar crystal cavities have been integrated into
configurations have been demonstrated to be able to achieve microlaser arrays.67
efficient lasing output, including photonic crystals, micro- In the polygonal crystal arrays, the square or hexagon has
cavities, whispering gallery mode (WGM) resonators (including attracted much attention because of its good light confinement
micro-disks, micro-cones, and micro-rings), diffraction con- and total internal reflection characteristics (see Fig. 4b–e).
figurations with optical grating structures, i.e., distributed Lasing oscillations have been observed in various small mole-
Bragg reflectors (DBR) and distributed feedback (DFB), etc. cular crystals over recent years.68–73 Besides, these crystalline
An updated comprehensive review regarding the advances on laser cavities are arranged into specific arrays, thus providing a
optical feedback structures has recently been summarized by method to realize multimode lasing with specific charac-
Kuehne and Gather.37 teristics on a single substrate.74 However, the length of the
It is generally considered that the laser with incorporating resonator cavity length is uncontrollable. Therefore, it is still a
an organic gain medium is ‘‘organic laser’’. Actually, numerous challenge to simultaneously realize high-quality single-crystal
examples of organic lasers consist of both organic gain medium resonators and the patterning of these cavities in a large area
and organic optical feedback structure. In some cases, the with a high spatial resolution at submicrometer level. From a
feedback structures are formed by the gain materials them- few reports, the template-assisted75,76 and substrate-assisted
selves, which are advantageous in simplifying the device manu- methods77–79 are much helpful to fabricate organic crystal
facturing. In this section, we emphatically discuss the recent arrays with high crystal quality. These methods make it possible
advancements of ‘‘organic’’ optical feedback structures. to design high-order large-area organic crystal arrays for flat-panel
2.4.1 Organic crystal-based cavities. Regular crystalline laser display applications.80,81
organic microcrystal can be acted as both active gain medium 2.4.2 Organic nanowires (ONWs) and fibers. Free-standing
and optical feedback micro-resonator. In order to form optical semiconductor nanowires are attractive building blocks for
feedback structures, one method is to use end crystal facets as creating electrically driven lasers, because their defect-free
Fresnel reflection in organic crystals. Fig. 4a depicts the sche- structures exhibit superior electrical transport characteristics
matic representation of the excitation direction and the Fabry– in high-quality planar devices. One dimensional (1D) inorganic
Perot resonator cavity constituted with the lateral facets of nanowires are emerging as promising candidates for integrated,
the crystal. The crystal has a group refractive index of up to subwavelength active and passive photonic devices, especially for
ca. 3 and allows a cavity length in an order of magnitude of electrically pumped lasers.61,82–84 Single nanowire can also be
100 mm. Although the Fresnel reflection at the interface used as an independent gain medium and optical cavity. Micro-
between the crystal and air is only ca. 30%, the Q factor has scopic dimensional Fabry–Perot resonators can be fabricated from
been reported to be greater than 1000.64–66 Compared with the wires and fibers, where the nanowires act as optical waveguides
traditional microcavity, the cavity length in the crystal is a and the end-facets act as mirrors. ONWs with submicrometer
multiple of l/2, thus enabling lasing output with wavelength diameters can be fabricated with various methods including

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Fig. 5 Nanowire lasing characterizations. (a) The experimental setup scheme used for single-nanowire/fiber waveguide characterization. Reproduced
with permission from ref. 86. Copyright 2008 Nature Publishing Group. (b) PL microscope image in dark-field of a polymer nanowire. The guiding
direction of light is shown as the red arrows. Reproduced with permission from ref. 87. Copyright 2014 American Chemical Society. (c) Fluorescence
microscopy image of PFO nanowires with scale bar of 5 mm. (d) Emission spectra collected from the tip (blue) and body (grey) of an isolated PFO
nanowire under uniform pulsed excitation (1.4 nJ per pulse). Inset: Fluorescence image of an excited wire with scale bar of 2 mm. (e) Emission spectrum
versus (vs.) pump energy at room temperature, collected from the tip of an isolated PFO nanowire under excitation. Reproduced with permission from
ref. 88. Copyright 2007 Nature Publishing Group.

electrospinning (ES), physical vapor deposition (PVD), solution (CTAB) solution, resulting in uniform single-crystalline ONWs
self-assembly method and template wetting.85 As shown in Fig. 5a with the assistance of the surfactant. ONWs were obtained with
and b, a better insight into the waveguide capability and lasing the lengths of several micrometers and diameters of less than
performance could be achieved by collecting the photolumines- 1 mm. TPP fluorescence was excited by femtosecond pulse laser
cence (PL) signal from a single nanofiber tip, which is excited by a on the wires. Upon cooling to 77 K, emission from exciton
tightly focused laser beam.86,87 O’Carroll et al. observed the first polariton emerged and lasing was achieved at threshold of
single conjugated-polymer nanowire lasing by using template- 60 nJ per pulse. Recently, various compounds, such as N,N 0 -bis-
wetting method.88 Fig. 5c shows a fluorescence micrograph of (1-ethylpropyl)-2,5,8,11-tetrakis(o-methylphenyl)-perylene-4:9,10-
random PFO nanowires. The microcavity effect in PFO nanowire tetracarboxylic acid diimide (mp-PDI-2),91 1,4-chloride-2,5-di[4 0 -
was demonstrated by observing the emission spectrum collected (methylthio)styryl-benzene] (CDSB),92 have been successfully
from the tip rather than the bulk spectrum (Fig. 5d), and the fabricated into ONWs by using this method for constructing
mode spacing is linearly related to the reciprocal of the length organic lasers.
of the ONW. In addition, lasing action with one dominated ES shows many advantages for constructing photonic
narrowed emission peak was observed above the lasing fluence systems based on ONWs because of its ability for the control
of ca. 2.89 mJ cm2 (100 nJ per pulse) (Fig. 5e). The lasing action of ONW morphology and diameter. Camposeo et al. reported
was also observed in small-molecular single-crystal ONWs lasing emission from electrospun PMMA nanowires embedded
(2,4,5-triphenylimidazole, TPI) via adsorbent-assisted PVD with coumarin 334, rhodamine 6G, and Nile Blue A perchlorate,
fabrication. The microcavity behaviors were affected significantly respectively.93 The fiber diameters were well controlled between
by the wire dimensions.89 100 and 600 nm. Lasing was observed at a threshold of
Because the solution self-assembly method is a simple 60 mJ cm2 from doped rhodamine 6G nanowire. Moreover,
alternative method for the preparation of ONWs, it is possible the electrospun fibers made of conjugated polymers can obtain
to use compounds that are easy to crystallize to prepare ONWs. the nonwoven fleeces consisting entirely of gain materials.
Zhang et al. reported two-photon-pumped (TPP) blue lasing By using room temperature nanoimprint lithography (NIL),
in 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)- Benedetto et al. prepared the electrospun conjugated polymer
1,3,5-triazine (DPBT) ONWs.90 A THF solution of DPBT with fibers with imprinted periodic structures, with significant
the molecular packing preference along one crystal axis, was waveguide enhancement along the fibers.86 Such a geometry
injected into an aqueous cetyltrimethylammonium bromide can be used for the enhancement of nanofiber forward emission,

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but lasing was not demonstrated. Recently, nanowire lasing from Fabry–Perot cavity was built up using MOF crystals as reflectors.
perovskites were also reported.94,95 As shown in Fig. 6f, TPP lasing around 640 nm with a threshold
2.4.3 Organic quasi-periodic structures. The constructions of 18.8 mJ cm2 (0.148 mJ per pulse) was observed in bio-MOF-
of the quasi-periodic structures as feedback structures, based 1*DMASM pumped at 1064 nm. This study provides a new way
on organic materials themselves have become a hot topic in to construct organic quasi-periodic structures, and opens a new
recent years. Metal organic frameworks (MOFs), also well application prospect for TPP microlasers with high efficiency
known as coordination polymers, were first reported in the for photonic integrated circuits. MOF crystal for three-photon-
mid-1990’s by Yaghi et al.96,97 It is a novel type of solid crystal- pumped (3PP) microlaser has been realized in ZJU-68*DMASM
line materials, which are able to combine the advantages via the same strategy by He et al.101 By sequentially changing
of both traditional organic and inorganic photoluminescent the polarity of the adsorbed solvents from water to toluene
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materials, manifesting unique properties. MOFs have emerged low-polarity, Wei et al. observed lasing behaviors with wave-
as multifunctional materials for various applications, including length tuning over 40 nm in a single MOF (DASP+@bio-
catalysis, chemical sensing, gas storage and separation, bio- MOF-100) based microlaser.102 Recently, stimulated emission
medicine, and optical/electronic/magnetic applications.98 from MOF single crystals were reported, which will be discussed
As host matrices, MOFs offer an unique platform to confine in Section [Link].103
and stabilize functional species, leading to unique behaviors in Covalent organic frameworks (COFs), as another kind of
the defined pore environments.99 By fixing the organic dyes crystalline porous polymers, also first reported by Yaghi’s group
into the MOF pore spaces, a Fabry–Perot cavity was constructed in 2005,104 provide specific spaces for the interactions among
by using the top and bottom facets of the rectangular MOF electrons, holes, photons, excitons and guest molecules,
crystal, which provides necessary feedback by efficiently reflecting thereby exhibiting specific properties and functions.105–107
the stimulated emission for lasing output. Yu et al. reported TPP Some fluorescent 3D COFs have been explored and used for
microlasers by encapsulating the cationic dye (4-[p-(dimethyl- explosive detection,108,109 however, COFs themselves acting as
amino)styryl]-1-methylpyridinium (DMASM)) into the anionic quasi-periodic structures or gain media remain challenging.
bio-MOF-1 (Fig. 6a).100 The resulting bio-MOF-1*DMASM exhib- 2.4.4 Random lasers. Usually, laser actions occur in
ited new fluorescence emission in orange to red region. The PL precisely configured resonant cavities. However, coherent laser
quantum yield (PLQY) of 25.9% was achieved for bio-MOF- actions may also occur in disordered systems, when excitation
1*DMASM, which is higher than that of DMASM solution and intensity exceeds a certain threshold, which is known as
powder (Fig. 6b–e). The significantly enhanced fluorescence effi- ‘‘random lasing’’. Optical structures can be created in a random
ciency and the large two-photon absorption (TPA) cross-section of laser by utilizing the intrinsic disorders in organic/inorganic
DMASMI dye (ca. 104 GM, 1 GM = 1050 cm4 s photon1 photonic materials. The lasing was ascribed to multiple scattering
molecule1) enabled bio-MOF-1*DMASM to be an outstanding resulted from refractive index inhomogeneities (e.g., impurities,
TPP up-conversion laser emitter. A high-quality (Q E 1500) crystallites and morphology variations) that provided a closed

Fig. 6 (a) Schematic illustration of bio-MOF-1 encapsulated by pyridinium hemicyanine cationic dye DMASM. (b–e) Fluorescence microscopic images
of bio-MOF-1*DMASM with different dye contents of (b) 0, (c) 0.04%, (d) 0.14% and (e) 40.00%. (f) Bio-MOF-1*DMASM TPP lasing spectra under
different pump energies. Inset: A single crystal microscopy image of bio-MOF-1*DMASM excited at 1.064 nm (left) and dependence profile of the
fluorescence intensity on pump energy (right). Reproduced with permission from ref. 100. Copyright 2013 Nature Publishing Group.

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light path for optical feedback without additional laser cavity. ‘‘organic dye lasers’’ and ‘‘OSLs’’, so it is vital to classify these
The primary competitive advantage of random lasers, compared materials.
with regular lasers, is cost-effective and facile processing. The Historically, the distinction between dyes and organic semi-
high-precision approaches for generating ultra-precise micro- conductors has been motivated by the pursuit of achieving
cavities/gratings are not demanded here. Additionally, the laser electrically pumped lasers. At present, most of the pumping
devices can be produced on large scales with high emission sources of organic lasers are still optical devices, and their
efficiency.110 Random lasers often show a multitude of narrow semiconducting properties have not been fully studied.
laser lines accordingly by changing the position and excitation In those cases, it seems irrelevant to distinguish dyes from
density.111 Resonance in random lasers is generally obtained by organic semiconductors according to their electrical properties.
multiple scattering with a random path and localized states in the In this review, we follow the viewpoint of Samuel et al. to
classify organic dyes and organic semiconductors.35 Three
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ill-defined and disordered gain media.

The random laser can be easily manufactured on an indus- properties are proposed to make a division for organic semi-
trial scale. The key point to realize random lasing is creating conductors, i.e., (i) easy processing in the thin film fabrication,
strong enough scattering, which determines the lasing process. (ii) a high PLQY even in neat film, and (iii) capability of charge
Various optical gain media were reported with random lasing transport.
property, such as liquid laser dyes with scatterers,112–114 laser In this section, we will introduce the development of organic
crystals and solid-state luminescent powders,115 alumina gain media, including organic dyes, fluorescent organic semi-
nanoclusters and scattering films,116 polymeric films with conductor emitters, triplet gain media, and others.
scatterers,117–119 porous media infiltrated with dyes and
others,120–122 etc. Owing to their advantages such as low cost, 3.1 Organic dyes
simple operation, strong robustness, random lasers have In the historical and usual sense, an organic dye is a substance
attracted much attention in both theoretical and experimental able to impart color to another one. Organic dyes have an
fields, and has potential applications in the fields of sensors,123 absorption band in the spectral region from ultraviolet (UV) to
micrometer-scale laser sources,110 and laser imaging.124 NIR. All these molecules involve multiple conjugated double
bonds, which strongly confine their spectral properties and
2.5 Pumping sources their chemical reactivities. One of the significant causes for the
rise of dye lasers is the huge panel of molecular structures,
In most cases, the pumping source for organic lasers is an which able to act as laser dyes. The emission of laser dyes cover
external, pulsed light source, which is used to directly pump the the whole visible spectrum, and even include the spectral
organic gain media. The pumping light sources could be lasers region of near UV and NIR. More than 500 different dyes can
(in most cases), laser diodes,125–127 LEDs,19,29,30 etc. Due to the be found on commercial websites, such as Luxottica|Exciton
low power densities needed for thresholds in some feedback (website link: [Link] with various
structures, such as DFB gratings and photonic crystals, they are absorption and emission bands. The categories based on their
promising in achieving abundant exciton densities for lasing chemical structures are usually used as laser dyes. The main
actions via electrical pumping. The typical electrical device laser dye series are coumarins (1), xanthenes (2), and pyrro-
structures to realize electric excitation are vertical OLED archi- methenes (3).
tecture and planar organic light-emitting transistor (OLET) The xanthene family has been widely used in history,
geometry. A recent work reported an example of organic lasing especially the high efficiency rhodamine dyes (rhodamine
from electrically pumped OLEDs with using electrical pumping 640, rhodamine 6G, etc.). Over the last decades, dyes have been
source (see Section 4 for more details).23 more particularly explored for lasing applications with enhanced
Using the optical structures of various gain media, including performance and photostability. Here, we briefly introduce some
TPP lasers, 3PP lasers and four photon pump lasers, the multi- well-known laser dyes.
photon pumped (MPP) frequency-upconversion lasers are also Coumarin dyes are an important family as their emission
realized.128 The gain media of MPP lasers include organic dye covering the wavelength range of violet to green. A generic
solutions, dye-doped solid rods, crystals, optical nanowires/ coumarin is the alliance of a cyclobenzene with a pyrone,
fibers, thin film waveguide structures, etc. attached with various substituents on this basic core, as
depicted in Scheme 1. The nature of these attached substituents
strongly dominate the spectroscopic properties of coumarin dyes
3. Organic gain media (the basic coumarin molecule is non-fluorescent). Seven samples
(coumarins 153, 343, 521, 504, 460, 6 and 540) (1a–1g) are given
Organic dyes dissolved in liquid solvents have been explored in Scheme 1. Coumarins are relatively efficient as laser dyes,
for lasing applications for decades.129 However, close packing however, their very weak photostabilities limit their appli-
of organic pigments often leads to self-quenching of cations.130
luminescence. Alternatively, doping dyes into non-conjugated Xanthenes are a class of dyes including rhodamines, eosins
polymers, such as polystyrene (PS) and PMMA, are suitable for and fluorescein. These molecules emit with high efficiency
OSSLs. Actually, there are fundamental similarities between and good photostability in the green to red spectral region.

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dyes provide a variety of functional positions, and the linked

end-cappers have significant impacts on the characteristics
of fluorescence and stimulated emission. Probably the most
well-known pyrromethene dyes for lasing are 1,3,5,7,8-penta-
methyl-2,6-diethylpyrromethene-difluoroborate (named as pyrro-
methene 567, 3a), where the two lateral end-cappers are C2H5,
and 1,3,5,7,8-pentamethyl-2,6-di-t-butylpyrromethene-difluoro-
borate (named as pyrromethene 597, 3c), where the two lateral
end-cappers are tert-butyles. The bulky tert-butyles in pyrro-
methene 597 (3c) may cause the enhanced steric hindrance,
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which makes the excited-state molecule non-planar, leading to

a lower PLQY than Pyrromethene 567 (3a).132 Massive efforts
have been made to demonstrate the 8-position (R2, symmetric
to the BF2 group) substitution’s influence by linking different
functional groups, such as alkyl, aryl133 and some more
complex groups.132,134–136 The novel pyrromethene dyes,
named as PA-BODIPY (3d)135 and EDOT-BODIPY (3e),136 are
listed in Scheme 1. The photostabilities of pyrromethenes were
relatively weak in solution. In fact, the singlet oxygen generated
at the 7,8 double bond of the central ring in the triplet states
during exciting the molecule generally induces a metastable
compound, and eventually destructs the dye structure.137 The
degradation influence of oxygen could be limited by adding
oxygen quenchers in deoxygenated solutions. The different 8
position substitutions also influence the photostabilities with-
out sacrificing the intrinsic spectral characteristics.137 Interest-
ingly, when incorporating pyrromethene dye into a solid-state
matrix, the dissolved oxygen quantity is lower, leading to
improved lifetime.
Additionally, there are some other laser dyes, including
stilbene dyes (e.g., stilbene 420 (4),138 as shown in Scheme 2),
cyanine dyes (e.g., LDS 698 (6),139 LDS 798 (7),140 and LDS
950 (8),141 as shown in Scheme 2), and oxazine dyes (e.g., Nile
Scheme 1 Dye examples, including coumarin dyes, rhodamine dyes and blue 690, as shown in Fig. 7). Scheme 2 also presents the
pyrromethene dyes. chemical structures of 4-(dicyanomethylene)-2-methyl-6-
(4-dimethylaminostryl)-4H-pyran (DCM, 5a) and 4-dicyano-
methylene-2-tert-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-
The basis core of rhodamine dyes (2a–2e) is two benzene rings pyran (DCJTB, 5b) that are extensively used for dye lasers.
associated with a pyran ring in the middle (see in Scheme 1). As shown in Fig. 7a, organic dyes exhibit broad emission
Among them, rhodamine 6G (2a) is extensively used and often tunabilities covering the whole spectral region from UV to NIR.
selected as the benchmark for other laser dyes. The singlet– Mhibik et al. demonstrated very broadly tunable lasers within
singlet absorption of rhodamine 6G is very strong with molar 230 nm range (from 440 nm to 670 nm), by using coumarin 460
extinction coefficient of 1.1  105 l mol1 cm1 at 540 nm. But (C 460, 1e), coumarin 540 A (C 540A, 1d), pyrromethene 567
at the same time, as one of the major issues for organic lasers, (P 567, 3a), pyrromethene 597 (P 597, 3c), and a blend of
triplet–triplet absorption (see Section 2.2) is also non- rhodamine 640 and C 540A (1d) as the doped emitters.142
negligible.131 An attractive way for improving the efficiencies Continuous wavelength tunability (within 50 nm) for a given
of dye lasers is to depress the triplet–triplet absorption, as material is obtained by rotating the Fabry–Perot interferometer
discussed later. inside the microcavity. PMMA-coated film is selected as Fabry–
Pyrromethene dyes (3a–3e) are a new category of laser dyes Perot interferometer. When C 540A (1d) was used as a doped
recently developed. Their chemical structures are depicted in emitter, a clear lasing threshold of 8.46 mJ cm2 (11 mJ per pulse) is
Scheme 1. The basic unit structure consists of two pyrroles detectable with a lasing slope efficiency of 8% and maximum
linked by a BF2 group and a methylene with high rigidity. output energy of 4.5 mJ per pulse. LDS798 (7) and LDS950 (8) are
Pyrromethene dyes exhibit good solubilities in organic solvents explored as NIR laser dyes. The ASE thresholds are ca. 12 mJ cm2
(or in polymer matrixes) and good thermal stabilities, high PLQYs and 0.22 mJ cm2 for LDS798 (7) and LDS950 (8), respectively.140,141
(40.9) and reduced rates of intersystem crossing, making them The laser dyes can be doped in organic semiconductor
generally outperform rhodamine 6G (2a). Moreover, pyrromethene materials to construct the guest–host systems. The organic

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Scheme 2. By doping cis-DCSQ (9) into a 4,4 0 -bis(9-carbazolyl)-

2,2 0 -biphenyl (CBP) host at a concentration of 0.5 wt%, a
marked increase of PLQY is achieved in the doped film because
of efficient FRET between CBP and cis-DCSQ and suppressed
aggregation-induced quenching. The doped film exhibited
stimulated emission with an ASE threshold of ca. 10 mJ cm2
and emission peak at 687 nm.
Compared with organic dyes, organic semiconductors are
much more favorable for lasing applications, due to their facile
chemical functionalization, relatively low lasing thresholds,
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and semiconducting electrical properties. Various organic

semiconductors have been explored and investigated for lasing
applications, which will be discussed extensively in the next
section. Owing to their facile synthesis, organic dyes are con-
venient and unique alternatives for generating tunable coherent
radiation in the full visible and NIR spectral regions.149 Recently,
Scheme 2 Other dye examples, such as stilbene 420, LDS 698, LDS 798, based on doped laser dyes as the emitters, nanowire lasers,93,150
LDS 950, DCM, DCJTB and cis-DCSQ. random lasers,113,114,151 and multi-photon pumped lasers152
have been reported.

semiconductor host could get rid of concentration quenching 3.2 Fluorescent organic semiconductor materials
of laser dyes by physically separating the emissive units, and In the late 1980s, Tang and Van Slyke at Kodak invented the
transferring efficient energy to the laser dyes via Förster energy first thin-film OLED with Alq3 as the emitter.16 The rapid
transfer (FRET). A typical example is Alq3:DCM (5a).143–145 progress of OLEDs has revolutionized our understanding on
In this case, the host material with high-energy band gap the relationship between molecular structures and optoelectronic
absorbs the pump energy, and then transfers its energy to the properties of organic semiconductor materials, which has
guest with low-energy band gap (DCM, 5a) via FRET. Compared inspired the remarkable advancements in OSLs. So far, a number
to the DCM (5a) doping system in a passive matrix, such as PS of materials have been reported as organic gain media. Fluores-
and PMMA, the guest–host energy transfer system enables cence materials for OSLs can be primarily categorized into organic
a much higher pumping source absorption; the resulting crystals, amorphous small molecules, dendritic starburst mole-
guest–host system is also conductive for charge transport via cules, conjugated polymers, etc. The latest triplet gain media will
Alq3 semiconductors. The enlarged Stokes shift consequently be individually discussed in Section 3.3.
reduces self-absorption. Moreover, in the resulting guest–host In the following sections, we present a summary covering
system where the laser dye act as the guest, the device exhibit the latest advances and highlight the fluorescent organic gain
semiconductor characteristics.146–148 For example, Adachi’s materials with outstanding behavior and high performance.
group recently reported deep-red ASE from a novel dye, According to data extracted from most reports, we summarize
named as cis-configured squaraine (cis-DCSQ, 9), under optical the emission wavelengths, required energy densities at thresholds
pumping.148 The chemical structure of cis-DCSQ (9) is shown in (areal energy densities, areal power energy densities), and gain

Fig. 7 (a) Wavelength tunable range for some dye families. (b) Tunable lasing results from five doped-emitters, i.e., coumarin 460 (C 460), coumarin
540 A (C 540A), pyrromethene 567 (Py 567), pyrromethene 597 (Py 597), and a blend of rhodamine 640 (Rh 640) and C 540A. Reproduced with
permission from ref. 142. Copyright 2013 American Institute of Physics.

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values of the gain media. We also discuss the gain materials with intermolecular interactions lead to low PLQYs (less than 9%) in
particular focus on the important optoelectronic parameters unsubstituted oligothiophenes (a-nTs). Oligothiophenes with
including PLQY, full width at half maximum (FWHM), ASE/lasing various functional groups or constructing fused oligothio-
energy density at threshold, optical gain, and the mentioned phenes have thus been explored to enhance the PL efficiencies
relevant values. in solid state by depressing the intermolecular interactions. For
3.2.1 Organic crystals. Lasing were recorded in doped and example, functionalization with two ketones at the thienyl
non-doped organic crystals by using anthracene (10) as the sulphur atom and adding some flexible chains in the rigid
emitter in 197214 and 1974,15 respectively. Since then, organic skeleton have significantly increased solid-state PLQYs (up to
crystals have drawn immense attention for their attractive 37%) and tunable PL emission.157
applications as laser photonics.24,25,27 Oligophenylenes (14–16) are another well-studied category
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Compared with amorphous materials, organic crystals of organic semiconductors, which exhibit high PLQYs in both
possess long-range molecular order, which provides advanta- solution and solid state. As a model compound, p-sexiphenyl
geous high anisotropy of the crystals and well-defined crystal- (p-6P, 16) crystal was investigated extensively regarding the ASE
line structure to form self-laser-cavity, leading to better thermal and self-optical feedback properties.158–160 Blue lasing were
and photochemical stabilities, superior charge-carrier trans- observed in both single p-6P (16) nanofiber and close packed
port properties, larger refractive indexes and polarized emis- crystalline nanofiber film. A high net gain value of up to
sion. Until now, ASE or lasing properties are quite inferior for 103 cm1 was detected in the nanofiber.161 ASE behaviors of
most of the existing organic crystals, including oligothio- the same material under femtosecond and nanosecond pumping
phenes, oligophenylenes, thiophene–phenylene co-oligomers conditions were different.162,163 The report by Losio et al. showed
(TPCOs), oligophenylene vinylenes (nPVs), fluorene/phenylene that under femtosecond lasing pulses excitation, there are dual-
co-oligomers, cyano derivatives, etc.25 For organic crystals, the wavelength ASE at 427 and 450 nm in p-6P (16) bulk crystals;
crystal quality, molecular stacking, and intermolecular inter- while excitation by nanosecond laser pulses led to only one peak
actions could play important roles in amplification (or lasing) at 450 nm. It suggested that the population inversion at 427 nm
behaviors.24,25 might has larger non-radiative loss compared to that at
450 nm.162 In fact, the sample morphologies significantly influ-
[Link] Thiophene and phenylene based crystals. a-Linked ence on ASE properties. The competitive dual-wavelength ASE at
oligothiophenes (11–13) are a typical class of materials for 0–1 and 0–2 transitions was also observed in other material
optoelectronic devices, especially crystal laser devices. Popula- system by varying the crystal thicknesses.164 The reabsorption
tion inversion was firstly demonstrated in non-doped a-8T process is considered to affect their net gain properties.
crystals (13).153 The linear a-8T molecules have quasi-planar Another class of organic crystals with stimulated emission
all-trans conformation, and are all parallel to each other in are TPCOs (17–27), in which the phenylene and thiophene are
crystal. The stimulated emission of a-8T (13) appeared initially hybridized at the molecular level. In the past decade, a large
with narrowed emission peak at 700 nm. With the further number of TPCOs have been developed, including block and
increase of pump energy, a second narrow emission appears alternating co-oligomer, phenyl-capped oligothiophenes, thienyl-
at 640 nm. In a-4T (11) and a-6T (12) crystals, similar pheno- capped oligophenylenes, etc.165–172 As shown in Scheme 3, the
mena were also observed.154–156 The stimulated emission lines extension of p-conjugated TPCO molecular backbones can be
correspond to 0–1 and 0–2 vibronic transitions. The strong adjusted by varying the total numbers of ring and arranging

Scheme 3 Materials based on anthracene, oligothiophenes, oligophenylenes, and TPCOs for organic single-crystal lasers.

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the phenylene and thiophene units at the molecular level. For These studies provide potential routes for the rational minia-
example, introducing a longer thiophene as the molecular block turized laser design.
with biphenyl groups as end cappers, the bandgap decreased in
the sequence of BP1T (22) 4 BP2T (24) 4 BP3T (26) (the chemical [Link] nPV crystals. PPV materials play vital roles in the
structures of BP1T(22), BP2T (24) and BP3T (26) are depicted in advance of polymer light-emitting diodes5 and polymer lasers.17,18
Scheme 3; the number of 1, 2, or 3 represents the number of Correspondingly, their oligomers with different vinylene
thiophene groups in the corresponding molecular structures). unit numbers (2PV (28), 3PV (29), 4PV(30)) are also important
For BP1T (22) crystal, ASE occurred at 466 nm,160 while the gain media for crystal lasers.179,180 Among nPV derivatives,
stimulated wavelength moved to 618 nm for BP3T (26).71 trans-distyrylbenzene (DSB/2PV, 28) is the most typical model
By extending the p-conjugated backbones, ASE emission shifted compound, and has been extensively explored as laser crystals.
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from blue- to red-spectral region in different TPCOs crystals. High efficient deep-blue emission is obtained in its dilute
Moreover, the various molecular shapes in TPCOs, e.g., bent, solution. The PLQY decreases sharply with obvious batho-
straight, and zigzag, are beneficial for weakening the inter- chromic shifted emission in solid state due to the formation of
molecular interactions and enhancing the PL emission.64,173–176 H-aggregates.181,182 Over the last few years, a number of
Recently, Dong et al. reported dual-wavelength lasing behaviors of distyrylbenzene derivatives (31–37, as shown in Scheme 4) with
hexagonal shaped BP2T (24) microcrystals.177 A WGM resonator different substituents have been developed for allowing a
was constituted of the flat surfaces and smooth end facets of the unique platform to understand the structure–property relation-
hexagonal BP2T (24) microdisk, and provided efficient feedback ships and exploring the applications of crystal lasers. In some
for lasing oscillation. The vibrational structured fluorescence unique dipole stacking motifs, such as cross dipole stacking
property of BP2T (24) microdisk brought dual-wavelength lasing (X-aggregate) and head to tail dipole stacking (J-aggregate), the
corresponding to the 0–1 and 0–2 vibronic transitions. The lasing fluorescence quenching could be suppressed and the fluores-
thresholds at 0–1 and 0–2 vibronic transitions were 27.2 mJ cm2 cence emission in solid state could even be enhanced.183 Spectral
and 31.8 mJ cm2 with lasing peaks at 527 nm and 562 nm, features and constants of PLQYs, lifetimes and radiative rates as a
respectively. Interestingly, under certain vibronic transitions, result of different DSB stacking systems are depicted in Fig. 8.
the dual-wavelength lasing could be reversibly switched by the The substitutions of benzene with alkyl- and alkoxy-flexible
modulation of the relative optical gain intensity by controlling chains, and the positions of benzene in the DSB phenyl units
the population via varying the operational temperatures. Also are important ways to achieve high solid-state PLQYs and low
reported by Dong et al., by adding optical absorber (BP3T, 26) ASE thresholds. Kabe et al. reported two different position
into BP1T (22) microcrystals, the output lasing wavelengths methyl-substituted DSB derivatives, named as 1,4-bis(4-methyl-
of BP1T (22) were switched across all vibronic bands (0–1, styryl) benzene (p-MDSB, 31) and 1,4-bis(2-methylstyryl)benzene
0–2, 0–3, and 0–4) covering the entire emission spectrum.178 (o-MDSB, 32).164 PLQYs of 54  1% and 67  1% were achieved

Scheme 4 DSB and their derivatives.

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benzene, and diphenylamine, were selected to develop DCS

derivatives.68,190–198 The reported DCS derivatives (38–46) for
organic crystal lasers are shown in Scheme 4. The corres-
ponding crystallographic and amplified emission properties
are listed in Table 1. Since the substitutions impact largely
the intermolecular interactions by secondary interactions
including local dipoles and hydrogen bonding, the emission
of DCS single crystals in solid state could be effectively adjusted
by elaborate modulation of the substitution patterns. Direc-
tional non-covalent interactions, such as hydrogen bonds,
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p–p interactions, induced crucial impact on the aggregation

patterns, and thus significantly affected the ASE/lasing
performance.196,197 Yoon et al. reported a range of system-
atically substituted novel DSB fluorophores with wavelength-
tunable emission in the single crystalline state, named as
a-MODCS (40), a-MODBDCS, b-MODCS and b-MODBDCS.192
Their chemical structures are depicted in Fig. 9a. All com-
pounds crystallized with different degrees of p–p overlap and
distance. The particular secondary bonding interactions,
including multiple hydrogen bonds of C–H  N and C–H  O,
donor–acceptor and local dipole interactions, etc., led to
fluorescence emission wavelength tuning from blue- to red-
Fig. 8 Optical absorption (right) and PL emission (left), as well as photo-
spectral region (see Fig. 9a and b). The spectral bathochromic
physical data (PLQYs, FPL; lifetimes, tPL; and radiative rate constants, kPL) of
DSB nanoparticles. Absorption and emission spectra from H- and shift was correlative with the increased intermolecular coupling
J-aggregates and excimers are indicated. Absorption and emission spectra by a systematic transition from a J-type motif (a-MODCS, 40)
in solution are also involved (dashed lines) for comparison. Reproduced towards an H-type stacking. In H-type aggregated single crystals
with permission from ref. 183. Copyright 2013 Royal Society of Chemistry. (a-MODBDCS, b-MODCS and b-MODBDCS), significant p–p
stacking gave rise to the pronounced intermolecular inter-
actions and thus excimeric emission features. Only a-MODCS
for p-MDSB (31) and o-MDSB (32) crystals, respectively. o-MDSB (40) with J-type aggregate exhibited ASE characteristic during
(32) single crystal exhibited an ASE threshold of 14 (2) mJ cm2, optical pumping process. No spectral narrowing was observed
which is reduced by two orders of magnitude compared with that in the H-type aggregated crystals due to the effective inter-
of DSB (28) (2.2 or 4 mJ cm2).181,184 Another methyl-substituted molecular vibronic coupling (as shown in Fig. 9c).
DSB (4mDSB, 33) with minimized p–p overlap was reported, in
which the electronic structure was only slightly modulated [Link] Other crystals. Apart from above-mentioned crystal
by switching the herringbone stacking to a cofacial motif.184 materials, ASE can be observed in several other organic crystals,
Compared with the other DSB derivatives, the 4mDSB (33) crystal such as azacyclic crystals, anthracene derivatives, fluorene/
exhibited a lower ASE threshold (780 mJ cm2) and a higher gain phenylene co-oligomers, chalcone derivatives, etc. (Scheme 5).
coefficient of 77 cm1. The phenyl-substitutes were introduced Wang et al. reported a new molecule, named as 4,4 0 -(thiazole-
into the DSB derivatives (PDSB, 34) to decrease the p–p overlap. [5,4-d]-thiazole-2,5-diyl)bis(N,N-diphenylaniline) (PTATA, 47).199
The induced phenyl bridgeheads could perish the parallel mole- Interestingly, by varying the crystal growing conditions, the
cular stacking, and formed X-/J-aggregate for high efficiency fluorescence emission of PTATA (47) crystal could be tuned from
fluorescence.185 The resulting high quality films in the phenyl green to orange. The reason for the different wavelength emis-
substituted DSB derivatives are favorable for the potential appli- sion properties is the slight differences in molecular stacking
cations in OLEDs186 and crystal lasers.187–189 Fu’s group tried arrangements and crystal shapes, which were introduced by
other methods to build up new DSB crystals. The cyano67 and crystal growing conditions. Only green-light-emission PTATA
thiomethyl65 substitutes were added on the terminated benzene, (47) crystal exhibited low ASE thresholds. Additionally, novel bi-
named as CNMODSB (36) and MSMODSB (37), to form 1,3,4-oxadiazole derivatives (BOXD-n, n = 1, 4) were designed by
J-aggregate or weak H-aggregate. The low-threshold microlasers Qu et al.200 The different terminal flexible chains of BOXD-n
were achieved by the formation of CNMODSB (36) and dominated the molecular self-assembly. The slipped p–p stacking
MSMODSB (37) nanowires. The lasing thresholds were recorded was achieved in BOXD-4 (48) single crystal with J-type aggregate,
as 1.09 mJ cm2 and 0.1 mJ cm2 for CNMODSB (36) and leading to highly polarized fluorescence and deep-blue ASE with
MSMODSB (37) nanowires, respectively. threshold of 200 mJ cm2 and peak at 403 nm.
DSB derivatives with substituted symmetrical di-cyano units Fluorene and anthracene units are widely used to construct
at the vinylene points (DCS) are also remarkable candidates for small-molecular, dendritic and polymeric gain media, for
crystal lasers. Various substituents, such as flexible chain, thin-film lasers. Due to their likelihoods of high PLQYs, large

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Table 1 Crystallographic, photophysical and amplified emission data of organic single crystals

Amplification Threshold [mJ cm2] Threshold

a b c
Compd Shape SG Arrangement Exciton coupling lem process (Q)d lASE or laser (at pulse length) [kW cm2] Ref.
a-4T Plate P21/c HB H 512, 553 ASE 553 10K: 100 (600 ps) 1.7  102 155

Chem. Soc. Rev.

a-6T Plate P21/n HB H 536, 589 ASE 589 300 K: 700 (30 ps) 2.3  104 156
Review Article

10 K: 35 (30 ps) 1.2  103

a-8T Plate P21/a HB H 640, 695 ASE 695 10 (33 ps) 1.7  102 153
p-4P Plate P21/c HB H 388, 408 160
p-5P Plate P21/c HB H 426, 448 ASE 426 100 (500 ps) 2  102 160
p-6P Plate P21/c HB H 427, 449 ASE, RA 427 110 (120 fs) 9.2  105 162 and 163
885 (7 ns) 1.3  102
AC5 Plate P21/c HB H 515 ASE, RE (2.5  104) 515 42 (500 ps) 84 173
440 (16 ns) 28 168
AC 0 5 Plate — — — 560, 595 ASE, RE 544 1500 (16 ns) 94 169
AC7 Plate — — — 540, 565 ASE, RE 565 2500 (16 ns) 160 169
AC 0 7 Plate P21/c HB H 528, 557 ASE, RE (1.1  104) 525/556 — — 170 and 171
BC4 Plate — HB H 499 ASE 499 27 (500 ps) 54 173
BP1T Plate P21/n HB H 695 ASE, RA (4.4  102) 695 27 (500 ps) 54 173
BP1T-OMe Plate Cmc21 HB H 470. 500, 530 ASE, RE (1.3  104) 5000 (16 ns) 3.1  102 72
BP2T Plate P21/c HB H 565 ASE, RE (1.1  102) 565 355 (500 ps) 7.1  102 173
RE (2.0  104/2.4  104) 527/562 27.2/31.8 (100 fs) 2.7  105/3.2 177
 105
BP2T-OMe Plate Pbca HB H 525, 562 ASE, RE (4.5  103) 525 200 (200 fs) 1.0  106 64
BP3T Plate P21/c HB H 580, 618 ASE, RE (1.6  104) 618 8 (500 ps) 16 71
P6T Plate P21/c HB H 688 ASE, RE (1.8  104) 688 750 (500 ps) 1.5  103 172
DSB/2PV Plate P21 HB H 444, 472 ASE 475 4  103 (100 ps) 4  104 181
Needle P HB 444, 472 ASE, RA 475 2.2  103 (300 ps) 7.3  103 184
3PV Needle — — H 495, 526 ASE 526 11 (500 ps) 22 180
4PV Plate P21/a HB H 525, 550 ASE 553 20 (600 ps) 33 179
pMDSB Olate Pbca HB H 461, 488 ASE 461 25 (500 ps) 50 164
oMDSB Plate P1 HB/p-stack H 460, 488 ASE 452 14 (500 ps) 28 164
4mMDSB Plate P Q H 442, 468 ASE 468 780 (300 ps) 2.6  103 184
RA 2.4  103 (300 ps) 8.0  103
PDSB Plate P1 Q N 452, 471 ASE 452 7.0  103 (10 ns) 7.0  102 187
Needle P21/c X N 444, 463 ASE 452 1.36  104 (10 ns) 1.36  103 188
DBASDSB Needle P1 Q N 532 ASE 532 1.5  102 (100 fs) 1.5  106 189
RA 532 TPA: 1.68  103 (100 fs) 1.7  107
CNMODSB Needle P21/c p-Stack J 533 RE (8.8  102) 533 1.1 (150 fs) 7.3  103 67
MSMODSB Needle P21/c Anisotropic wH 500, 525 ASE/RE (1.0  103) 501 0.22 (150 fs) 1.5  103 65
TPA: 55 (120 fs) 4.6  105 217
aDCS Plate Pbca m-HB J 440 ASE 501 1.8  104 (10 ns) 1.8  103 197
bDCS Tube P1 m-HB H 482 ASE 482 360 (10 ns) 36 196
aMODCS Needle P21/c p-Stack wJ 495 ASE, RA 496 2.1  103 (300 ps) 7.0  103 192
bPDCS Plate P1 Q J 470 ASE 470 400 (10 ns) 40 194
4.6 (200 ps) 23 190
bDBDCS Plate P21/c m-HB H 484 ASE, RA, RE (8.7  103) 484 0.4 (300 ps) 1.3 68
aDBADCS Plate J 597 ASE, RA 597 1.8  103 (300 ps) 6.0  103 191
aDPADSB Needle — — — 520 ASE 520 TPA: 2.9  102 (120 fs) 2.4  106 193
aDPADCS — P1 Q N 600 ASE 600 TPA: 1.5  102 (120 fs) 1.3  106 198
bDPADPDCS Plate P1 Q N 562 ASE 562 305 (10 ns) 30.5 195
561 TPA: 4.4  103 (100 fs) 4.4  107 218
a
SG = space group. b Arrangement: HB = herringbone, Q = quasi-isolated, X = cross-stacked, m = local (see main text). c H = H-aggregate, J = J-aggregate, N = no preferred coupling, w = weak.
d
ASE: amplified spontaneous emission, RA: random lasing, RE: regular lasing emission (Q-factor).
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Fig. 9 (a) Chemical structures and the fluorescence images of the corresponding single crystals. (b) Normalized fluorescence spectra of a-MODCS
(cyan color), a-MODBDCS (green color), b-MODCS (orange color) and b-MODBDCS (red color) single crystals. (c) Dependence of emission intensity on
excitation lasing fluence in these crystals; Inset: FWHMs of these crystals under different pumped pulse energies. Reproduced with permission from
ref. 192. Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

radiative decay rates, and superior quasi four-level system Fluorescence spectral narrowing with threshold of 200 mJ cm2
characteristics, a variety of single crystals (49–57) have been was observed in single crystal of HIP-Ac (58). 2 0 -Hydroxychalcone
explored as gain media for crystal lasers.201–205 Recently, Kreiza was selected to build up donor–p–acceptor (D–p–A) skeleton, in
et al. reported one of the lowest ASE threshold (3.5 mJ cm2) in which the intramolecular H-bond with ESIPT nature enabled its
single crystals, by using two bifluorene compounds, FpF1 (50) ASE/lasing applications.73,207 2 0 -Hydroxychalcone derivatives
and F2pF1 (51), as gain media.201 The low thresholds were (HDDP-n, n = 1–3, 59–61) displayed relatively high PLQYs
ascribed to the negligible influences of photoinduced absorp- (0.25–0.32) with emission peaks above 680 nm.207 Among them,
tion (PIA) in the gain region, high radiative rates (ca. 1.5  HDDP-1 (59) showed the lowest ASE threshold of 92 mJ cm2 with
109 s1, along with inherent intramolecular property), and NIR stimulated emission with peak at 714 nm. Through fabri-
excellent wave-guiding properties of favorable oriented single cating HDDP-1 (59) nanowires and microdisks, the HDDP-1 (59)
crystals. By introducing some different bridging groups, such microcrystals demonstrated shape-dependent resonator proper-
as acetylene, tolane, ethylene, and stilbene, into bifluorene, ties with the Fabry–Perot mode in 1D nanowire and the WGM
Baronas et al. synthesized the bifluorene crystals, named as resonator in two dimensional (2D) microdisk for lasing
BF-a (52), BF-t (53), BF-e (54), and BF-s (55).205 The rigid oscillation.73 The 2D microdisk of HDDP-1 (59) exhibited lower
bifluorenes bridges enabled enormous increase of radiative lasing threshold (0.43 mJ cm2 vs. 1.05 mJ cm2) and only one
decays with high radiative decay rates (ca. 5  108 s1) in these high-Q mode (ca. 7500) compared with 1D nanowire of HDDP-1
single crystals, which are resulted from enhanced PLQYs (59). Expanded p-conjugated systems, 1-hydroxynaphthalen deri-
(470%) and short decay lifetimes (o2.5 ns). A rather low ASE vatives (DPHP (62) and DMHP (63)), were then explored for
threshold of 2.0 mJ cm2 was achieved in BF-a (52) crystal, nanowire lasers.208,209 Interestingly, the dual-wavelength lasing
which was even lower than that in fluorene-based small- at the 0–1 and 0–2 vibronic oscillations were also obtained for
molecule amorphous neat films (see Section [Link]). The DMHP (63) nanowires with corresponding peaks at 660 nm and
relevant optical data are summarized in Table 2. 720 nm.209 The short ONWs with lengths between 5 and 28 mm
Fluorophores with excited-state intramolecular proton trans- provided lasing action at the 0–1 vibronic oscillation with peak at
fer (ESIPT) property are important components in constructing 660 nm. For the nanowires with lengths longer than 48 mm with
long-wavelength organic fluorescent molecules due to their significant self-absorption effect, NIR lasing actions at the
large Stokes-shifted emission. Park et al. reported a novel 0–2 vibronic oscillation with peak at 720 nm were achieved.
imidazole-based single crystal, i.e., hydroxy-substituted tetra- Dual-wavelength lasing actions with peaks at 660 nm and
phenyl imidazole (HPI-Ac, 58) with intense blue fluorescence 720 nm were obtained for the ONWs with lengths from
and ASE.206 The large size (25 mm  20 mm  5 mm), well- 30 and 45 mm. Some ESIPT molecules, 2-(2 0 -hydroxyphenyl)-
defined and transparent HIP-Ac (58) single crystals were benzothiazole (HBT, 64)150 and 2-(1,4,5-triphenyl-1H-imidazole-
prepared from its dilute solution. The results showed that 2-yl)phenol (HPI, 65),210 were explored for microcrystal lasing
the four phenyl substituents on the HIP-Ac (58) imidazole applications, and some other crystals, 1,1,4,4-tetraphenyl-1,3-
ring limited the intermolecular vibrational coupling and non- butadiene (TPB, 66) and di(p-methoxyl-phenyl) dibenzofulvene
radiative transitions, and reduced the possibility of fluores- derivative (DPDBF, 67), were reported with ASE and random
cence quenching by confining the excessively tight p–p stacking. lasing characteristics.211,212

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Scheme 5 The crystals in Sections [Link] and [Link].

[Link] Crystals for TPP lasers. Compact upconversion lasers Scheme 4),193 1,4-bis[1-cyano-2-(4-(diphenylamino)phenyl)vinyl]-
have been extensively studied because of their massive benzene (aDPADCS (45), as shown in Scheme 4),198 1,4-bis(a-
variety of applications in the fields of lithography, optical cyano-4-diphenylaminostyryl)-2,5-diphenyl benzene (bDPAPDCS
communication, data storage, etc. TPP lasers can provide (46), as shown in Scheme 4),218 and 2-(N,N-diethylanilin-4-yl)-
frequency-upconversion coherent light with excitation wave- 4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (DPBT (68), as
lengths in an extensively broad spectral region. TPP lasers in shown in Scheme 5).90 The relevant optical data are summarized
a small quantity of organic material systems were demon- in Table 2. There is an enormous demand to explore novel crystal
strated in solutions213,214 and films.215,216 Up to now, efficient candidates, which are of low ASE/lasing thresholds and large TPA
TPA properties are only reported in a few organic crystals, such cross-sections, for high efficiency upconversion lasers.
as E,E-1,4-bis[4 0 -(N,N-dibutylamino)styryl]-2,5-dimethoxy-benzene 3.2.2 Amorphous small molecules. Fluorescent small-
(DBASDSB (35), as shown in Scheme 4),189 MSMODSB (37) (as molecular materials with well-defined molecular structures
shown in Scheme 4),217 (N-(4-(4-(4-diphenylamino)styryl)styryl)- and high purities (i.e., without obvious catalyst residues, side-
phenyl)-N-phenyl-benzene amine (aDPADSB (44), as shown in products, and chemical defects) can be obtained via column

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Table 2 Crystallographic, photophysical and amplified emission data of organic single crystals

Exciton Amplification Threshold [mJ cm2] Threshold

Compd Shape SGa Arrangementb couplingc lem process (Q)d lASE or laser (at pulse length) [kW cm2] Ref.
PTATA Needle P21/c Other H/J 530 ASE 530 95 (10 ns) 9.5 199
BOXD-4 Plate P21/n A wJ 403 ASE 403 200 (10 ns) 20 200
FP-THP Needle Pbca m-HB — 410 ASE 410 — Ca. 2.0  102 202
FpF1 Plate — — — 413 ASE 413 9.2 (5 ns) 1.8 201
F2pF1 Plate — — — 426 ASE 426 3.5 (5 ns) 0.7 201
BF-a Plate — — — 412, 437, 465 ASE 438 2.0 (5 ns) 0.4 205
BF-t Plate — — — 404, 449, 481 ASE 446 150 (5 ns) 30 205
BF-e Plate — — — 421, 450, 472 ASE 449, 472 17.0 (5 ns) 3.4 205
BF-s Plate — — — 434, 462, 484 ASE 460, 485 250 (5 ns) 50 205
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BMSA Needle P21/c p-Stack Q 525 ASE 525 10 (60 ps) 1.7  102 203
BDTVA Needle P1 — Q 509 ASE 509 265 (10 ns) 27 204
HPI-Ac Plate P1 other H/J 468 ASE 468 200 (25 ps) 8.0  103 206
HDDP-1 Plate/ P21/c p-Stack H/J 710 ASE 714 92 (10 ns) 9.2 73
needle and 207
Needle 650 RE (1.3  103) 650 1.05 (150 fs) 7  103 73
Plate 650 RE (7.5  103) 658 0.43 (150 fs) 2.9  103 73
HDDP-2 Plate/ P21/c p-Stack H/J 680 ASE 682 82 (10 ns) 8.2 207
needle
HDDP-3 Plate/ P21/c p-Stack H/J 716 ASE 746 1.0  103 (10 ns) 100 207
needle 687 220 (10 ns) 22 207
DPHP Sphere — p-Stack H/J 643, 687, 756 RE (1.4  103) 705 5.1 (150 fs) 3.4  104 208
DMHP Needle — p-Stack H/J 660 RE 660/720 0.78/1.24 (150 fs) 5.2  103/8.3  104 209
HBT Needle — p-Stack H/J 514 RE (1.5  103) 514 0.20 (150 fs) 1.3  103 150
HPI-CF3 Needle — p-Stack H/J 478 ASE 475 1.3  104 (25 ps) 5.2  105 210
TPB Plate P21/c m-HB Q 430 ASE, RA 430 500 (600 ps) 8.3  102 212
DPDBF Needle P21/n X Q 525 ASE 529 5.3 mJ (200 fs) — 211
DPBT Needle — — — 466 RE (57) 475 77K, TPA: 60 nJ — 90
(200 fs)
a
SG = space group. b Arrangement: HB = herringbone, Q = quasi-isolated, X = cross-stacked, m = local (see main text). c H = H-aggregate,
J = J-aggregate, N = no preferred coupling, w = weak. d ASE: amplified spontaneous emission, RA: random lasing, RE: regular lasing emission
(Q-factor).

chromatography. Due to the small molecular weights (usually less than 1.3  104 cm2 V1 s1, which is comparable with other
less than 1000 Da), the small molecular films can be fabricated glassy fluorene derivatives. On the other hand, with the increase
by thermal evaporation. By incorporating proper solubilizing of p-conjugated fluorene skeletons, the alkyl-functionalized
side groups, the resulting small molecules are well suited for oligofluorenes could act as solid-state gain media. Choi et al.
forming amorphous smooth films by solution process with reported a series of linear oligofluorenes with hexyl chains
high uniform optical and waveguide properties. functionalized at each C9 position of fluorene units (the numbers
In this section, traditional fluorescent small-molecular of fluorene unit are 3, 5, and 7, named as TerF (71), PentaF (72),
gain media will be discussed at length. The material design and HeptaF (73), respectively).220 The ASE thresholds measured
strategies for small-molecular gain media, which could reduce in nitrogen environment were 1.3, 1.2, and 0.4 mJ cm2 for TerF
the effect of quenching, are summarized, such as functionalizing (71), PentaF (72), and HeptaF (73), respectively. TerF (71) film
with branched chains and sterically demanding substitutions, didn’t exhibit any ASE characteristic with excitation densities
constructing D–p–A architectures, etc. The triplet small-molecular lower than 12 mJ cm2 under ambient conditions. Typical ASE
gain media will be discussed in Section 3.3. thresholds measured in air were 5 mJ cm2 and 8 mJ cm2 for
PentaF (72) and HeptaF (73), respectively. High ASE thresholds
[Link] Fluorescent small molecules based on fluorene. and fast optical degradations under ambient conditions indi-
Fluorene is a common fluorescent building block, which is cated the significant oxygen-induced fluorescent quenching
easily functionalized with functional units and solubilizing (or degradation) in alkyl-functionalized oligofluorenes. Then,
groups by cross-coupling reactions, and thus reproduce a variety liquid 9-(2-ethylhexyl) carbazole was selected as a host and doped
of fluorene-based molecules. Fluorenes are generally powders, with HeptaF (73). Relatively efficient lasers were achieved by
even with alkyl chains functionalized at the 9,9 0 -position. spreading the nonvolatile emitter blend on substrate containing
Fluorene derivatives substituted with double branched long alkyl DFB gratings. For a blend with 10 wt% HeptaF (73), the lasing
groups may exhibit viscous liquid-state and crystallize slowly. threshold as low as 2 mJ cm2 was demonstrated even for a laser
Fluorene homologues functionalized with siloxane groups repetition rate of 4 MHz, indicating the potential quasi-CW lasing
(DF-SiO and TF-SiO) (69 and 70) were obtained as liquid oils. applications.221
ASE thresholds of 1.4 mJ cm2 and 22 mJ cm2 were demonstrated A pervasive method to improve ASE stability is dispersing
in these fluorene dimers and trimers, respectively.219 The non- small-molecular oligofluorenes in PS or PMMA. Kazlauskas et al.
volatile liquid-state fluorene derivatives exhibited hole mobilities reported ASE properties and photostabilities of fluorene- and

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benzofluorene-cored oligomers (BF-Et (74), BF-Hex (75), F-Et (76) gain media. Pyrenyl-capped benzofiurene was selected as mole-
and F-Hex (77)) in organic matrices.222 The ASE thresholds were cular skeleton, and functionalized with different flexible alkyl
much lower in blended films (in PS) than those measured in chains on diaryl groups at each C9 position of fluorene
oligomer neat films. The ASE photostability half-lifetimes (tASE
1/2 ) units.228,229 The selected pyrenyl-capped benzofiurene deriva-
of the blended samples were up to 104 pulses, much longer than tives (PFP-n, n = 1–3) (83–85) are shown in Scheme 6. PFP-3 (85),
those of the neat films. Another method to improve the stability with phosphonate polar pendant groups at C9 position of the
of fluorene-based gain media is to incorporate C9-substituted fluorene units, exhibited blue-shifted emission and much
alkyl pendant groups onto the fluorene unit or introduce spiro higher ASE thresholds, compared with that recorded from
unit into the molecular architectures. PFP-1 (83) and PFP-2 (84). PFP-1 (83) was selected to further
Ter(9,9-diarylfluorene)s (TDAFs, 79, 81, 82) are promising investigate the lasing performance due to its higher PLQY,
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gain media with high glass transition temperature (4200 1C), lower ASE threshold, and better photoelectrical property.
excellent morphological, electrochemical and thermal stability, By varying the film thicknesses, the lasing wavelength could
high PLQY, and excellent OLED performance due to the ambi- be tuned within a range of 16 nm (from 456 nm to 472 nm)
polar transport with high hole and electron mobilities.223–225 in the blue spectral region. The lowest lasing threshold of
Among them, TDAF-1 (79), with methylbenzene substituents 1.4 mJ cm2 was obtained with lasing peak at 456 nm.
on the C9 positions, has been extensively studied. Vacuum- The spiro concept, based on the connection of two molecular
deposited films became optically isotropic after annealing. As a p-systems through a sp3-hybridized carbon atom with equal or
result, the ASE threshold after annealing was higher than that different functions, has been used in the design of organic gain
of as-deposited film (14 mJ cm2 vs. 7 mJ cm2).53 With a pump media. The use of such a linkage has been demonstrated to
energy of 300 mJ cm2, a gain coefficiency of 78 cm1 was achieved effectively depress the excimer formation and the ketonic defects,
for the as-deposited film; while after annealing, the net gain increase the thermal and spectral stabilities, and thus strongly
values became intrinsically lower with 15–30 cm1 under the enhance PLQYs and ASE/lasing properties. Due to the facile
same laser energy densities. By using the same method (annealing functionalization at C-2, C-7, C-10, and C-15 positions of spiro-
the films), the DFB lasing wavelengths were adjusted from bifluorene unit, various spiro-functional materials, including
447.2 nm to 430.5 nm with the grating period of 280 nm.226 small molecules (as discussed in this section and shown in
Oyamada et al. reported ASE performance of bi(9,9-diaryl- Scheme 7), dendrimers (see Section [Link]), and polymers (see
fluorene)s (BDAFs) and other TDAFs.227 The chemical structures Section [Link]), have been explored for lasing applications.
of BDAF-1/2 (78 and 80) and TDAF-2/3 (81 and 82) are depicted in For example, Spehr et al. reported the lasing performance
Scheme 6. The optical and ASE results are summarized in Table 3. based on an active gain medium, spiro-terphenyl (Sp-TP, 86), in
All of them showed inferior ASE performance compared with that a second-order DFB structure.230 Sp-TP (86) showed ASE in the
of TDAF-1 (79) in the same excitation lasing system. UV spectral region with emission peak at 381 nm. With DFB
Pyrene was introduced to construct new organic gain media. grating periods from 200 nm to 230 nm, the lasing wavelengths
Lai et al. reported pyrenyl-capped benzofiurene derivatives as of thin-film devices were operated in a range of more than

Scheme 6 Fluorene-based small molecules as gain media.

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Table 3 Physical and amplified emission properties of small molecular gain media

ASE Lasing
Threshold Threshold
Threshold [mJ cm2] Threshold [mJ cm2] Slope
b
lema PLQYa lASE FWHMb Gain [nJ per (at pulse Feedback FWHM [nJ per (at pulse efficiency
Chem Soc Rev

Compd [nm] [%] [nm] [nm] [cm1] pulse] length) structurec llaser [nm] pulse] length) [%] Ref.
DF-SiO 364, 384 55 386 5 — 76 1.4 — — — — — — 219
TF-SiO 409, 429 80 430 10 — 450 22 — — — — — — 219
TerF 400, 421 45 423 6 — 18.2 1.3 — — — — — — 220
PentaF 418, 443 62 442 6 — 16.8 1.2 — — — — — — 220
HeptaF 421, 447 51 445 6 — 5.6 0.4 — — — — — — 220
BF-et 423, 442 33 441 12 — — 5  104 — — — — — — 222
BF-hex 425, 445 26 441 12 45 — 7.5  103 — — — — — — 222
F-et 402, 423 46 420 6 — — 60 — — — — — — 222
F-hex 400, 420 46 420 6 77 — 22 — — — — — — 222
TDAF-1 403, 429 75 430 5 78 336 7 DFB 423, 430–447 0.11 19 5.3@423 — 53 and 226
430 5 — 25 0.5 — — — — — — 227

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TDAF-2 430 72 432 5 — 50 1.0 — — — — — — 227
TDAF-3 431 52 434 5 — 100 2.0 — — — — — — 227
BDAF-1 395 47 398 5 — 55 1.1 — — — — — — 227
BDAF-2 395 66 398 5 — 265 5.3 — — — — — — 227
PFP-1 472 46 454 8.7 — 410 22.8 DFB 456–472 0.3 5.6 1.4@456 — 228
PFP-2 473 38 450 8.5 — 580 32.5 — — — — — — 228
PFP-3 439 46 442 10 — 3.2  103 178 — — — — — — 229
Sp-TP 367, 387, 406 381 9 — — 0.5 DFB 362–394 o1 45 8.9@383 — 230
Sp-HBP 398, 419 78 — — — — — DFB 409 0.1 1.9  103 42 3.6 231
Sp-SPO 420 — 419 5.4 — — 1 — — — — — — 232
Sp-Cz 380, 402 10 396 6 — 1.5  103 30 — — — — — — 233
Sp-SBCz 447, 472 42 474 5 — 22 0.43 — — — — — — 233
Sp-BCz 405, 424 — 424 4 — 44 1.1 — — — — — — 234
Sp-DPA 428, 451 — 452 4 — 100 2.5 — — — — — — 234
Sp-SDPA 468, 494 492 7 — 100 2.0 — — — — — — 234
2L-F 427 24 430 4.5 74 90 5.0 — — — — — — 235
2LPh-F 437 24 447 5.1 82 74 4.1 — — — — — — 235
3L-F 444 27 450 4.5 90 61 3.4 — — — — — — 235
3LPh-F 457 28 459 5.0 92 63 3.5 — — — — — — 235
4L-F 441, 465 39 468 5.1 93 58 3.2 DFB 454–469 0.3 5.3 2.2@460 — 235
4LPh-F 450, 472 56 474 6.0 92 36 2.0 DFB 457–479 0.3 1.3 0.5@471 — 235
4L-Cz 413, 436 25 444 5 82 10 0.53 DFB 433–452 0.35 0.6 0.17@444 5.9 236
COPV-1d 367, 385 100 385 7 — 4.4  104 2.5  103 DFB 408 o0.13 8  103 8  104 — 241
COPV-2d 435, 463 100 463 9 — 5.8  103 3.3  102 DFB 465, 491 o0.13 9  103 9  102@591 — 241
COPV-3d 481, 513 100 515 8 — 700 40 DFB 516 0.13 100 10 — 241
COPV-4d 508, 546 100 548 9 — 1.4  103 80 DFB 557 o0.13 100 10 — 241
COPV-5d 525, 569 100 571 9 — 9.6  103 5.5  102 DFB 573 o0.13 2  103 200 — 241
COPV-6c 537, 580 94 583 9 Ca. 60 1.8  103 100 DFB 573–591 o0.13 70 7@587 — 241
TPDc 402, 421 — 421 9 16 1.1  104 154 DFB 415–427 2 6  103 537@418 — 244
BMT-TPDd 420, 440 — 438 7 — 5.4  103 77 — — — — — — 244
BMQ-TPDd 438, 458 — 459 7 — 2.9  103 42 — — — — — — 244
DPABPc 400, 419 — 420 5 — 5.3  104 7.6  102 — — — — — — 245
FVIN 631 20 660 15 50 — 22 DBR 647 1 — 60 — 247
SBD-1 — 62 474 — — 60 1.2 — — — — — — 248
SBD-2 — 57 496 — — 240 4.8 — — — — — — 248
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Table 3 (continued)

ASE Lasing
Threshold Threshold
Threshold [mJ cm2] Threshold [mJ cm2] Slope

Chem. Soc. Rev.

PLQYa FWHMb Gain [nJ per (at pulse Feedback FWHMb [nJ per (at pulse efficiency
Review Article

lema lASE
Compd [nm] [%] [nm] [nm] [cm1] pulse] length) structurec llaser [nm] pulse] length) [%] Ref.
SBD-3 — 49 455 — — 465 9.3 — — — — — — 248
SBD-4 — 92 504 — — 4.5  103 90 — — — — — — 248
SBD-5 — 91 443 — — 4.6  103 91 — — — — — — 248
CBP 393 61 394 4.3 13 65 1.3 — — — — — — 249
mCBP 400 49 401 Ca. 4 4 85 1.7 — — — — — — 249
dCBP 409 60 409 Ca. 4 7.8 75 1.5 — — — — — — 249
BSB-1 — 93 528 — — 45 0.9 — — — — — — 248
BSB-2 — 81 497 — — 35 0.7 — — — — — — 248
BSB-3 — 65 514 — — 200 4.0 — — — — — — 248
BSBCz 437, 461 100 461 3.4 — 16 0.32 DFB 478 o2 0.02 0.09 — 21 and 248
DTBT 622 61 644 10.4 — 5.9  103 3.8  102 DFB 635–650 o0.5 30 118@650 — 252
PTA-1d 413 24 414 5 — 1.9  103 1.0  102 — — — — — — 253
PTA-2d 510 76 511 9 — 4.5  103 2.4  102 — — — — — — 253
PTA-3d 525 82 573 13 — 1.4  104 7.5  102 — — — — — — 253
PDI-C6 536, 575 — 579 6 — 2.2  103 1.2  102 DFB 572 0.5 1.8  103 1.6  102 — 259 and 260
PDI-o 536, 575 — 578 7 — 5.6  102 30 DFB 576 0.3 2.2  102 22 — 260
b-PDI-C8 574 76 622 8 — 1.2  103 70 DFB 622 0.4 6 5.5  102 — 258
mp-PDI-1 560, 595, 645 15 — — — — — WGM 595 0.8 — 10.8 — 69
mp-PDI-2 549, 575, 625 18 — — — — — NW 575 o1 — 9.1 — 91
An-Cz-1 441 68 454 4.6 23 750 46.9 DFB 467–469 o1 5.7 17.7@460 3.6 265
An-Cz-2 442 58 455 4.6 19 1.1  103 68.8 DFB 465 o1 27.8 86.1 3.2 265
5pN 393 35 409 10 — 9.8  103 Ca. 140 — — — — — — 266
TPE 370, 510 — — — — — — NW 372 0.3 43 5.5  104 — 269
TDPVBi 488 80 488 16 18.5 — 60 — — — — — — 270
DBDK-1 630 32 630 6.6 — 4.2  104 4.2  103 — — — — — — 271
DBDK-2 631 48 631 9 — 9.8  104 9.8  103 — — — — — — 271
DBO 637, 686 79 691 6 — 1.2  102 60 — — — — — — 272
a b d
Measured in films. Full width at half maximum (FWHM). c DFB: distributed feedback; DBR: distributed Bragg reflector; WGM: whispering gallery mode; NW: nanowire. Doped in polymer
matrix.
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which will be discussed separately in polymer gain media part

(see Section [Link]). Ladder-type oligo(p-phenylene)s also have
been explored as gain media most recently. Lai et al. reported a
novel set of D–p–A ladder-type oligo(p-phenylene)s with func-
tional end-cappers of diphenyl-amino (donor) and fluorophenyl/
fluorine (acceptor) units, named as nL-F (94, 96, 98) and nLPh-F
(95, 97, 99) (n = 2–4), as gain media for lasing applications.235
The ASE thresholds decreased with the extension of the
p-conjugated system for end-capper functionalized oligo(p-
phenylene)s. In 4LPh-F (99) film with the largest p-conjugated
system, relatively low ASE threshold of 1.97 mJ cm2 was
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recorded. Excellent optical waveguiding properties with gain

coefficient higher than 90 cm1 and loss coefficient lower than
2.0 cm1 were also demonstrated in 4LPh-F (99) film. 4LPh-F (99)
showed good photothermal stability, and ASE could still be
detectable even up to 280 1C. Lasing thresholds of 2.2 mJ cm2
and 0.5 mJ cm2 with corresponding peaks at 460 nm and
471 nm were demonstrated in 1D DFB lasers using 4L-F (98)
and 4LPh-F (99) as gain media, respectively. Carbazole was also
explored as end-capper in linear ladder-type oligo(p-phenylene)s,
named as 4L-Cz (100), as a deep-blue gain medium.236 Blue ASE
Scheme 7 Spirobifluorene molecules as gain media.
with a low ASE threshold of 0.53 mJ cm2 and emission peak at
446 nm was demonstrated in 4L-Cz (100) film. A high gain value
of 82 cm1 and a low loss value of 3.9 cm1 were recorded. The
30 nm between 362 nm and 394 nm. The minimum threshold best 1D DFB laser device showed a threshold of 0.17 mJ cm2
of 8.9 mJ cm2 with peak at 383 nm was achieved under optical with lasing slope efficiency up to 5.9%. A lasing wavelength
pumping. By increasing the p-conjugated system (e.g., adding tunable window of 19 nm was achieved in the blue spectral
the phenyl numbers for Sp-HBP (87)) or linking acceptor units region.
(e.g., linking oxadiazole for SP-SPO (88)), the ASE/lasing spectra COPVs is another interesting type of all carbon skeleton
of spirobifluorene molecules showed bathochromic shifts to materials. The synthetic method was firstly reported by Zhu
the blue spectral region.231,232 et al. in 2009.237 The chemical structures of COPV-n (101–106)
Spirobifluorene molecules linked with donor or acceptor (n = 1–6) are shown in Scheme 8. As illustrated in Fig. 10a and b
groups were studied as small molecular gain media. Donor for COPV4 (104), the planar p-conjugated molecular skeleton
units, such as diphenylamine or carbazole units, were usually was sterically protected from aggregation and degradation by
used to construct donor–p–donor structures. The film of incorporating bulky p-octylphenyl units, which also enabled
carbazole-functionalized spirobifluorene, named as Sp-Cz good miscibilities with organic solid matrixes and good
(89), showed an ASE threshold of 25 mJ cm2 with emission solubilities in organic solvents. The absorption spectra of
peak at 396 nm.233 Molecular extension with phenylene–viny- COPV-n (101–106) showed obvious bathochromic shifts with
lene groups (Sp-SBCz, 90) increased the p-conjugated system, the increase of the p-conjugated system, indicating the effective
resulting in bathochromic-shifted amplification with a much conjugations of COPV-n (101–106) have significantly increased
lower threshold of 0.43 mJ cm2. When doped into CBP host, in this process (Fig. 10c).238 The slope efficiency between energy
the Sp-SBCz (90) blend film exhibited an ASE threshold down bandgap and the reciprocal number of repeating units (1/n) was
to 0.11 mJ cm2, which represented one of the lowest ASE 1.76, much higher than that recorded in ladder-type oligo-
thresholds for organic emitters by far. More rotational freedom (p-phenylene)s239 and oligofluorenes.240 Very broad fluores-
could be provided for the individual phenyl rings when the end- cence emission range was observed in COPV-n (101–106) with
capped carbazole units are replaced by diphenylamine groups. different numbers of repeating units (n) (Fig. 10d). By fabricating
The respective diphenylamine-functionalized spirobifluorene is DFB lasers, single mode lasing of COPV-n (101–106) doped in PS
Sp-DPA (93). The stimulated emission wavelength (at 452 nm) film exhibited remarkably low thresholds (7 mJ cm2), tunable
of Sp-DPA (93) showed a red shift compared with the ASE wavelength from deep-blue- to red-spectral region (408–591 nm)
peak of Sp-BCz (92).234 The end-capped with diphenylamine and long operational lifetimes (43  105 pump pulses for
phenylene-vinylene extended spiro-bifluorene (Sp-SDPA, 91) oligomers with three to six repeating units) (Fig. 10e and f).241
showed an ASE threshold of 2 mJ cm2.234
[Link] Phenylamine and benzocarbazole derivatives. Triphenyl-
[Link] Ladder-type oligo(p-phenylene)s and carbon-bridged diamines, which are well-known as hole-transporting materials,
oligo (p-phenylenevinylene)s (COPVs). Ladder-type poly(p-phenylene)s have been widely used as one of the functional layers in OLEDs
(LPPP) is a vital series of polymeric material system for OSLs, and OSCs. Also as an individual, triphenyldiamine is a

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Scheme 8 Ladder-type oligo(p-phenylene)s and COPVs as gain media.

Fig. 10 (a) Chemical structure of COPV-4 with Ar denoting 4-octylphenyl. (b) Top- and side-view of COPV-4 single-crystal X-ray analysis. (c and d)
Absorption spectra (c) and fluorescence spectra (d) of COPV-1–6 in dichloromethane. (e) ASE intensity vs. the number of pump pulses and time (t) (top
and bottom axes, respectively) excited under soft laser energy (SP, 2-fold ASE threshold) and extremely high laser energy (EP, 103-fold ASE threshold)
conditions for a 2 wt% COPV6-doped film. (f) DFB lasing spectra based on COPV-n-doped films (n = 1–6) spread on resonators with different grating
periods. (a, e and f) Reproduced with permission from ref. 241. Copyright 2015 Nature Publishing Group. (b–d) Reproduced with permission from ref. 238.
Copyright 2012 American Chemical Society.

fluorescent material with deep-blue emission. N,N 0 -Bis(3-methyl- triphenyldiamine derivative. When mixed TPD (107) into PS matrix
phenyl)-N,N 0 -diphenylbenzidine (TPD, 107) is a well-studied with concentrations from 2.1 wt% to 70 wt%, the doped films

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showed tunable ASE spectra between 413 and 421 nm.242 A net electron-withdrawing groups onto the triphenylamino core,
gain value of 16 cm1 was recorded for 20 wt% TPD-doped film. multi-color emission from blue to red were observed through
Spin-coated onto a DFB grating resonator with grating period of the combination of inter-branch electronic energy transfer and
270 nm, the 30 wt% TPD-doped film emitted lasing at 418 nm intramolecular charge transfer (ICT).246 4-di(4 0 -tert-butylbi-
when the pumping energy density was above 537 mJ cm2 phenyl-4-yl)amino-4 0 -dicyano-vinyl-benzene (FVIN, 112), coupled
(6 mJ per pulse).243 Other TPDs, including 1,4-bis(diphenyl- to the triphenylamino core with dicyanovinyl units, was used as
amino)biphenyl (DPABP, 108), N,N 0 -bis(3-methyl-phenyl)-N,N 0 - red-emitting organic gain medium.247 The non-doped FVIN (112)
diphenyl-[1,1 0 :4 0 ,100 -terphenyl]-4,400 -diamine (BMT-TPD, 109), film exhibited an ASE threshold as low as 22 mJ cm2 and an
N,N 0 -diphenyl-N,N 0 -bis(1-naphthyl)-1,1 0 -biphenyl-4,400 -diamine optical gain of 50 cm1, indicating tremendously reduced
(NPB, 110), and N,N 0 -bis(3-methylphenyl)-N,N 0 -diphenyl- quenching effects in comparison with classical dyes such as
[1,1 0 :4 0 ,100 :400 ,1 0 0 0 -quaterphenyl]-4,4 0 0 0 -diamine (BMQ-TPD, 111)
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rhodamine 6G and DCM. Lasing in the red region at 647 nm

(Scheme 9), were explored as doped gain media by Ma with a threshold of 60 mJ cm2 was obtained with a patterning
et al.244,245 Among them, BMQ-TPD (111) showed the lowest DBR resonator. Triarylamine linked with other units, such as
ASE threshold (42 mJ cm2), while there was no evidence of ASE ethene-diyldibenzene, vinyl-carbazole, vinylquinoline, and vinyl-
in NPB (110) doped film. Molecular geometries were calculated naphthalene, named as SBD-n (113–117) (n = 1–5), were reported
to simulate the four-level system in these molecules. A series of with ASE phenomena using CBP as the host in the guest–host
energy sublevels were estimated in NPB (110) from various system. The chemical structures of SBD-n (113–117) (n = 1–5) are
elongated low-frequency modes between 11 cm1 and depicted in Scheme 9, and the ASE properties are summarized in
689 cm1 deriving from naphthyl unit, which are adverse to Table 3.248
the construction of four-level system. For comparison, the CBP (118) is one of the most studied bipolar hosts in OLEDs
strong elongated high-frequency modes from 1199 cm1 to and guest–host gain systems. The UV ASE were investigated by
1664 cm1 deriving from benzene unit in TPD (107), DPABP using CBP and its derivatives, 4,4 0 -bis(3-methylcarbazol-9-yl)-
(108), BMT-TPD (109), and BMQ-TPD (111) contributed to the 2,2 0 -biphenyl (mCBP, 119) and 4,4 0 -bis(3,6-dimethyl-carbazol-9-
evident vibronic band in the fluorescent emission, indicating yl)-2,2 0 -biphenyl (dCBP, 120), as the emitters.249 For undoped
an efficient four-level system for stimulated emission. CBP (118) films, ASE at 394 nm was observed with a threshold
Triarylamine is mainly used as an electron-donating unit of 1.3 mJ cm2. The red shifted ASE spectra centered at 401 nm
in the applications of OLEDs and OSCs. By linking various and 406 nm were demonstrated in mCBP (119) and dCBP (120)

Scheme 9 Phenylamine and benzocarbarzole derivatives.

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films, with the corresponding thresholds of 1.7 mJ cm2 and doped BSBCz (124) film) operating under long-pulse width of
1.5 mJ cm2. The neat gains were strongly dependent on their 30 ms as well as pulse repetition rate up to 80 MHz.21 CBP was
chemical structures. CBP (118), mCBP (119), and dCBP (120) used as host in the guest–host system. As shown in Fig. 11a, in
exhibited gain values of 13, 4.0, and 7.8 cm1, respectively. order to greatly improve the DFB laser stabilities and efficien-
Bis-styrylbenzene derivatives are interesting laser materials cies operating in the quasi-CW regimes, CYTOP was spin-
as crystal gain media. The ASE characteristics of a series of bis- coated onto the organic layers to encapsulate the devices.
styrylbenzene derivatives end-capped with triarylamine and Mixed-order DFB grating was fabricated to provide a sufficient
benzocarbazole (BSB-n, n = 1–3, and BSBCz, 121–124) doped out-coupling of the laser radiation (Fig. 11b). Fig. 11c and d
into CBP host were reported by Adachi’s group.248 Among show the images of lasing oscillations in the encapsulated
them, the 6 wt% doped BSBCz (124) film demonstrated the blended mixed-order DFB laser device under different pulse
lowest ASE threshold of 0.32 mJ cm2. Since then, BSBCz (124)
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repetition rates captured by streak camera. The encapsulated

was used in quasi-CW operation of OSLs, due to its very high blended mixed-order DFB laser device held the lowest thresh-
PLQY (nearly 100%), extremely weak population of triplet olds (from 0.06 mJ cm2 to 0.25 mJ cm2) under the pulse
excitons via intersystem crossing, and inappreciable excited- repetition rate varying from 10 kHz to 80 MHz, and was the
state absorption in the lasing region.250,251 Recently, Adachi only live device after operating at 80 MHz (Fig. 11e). With the
et al. reported the low-threshold quasi-CW DFB lasers (based on same tendency, a reduced lasing threshold was also observed in

Fig. 11 (a) Chemical structures of CBP and BSBCz as host and guest materials for organic lasing. The chemical structure of CYTOP polymer for
encapsulation. (b) Schematic illustration of the mixed-order DFB resonator. (c and d) The images of lasing oscillations captured by streak camera from a
encapsulated doped (BSBCz concentration of 6 wt%) mixed-order DFB device with repetition rate varying from 0.01 to 80 MHz over a period of (c) 500 ms
or (d) 200 ns (80 MHz only). (e) Dependence of the lasing threshold on the pulse repetition rate for several types of DFB devices. (f) The images of lasing
emission captured by streak camera from an encapsulated doped (BSBCz concentration of 20 wt%) mixed-order DFB device with pulse widths of 30 ms
(top) and 800 ms (bottom). And the corresponding pump energy were 2.0 kW cm2 and 200 W cm2, respectively. (g) Lasing threshold as a function of
excitation pulse width in various DFB devices. (h) Laser intensity vs. the number of incident pulse from several types of DFB devices in the quasi-CW
regime at long-pulse photoexcitation (100 ms and 200 W cm2). Reproduced with permission from ref. 21. Copyright 2017 AAAS.

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the encapsulated blended mixed-order DFB laser device in the were built up with incorporating PTA-2 (127) and PTA-3 (128) as
quasi-CW regime at long-pulse photoexcitations (Fig. 11f and g). guest and PTA-1 (126) as host, which yielded lower ASE thresholds
As shown in Fig. 11h, the ultra-high energy-induced thermal than that in PS host by facilitating energy transfer from host to
degradation of active layer led to the irreversible decreased laser guest. In this way, ASE threshold of 370 mJ cm2 with emission
intensity during operation in all devices. Noticeably, the device peak at 573 nm was observed for PTA-3 (128).253
lifetime was greatly enhanced by encapsulation. Only 3% emis-
sion intensity decreased after 500 pulses (pulse width: 100 ms)
[Link] Perylenediimide (PDI) derivatives. Perylenediimide
in the encapsulated blended device. This work represented
(PDI) derivatives are mainly studied for OTFTs and OSCs, due
an important breakthrough toward the realization of organic
to their facile chemical structure tunabilities, excellent thermal
solid-state CW laser technology.
stabilities and optical stabilities, and strong electron accepta-
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Based on the same gain medium, an electrically pumped

bilities.254–256 High fluorescent efficiencies (nearly 100%) of
organic laser was reported by Adachi’s group in 2019, which
PDI monomers in dilute solution enable their applications in
will be discussed further in Section 4.23
single molecule spectroscopy, optical sensing, and lasing.
[Link] Thiophene-based small molecules. In Section 3.2.1, we Nonetheless, in solid state, the strong p–p intermolecular
have introduced the oligothiophene and TPCO crystals for interactions give rise to the formation of cofacially stacked
lasing. Some thiophene-based amorphous small molecules H-aggregates in PDI molecules, quenching fluorescence emis-
were also reported as gain media (Scheme 10). For example, sion unfavorably and strongly.257 The crystallization of PDI
Huang et al. reported a novel material (DTBT, 125) based on the molecules is depressed by attaching alkyl or other bulky sub-
core of dithienylbenzothiadiazole and the end-cappers of stituted groups, accompanying with the increased fluorescent
3,5-bis(1-naphthyl)-phenyl.252 DTBT (125) film exhibited ASE efficiencies. PDI monomers are functionalized with various
characteristics with a threshold of 380 mJ cm2 and emission alkyl and aryl flexible solubilizing chains, e.g., PDI-C6, PDI-o,
peak at 644 nm. DFB laser devices were fabricated by spin- and b-PDI-C8 (129–131, Scheme 11).258–260 Incorporating
coating DTBT (125) onto the grating with period of 410 nm. N,N 0 -di-(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic diimide
By varying the spin-coated film thicknesses from 410 nm to (PDI-C6, 129) into PS matrix with concentrations from 0.5 to
560 nm, a lasing wavelength tunable window of 15 nm was present 5 wt%, stimulated emission was determined with the optimized
with the lowest lasing threshold of 118 mJ cm2 (at 650 nm). threshold as low as 120 mJ cm2 at concentration of 0.5 wt% of
Fused thiophenes, for example, pentathienoacenes (PTA), PDI-C6 (129) in the matrix.260 The doped film onto DFB
are interesting for various applications due to the combination resonator manifested a lasing threshold of 160 mJ cm2.259
of the rigid planarity from acenes and the chemical stability The laser showed an operation lifetime of 3.1  105 pump
from oligothiophenes in their chemical structures. Incorporating pulses (more than 8 h) with pumped energy of 2.2-fold lasing
three PTA derivatives (PTA-1/2/3) (126–128) into host matrix PS threshold and pulse repetition rate of 10 Hz. The lasing
with concentration of 10%, the doped films exhibited ASE thresh-
olds of 100, 240 and 750 mJ cm2 for PTA-1 (126), PTA-2 (127), and
PTA-3 (128), respectively. Alternatively, guest–host gain systems

Scheme 10 Thiophene-based small molecules. Scheme 11 Perylenediimide (PDI) derivatives.

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characteristics of PDI-o (130) and b-PDI-C8 (131) are listed in

Table 3.
In another study, WGM hexagonal microdisk microcavity
and nanowire of PDI molecules, named as N,N 0 -bis(1-ethyl-
propyl)-2,5,8,11-tetrakis(p-methyl-phenyl)-perylenediimide (mp-PDI-1,
132) and N,N0 -bis(1-ethylpropyl)-2,5,8,11-tetrakis(o-methylphenyl)-
perylene-3,4:9,10-tetraarboxylic acid diimide (mp-PDI-2, 133), were
obtained via the reprecipitation method and solution self-
assembly method.69,91 The hexagonal WGM microdisk of mp-
PDI-1 (132) exhibited a PLQY of ca. 15%, a fast fluorescence decay
time (ca. 0.05 ns), and a lasing threshold around 10.8 mJ cm2.
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[Link] Other small-molecular gain media. Like organic crystals,

anthracene was studied as gain media for lasing applications.14,15
Since the first report on the high fluorescent efficiency and
outstanding stability of 9,10-di-(2-naphthyl)anthracene,261 there
are intense interests in exploring novel anthracene derivatives as
promising candidates with deep-blue emission for OLEDs.262–264
Niu et al. reported two asymmetric 9,10-disubstituted anthracene Scheme 12 Other small molecules as gain media.
molecules, named as An-Cz-1 and An-Cz-2 (134 and 135), as thin-
film gain media.265 The molecular difference between An-Cz-1
(134) and An-Cz-2 (135) was the different units substituted on the ASE threshold of 60 mJ cm2. These works suggest the possibility
anthracene 9-position, which are 3,5-bis(4-t-butylphenyl) phenyl of AIE molecules for lasing applications.
and 3,5-bis(2,4-difluorophenyl) phenyl, respectively. An-Cz-1 (134) Some other molecules, such as diarylboron diketonates
exhibited a lower ASE threshold (46.9 mJ cm2 vs. 68.8 mJ cm2) (DBDK-1 and DBDK-2, 141 and 142)271 and dibenzo[hi,st]-
and a higher gain value (23 cm1 vs. 19 cm1) relative to An-Cz-2 ovalene (DBO, 143),272 were reported with ASE phenomena.
(135). 1D DFB lasers of An-Cz-1 (134) with a minimum lasing The chemical structures of DBDK-1 (141), DBDK-2 (142), and
threshold of 17.7 mJ cm2 and a corresponding slope efficiency of DBO (143) are depicted in Scheme 12. The optical character-
3.6% were achieved. istics are summarized in Table 3.
The ASE and lasing phenomena could be observed from 3.2.3 Dendritic starburst molecules. Dendritic starbursts
oligophenylenes (p-nP) as crystals (see Section [Link]). But there are an important category of organic gain media, which are
was no gain-narrowing and light amplification even pumped with usually constituted by a central core and multiple functiona-
a high enough energy in p-nP thin films.266 Introducing peripheral lized p-conjugated arms. Combining the merits of small mole-
naphthyl units onto the oligophenyls (npN, N = 1–3, 136–138) cules and polymers, dendritic starburst molecules contribute to
caused obvious sterical dimensions, weakened intermolecular organic optoelectronics with well-defined molecular structures,
interactions and suppressed p–p stacking. The amorphous 3pN– good film-forming characteristics, excellent thermal- and
5pN (136–138) films showed PLQY values between 22% and 35%, optical-stabilities, and thus outstanding optoelectronic proper-
manifesting common ASE performance.266 ties. The suppressed aggregates and self-quenching induced by
Generally, due to the notorious generation of excimers and the highly branched arms enable dendritic starburst molecules
exciplexes, most chromophores endure aggregation-caused as promising candidates for OSLs. In the past decade, several
quenching (ACQ) in solid state, even with high fluorescence reviews have comprehensively summarized dendritic starburst
efficiency in dilute solution. An inverse effect known as molecules and their applications for organic electronics and
aggregation-induced emission (AIE) was reported by Tang and photonics.273–276 The recent advances in organic synthetic
co-workers in 2001.267 Since then, the research of organic technologies make it possible to design and synthesize novel
fluorophors with AIE characteristics becomes a hot topic.268 materials with bulky structures and complex branches, achieving
AIE molecules as the emitters generally exhibit bright emission. excellent functional characteristics like well-defined small
Cheng et al. reported a UV lasing from tetraphenylethylene molecules and high-molecular-weight polymers. In this part,
(TPE, 139), which was a famous and easily functionalized AIE we confine the discussion on the recent reported starburst
fluorogen, doped in PMMA polymer nanowires.269 The polymer molecules as organic gain media and their lasing characteristics.
nanowires were fabricated by template wetting in the anodic
aluminum oxide channels. Output lasing at 372 nm from [Link] Oligofluorenes. PFO is an important commercial
individual nanowire with threshold of 55 mJ cm2 was polymer, which has been widely used in laser physics, and
observed at 10 K. Another AIE molecule, named as 2,5,2 0 ,5 0 - regarded as the benchmark for organic gain media (see
tetrakis(2,2-diphenylvinyl)biphenyl (TDPVBi, 140), also shows Section [Link]). Correspondingly, the fluorene oligomers, espe-
distinct ASE behavior.270 TDPVBi (140) film fabricated by cially starburst oligofluorenes, also form an important class of
vacuum-depositing process showed high PLQY (80%) and an organic gain media.

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In 2007, Burn’s group reported a series of bisfluorene-cored (B2, B3 and B4, 151–153) and truxene (T3 and T4, 154 and
dendrimers for lasing applications.277,278 Different dendrimers 155) are shown in Scheme 13. The truxene dendrimers exhibited
are formed by attaching biphenyl (BP), biphenylcarbazole lower ASE thresholds (T3 = 8.4 mJ cm2, T4 = 16 mJ cm2)
(BPCz), and E-stilbenyl (ESB) onto the bisfluorene core, named compared with the benzene-cored dendritic oligofluorenes
as BP-1 (144), BPCz (146), and ESB (147), respectively. The ASE (B3 and B4 = 18 mJ cm2). The truxene dendrimers exhibited
peak occurred at 431 nm in BPCz (146), exhibiting a redshift high PLQYs in solid state (78–87%); while the benzene-cored
emission compared with BP-1 (144) and ESB (147). The BP-1 counterparts showed the values ranging from 36% to 86%.
(144) presented the lowest threshold with a value of 16 mJ cm2 Among them, T3 (154) exhibited the highest optical gain of
and the highest gain of 51 cm1.278 With the development from 38 cm1 (Table 4), which was only half of PFO gain value
the first generation (BP-1, 144) to the second generation (BP-2, (74 cm1).49 The combination of these two family materials
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145), a rise in PLQY from 42% to 75% was observed. By using allowed for broad wavelength tuning of 70 nm (402–473 nm) in
etched silica substrates DFB grating, BP-2 (145) exhibited an the deep-blue spectral part for the DFB lasers. Interestingly,
improvement in lasing performance compared with BP-1 (144). pure T3 (154) material achieved very broad lasing spectra
BP-1 (144) showed a lasing threshold of 90 nJ per pulse and a (51 nm) from the 1D and 2D DFB lasers with a range of film
slope efficiency of 0.3%; while BP-2 (145) laser had a half lower thicknesses. The lowest lasing threshold was 2.06 mJ cm2 for
threshold and more than 5-times higher slope efficiency. DFB T3 (154) lasers.281 Six-substituted truxene-based oligomers
By using a soft lithographic technique called as solvent assisted (Tr6-n, n = 1–4) demonstrated highly efficient blue emission
micromoulding (SAMIM), a micromoulded BP-2 (145) laser with (0.50–0.90) in the solid state. In these six-substituted oligomers,
a very high slope efficiency of 14% could be achieved.277 the enhanced steric hindrance between the arms and core and
In addition, a series of H-shaped oligofluorenes, bearing one the consequently low p-conjugated degree led to blue-shifted
rigid arm of diarylfluorenes and another arm of trifluorene with absorption and emission, as compared with the three-armed
alkyl chains, have been developed in Huang’s group.279 The analogues.12,240,288 Low-threshold 1D DFB lasers (1.3 mJ cm2)
H-shaped hybrid oligomers linking trifluorene, carbazole, and with tunable wavelengths from 421 nm to 443 nm were demon-
diarylfluorene groups, i.e., H– (148), H–CF3 (149) and H–Ph strated for the resulting starburst oligomers Tr6-3 (156).12
(150), exhibited very low ASE thresholds (Table 4) and excellent In the electron donor/acceptor cored dendritic starburst
thermal stabilities. The ASE thresholds of samples increased systems, the absorbed energy can be transferred from the arms,
by less than 3-fold annealing up to 200 1C under ambient which act as absorbing antennas, to the core through ICT. The
conditions. An only 5.6-fold threshold increase with annealing typical examples were sky-blue multi-armed molecules based
temperature up to 250 1C was recorded for H–F (148). The key on pyrene as core and oligofluorenes as arms (Py-2 and Py-3,
data of DFB lasers are listed in Table 4. 157 and 158, Scheme 13).47,289 The sufficient spectral overlap
Traditional starburst oligofluorenes usually contain a central between the absorption of pyrene core and the emission of
core and multiple functionalized arms of oligofluorenes. Various oligofluorene arms facilitates energy transfer to the central
cores, such as benzene,280 truxene,12,281,282 pyrene,47 and pyrene core efficiently. Both Py-2 (157) and Py-3 (158) showed
1,4-diketo-2,3,5,6-tetraphenyl-pyrrolo[3,4-c]pyrrole (DPP),283 very high solid PLQYs (490%), low ASE thresholds (Py-2:
have been used to construct a variety of starburst oligofluorenes 1.75 mJ cm2; Py-3: 1.78 mJ cm2), relatively high gain values
(151–166) as organic gain media. The selection of central cores (75–78 cm2), and excellent lasing performances. ASE thermal
is important to construct dendritic architectures. For example, stabilities were measured to evaluate the gain properties of Py-2
as three overlapped fluorene fragments, truxene provide an (157) and Py-3 (158) at high working temperature. For Py-3
alternative core structure to construct 2D starburst oligo- (158), the ASE threshold still kept at a low level even heated up
fluorenes (154–156). The oligomers consisting of the central to 200 1C. The ASE thermal stabilities of Py-2 (157) and Py-3
truxene core and oligofluorene arms could be virtually consi- (158) were much better than that of their polymer counterpart,
dered as uniform starburst oligofluorenes with homogeneous PFO, mainly due to the stable glassy structures and relatively
fluorene units.240,284,285 Some other cores, such as triaza- stable amorphous rubber-like structures formed upon increasing
truxene,286 triphenylamine,287 pyrene,47 and DPP,283 which the heating temperature. 1D DFB grating lasers were achieved
act as electron donors or acceptors, could strongly modulate with lasing thresholds down to 0.16 mJ cm2, lasing slope
the spectral and electrical properties of oligofluorenes arms. efficiencies up to 3.9%, and ca. 40 nm wavelength tuning in
It should be noted that pyrene-cored starbursts or pyrene- the blue- and sky-blue-spectral region. Impressively, the non-
capped starbursts were reported as attractive gain media encapsulated devices survived even operating at 10-times thresh-
because of the high PLQY, excellent thermal stability, and old energy with more than 1.1  105 pulses operation lifetime.
high charge carrier mobility of pyrene unit. The details will Another reported type of dendritic starburst gain media through
be discussed separately in the next section. In this section, we ICT was the functionalized starburst molecules based on DPP
discuss the construction of a series of pyrene-cored gain media core with four oligofluorene arms (DPP-star, 159, as shown in
system by ICT through the oligofluorenes arms to pyrene core. Scheme 13).283 Different from the fully p-conjugated system in
Three-arms oligofluorenes based on benzene and truxene pyrene-cored starbursts (Py-2 and Py-3, 157 and 158), the DPP-star
were explored as gain media by Skabara and coworkers.280–282 (159) had a p-conjugated axis and a non-conjugated axis.
The three-arms oligofluorenes materials based on benzene To understand the effects of conjugated pathway, linear molecules

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Table 4 Physical and amplified emission properties of dendritic starbursts

ASE Lasing
Threshold Threshold
Threshold [mJ cm2] Threshold [mJ cm2] Slope

Chem. Soc. Rev.

lema PLQYa lASE FWHMb Gain [nJ per (at pulse Feedback FWHMb [nJ per (at pulse efficiency
Review Article

Compd [nm] [%] [nm] [nm] [cm1] pulse] length) structurec llaser [nm] pulse] length) [%] Ref.
BP-1 400, 420 92 421 5–6 51 300 16 DFB 418 — 6 4.5 8.3 278
42 DFB 408 0.7 90 — 0.3 277
BPCz 412, 442 43 422 5–6 9 469 25 — — — — — — 278
ESB 392, 415 52 431 5–6 21 938 50 — — — — — — 278
BP-2 400, 420 75 — — — — — DFB 408 0.7 50 — 1.6 277
DFB 408 0.6 60 — 14 277
H-F 405 86 424 — 19.7 7.6 DFB 407–426 0.6 0.35 0.71@415 3.2 279
H-CH3 423 78 423 — 27.8 10.7 DFB 412 0.6 22 45@412 0.67 279
H-Ph 450 77 424 — 12.4 4.8 DFB 411–441 0.6 0.22 0.49@426 3.82 279
B2 388, 408 40 408 7 18.2 1.16  103 100 DFB 402–410 0.1–0.3 84 0.73@415 3.0 280
B3 408, 430 47 476 7 21.6 108 18 DFB 416–453 0.1–0.3 16.8 0.28@431 5.0 280
B4 413, 437 55 484 7 19.6 108 18 DFB 452–462 0.1–0.3 18 0.30@452 6.6 280
T3 414, 438 86 439 4 38 76 8.4 DFB 422–473 — 20 2.1@430 — 281
T4 420, 440 73 440 — 23 37 16 DFB 428–453 — 54 2.7@446 — 282
Tr6-3 420 90 — — — — — DFB 421–443 — 0.4 1.3@437 5.3 12
Py-2 476, 488 95 490 — 78 28 1.75 DFB 471–512 — 0.05 0.15 3.9 47
Py-3 477, 489 90 486 — 75 28.5 1.78 DFB 472–510 — 0.08 0.26 3.7 47
Linear-c 633 11 627 — — — 42 — — — — — — 283
DPP-Star 634 20 Non Non Non Non Non — — — — — — 283
TAT-2 439 65 456 17 398 24.9 — — — — — — 291
TAT-3 438 75 459 20 126 7.9 — — — — — — 291
TAT6-2 444 68 462 32 50 3.1 — — — — — — 291
TAT6-3 442 76 464 24 79 4.9 — — — — — — 291
TF-1 400, 416 65 419 6.2 — 95 4.3 DFB 430–446 — 8.71 17.8@431 — 292
TF-2 421, 438 41 441 4.7 — 227 10.3 DFB 438–452 — 2.21 4.5@439 — 292
PyP-1d 435 90 — — — — — DFB — — 180 339 — 296
PyP-2d 447 91 — — — — — DFB — — 100 188 — 296
PyP-3d 451 85 — — — — — DFB — — — — — 296
PyP-4d 453 85 — — — — — DFB — — 130 245 — 296
PyA-1d 453 91 — — — — — DFB — — 120 226 — 296
PyA-2d 453 90 — — — — — DFB — — 290 546 — 296
Py-4TAT 514 66 530 8 — 450 20.5 DFB 535–556 0.3 60 112.5@547 — 297
Py-2TAT 487 16 508 12 — 150 6.8 DFB 484–505 0.3 21 39.3@494 — 297
PyF1CN 484 41 501 9 55 36 2.0 DFB 481–502 0.3 1.9 0.79@502 — 298
PyF2CN 478 48 493 9 52 32 1.78 — — — — — — 298
PyF3CN 475 44 489 9 46 38 2.11 — — — — — — 298
PyF1NPh 485 65 498 — 74 119 6.6 — — — — — — 299
PyF2NPh 474 90 489 — 82 42 2.3 DFB 475–495 0.2 25 102@475 — 299
PyF3NPh 471 88 479 — 79 83 4.6 DFB — — — — — 299
Sp-P1 387, 410 — 387 2.2 — B2.4  104 B50 — — — — — — 302
Sp-P2 399, 424 — 422 2.9 — B2.4  103 B5 — — — — — — 302
Sp-P3 430 — 428 9.3 — — 30 — — — — — — 232
Sp-P4 433 — 425 4.6 — — 3 — — — — — — 232
Sp-Cz 382, 402 — 400 7.9 — — 50 — — — — — — 232
Sp-F 367, 387 — — — — — — DFB 378–395 0.19–0.35 — 62@382 — 303
Sp-DPVBi 465 — — — — — — DFB 435–499 — 5 0.32@460 — 304
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Ref.

300
300

301
301
305
305
305
306
306
284
284
284
with DPP unit as the central core in the conjugated orientation
(linear-DPP-c, 160, as shown in Scheme 13) and the non-
conjugated orientation (linear-DPP-nc) were synthesized and

efficiency
Slope investigated as well. DPP-star (159) and linear molecules exhibited

[%]
PLQYs lower than 6% when excited at the oligofluorene absorp-

—
—

—
—
—
—
—
—
—
—
—
—
tion bands; while a PLQY up to 20% was achieved when excited in
DPP-core absorbed spectral region. The insufficient spectral (and
Threshold

36.5@451
46.5@457

3.85@451
[mJ cm2]
(at pulse

6.0@457
energetic) overlap between the absorption of DPP core and the
length)

emission of oligofluorenes arms led to a rather unsuccessful

—
—
—
—
—
—
—
—
energy transfer from the oligofluorenes arms to the DPP core.
Published on 16 July 2020. Downloaded by Carleton University on 7/16/2020 [Link] PM.

DPP-star (159) molecule didn’t exhibited the presence of ASE;

Threshold

while spectral narrowing was observed for linear-DPP-c (160), in

[nJ per
pulse]

particular pumping DPP core directly. The ASE thresholds are 106

Detected at the same optical density (OD, OD = 0.16).

133
169

mJ cm2 excited at 355 nm (pumping the oligofluorenes arms) and

24
16
—
—
—
—
—
—
—
— 42 mJ cm2 excited at 532 nm (pumping the DPP core). Triaza-
truxene, an electron-rich unit, was also used as the core skeleton
FWHMb

to construct three or six armed oligofluorenes (TAT-2, TAT-3,

[nm]

0.2

TAT6-2, TAT6-3, 161–164).286,290 Compared with the corres-

0.2

0.2
0.2
—
—
—
—
—
—
—
—

ponding truxene-cored counterparts (T-n and Tr6-n), TAT-n

(n = 2 and 3, 161 and 162) and TAT6-n (n = 2 and 3, 163 and
448, 457
442–459
476–505
442–472

164) exhibited nearly 30 nm bathochromic shifts of the fluores-

llaser

—
—
—
—
—
—
—
—

cence spectra, suggesting ICT occurred between the arms and

the core. Levermore et al. reported the ASE performance of triaza-
structurec

truxene-cored oligofluorenes.291 The six-armed oligofluorenes

Feedback
Lasing

(TAT6-2 and TAT6-3, 163 and 164) exhibited low ASE thresholds
DFB
DFB
DFB
DFB

(r5 mJ cm2), and ordinary gain values (around 25 cm1).

—
—
—
—
—
—
—
—

Recently, Lai et al. reported a novel donor–acceptor core for

dendritic starburst design, in which triazine with electron-
Threshold
[mJ cm2]
(at pulse
length)

withdrawing nature and favorable electron-transporting ability

d
Non

Non
11.2

4.22
4.12
1.60
Full width at half maximum (FWHM). c DFB: distributed feedback.
156

was selected as the center, and carbazole and diphenylamine

6.3
5.4
6.6

83

60

units with electron-donating nature were attached onto the

triazine center to modulate the electrical properties by the con-
1.01  104
5.81  103
Threshold

struction of heterogeneous donor–acceptor core structure.292–294

[nJ per

Different p-conjugated oligofluorenes were again selected as the

pulse]

Non

Non
180
105

103
119

arms to construct dendritic starbursts, named as TF-1 (165)

76
74
29
97

and TF-2 (166). The chemical structures of TF-1 (165) and TF-2
(166) are shown in Scheme 13. The six-branched TF-1 and TF-2
[cm1]
Gain

Non

Non

exhibited fluorescence emission in deep-blue region with PLQYs

19
32
—
—

—
—
—
—
—

over 40%. The ASE thresholds of TF-1 (165) and TF-2 (166)
samples were recorded as 4.3 mJ cm2 and 10.3 mJ cm2,
FWHMb

respectively. Remarkably, TF-1 (165) and TF-2 (166) manifested

[nm]

Non

Non
4.0
4.2
4.1

enhanced ASE stabilities without significant spectral shifts (within

—
—

—
8

5
5
6

2 nm for TF-1 (165) and 1 nm for TF-2 (166)) and obvious changed
ASE thresholds annealing up to 200 1C in air.
[nm]

Non

Non
lASE
ASE

449
445

561

457
465
477
491

401
463
451

[Link] Starbursts with pyrene as the central core and/or the

PLQYa

end-cappers. Owing to high PLQY, excellent thermal stability,

[%]
56
60
74
62
66
52
35
27
52
30
27
32

and high charge carrier mobility of pyrene, pyrene derivatives

have attracted much interests.295 Pyrene derivatives with large
498
451
401
463
407

451
463
473
b

steric hindrance have been demonstrated as optional candi-

Table 4 (continued)

Measured in films.

dates for lasing applications. Generally, planar pyrene mole-

[nm]
lema

485,
434,
381,
435,
389,

427,
436,
451,
451
449

561
507

cules in solid state tend to form p–p stacking and excimers,

accompanying with red-shifted emission and reduced fluores-
cent efficiencies. The likelihood of pyrene aggregation can be
Compd
TrF1Py
TrF2Py

Tr-2BT
Tr-5BT
TrCSp
TrTSp
SpFPy
PyFPy

TrL-1
TrL-2
TrL-3

reduced by the introduction of bulky groups and/or constructing

TrSp

dendritic starburst structures. In this section, we introduce the

a

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Scheme 13 Dendritic starburst molecular structures based on oligofluorenes.

recently reported pyrene-cored or pyrene-capped dendritic were fixed at n = 6 and 7, which ensured good solubilities and
conjugated starbursts as efficient emitters for OSSLs. ordered films in CLCs to achieve CLC DFB lasers. Interestingly,
In 2010, Uchimura et al. developed a series of star-shaped the resulting lasing thresholds were very different. Taken PyP-3
molecules using pyrene as the central core and benzene, (169) and PyP-4 (170) as examples, a lasing threshold of PyP-4
diphenyl, terphenyl or anthracene units as the substituted (170) was recorded of 245 mJ cm2, but the lasing signal of
arms, named as PyP-n (n = 1–4) (167–170) and PyA-m (m = 1, PyP-3 (169) could not be detected under the same optical
2) (171 and 172).296 By doping these pyrene derivatives into density (OD, OD = 0.16). Due to its better solubility, PyP-4 (170)
cholesteric liquid crystals (CLCs), DFB lasers were constructed. could achieve lower threshold for CLC lasers (Eth = 43.3 mJ cm2)
In this study, the chain lengths [–(CH2)n–] of the alkyl groups with much higher OD (OD = 1). The corresponding data are

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summarized in Table 4. This work indicated that the flexible This work indicated that the long oligofluorene arms may be
chains could play a crucial role in the design of organic gain not the optimized choice for contributing dendritic starbursts.
media, coinciding with our previous work.228 Triazatruxene was Due to superior ASE performance of TrF1Py (181), the pyrene-
also introduced to link the planar pyrene core at 1,6- and 1,3,6,8- capped fluorene arms were further selected to construct stable
positions (Py-2TAT, and Py-4TAT, 173 and 174) to construct organic gain media. Lai et al. constructed four-armed starburst
monodisperse starburst architectures.297 Compared with the macromolecules as gain media, with spirofluorene and pyrene
reference linear counterpart (Py-2TAT, 173), Py-4TAT (174) showed as the central core.301 The chemical structures of the four-
a much higher PLQY (66% to 16%) resulted from the steric armed dendritic starbursts (PyFPy and SpFPy, 183 and 184) are
starburst molecular structure. But Py-4TAT (174) exhibited inferior depicted in Scheme 14. PL spectrum of PyFPy (183) showed
ASE/lasing properties, mainly due to the detrimental ICT between bathochromic shift (440 nm) compared with that of SpFPy
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pyrene core and four triazatruxene substituents. (184) in film, due to the efficient energy transfer between
In Section [Link], pyrene-cored starburst oligofluorenes pyrene-capped arms and pyrene core. The two samples mani-
(Py-n, 157 and 158) were introduced as gain media, which fested high PLQYs (74% for PyFPy, 183 and 62% for SpFPy,
had relatively excellent hole-injection abilities (the highest 184), low ASE thresholds (5.4 mJ cm2 for PyFPy, 183 and
occupied molecular orbital, HOMO levels), high PLQYs, low 6.6 mJ cm2 for SpFPy, 184) and stable ASE behaviors. ASE
lasing thresholds, net gain values of ca. 70 cm1, and superior could still be detectable for the two samples even upon annea-
thermal and environmental stabilities.47 But the low electron- ling up to 300 1C. To further estimate the optical stability,
affinity of pyrene would reduce the current density and hinder standard ASE measurements were conducted after soaking the
the potential application in electrically pumped OSLs. Electron- samples in water (80 1C) for 10 min and then drying by blowing
donating (or electron-accepting) groups, e.g., cyanophenyl298 and annealing in nitrogen environment. The ASE thresholds
and diphenylamine units,299 were incorporated onto the of PyFPy (183) and SpFPy (184) showed slight increase with
pyrene-based starburst oligofluorenes (PyFnCN, n = 1–3, 2.6-fold and 4-fold after 7 test cycles, respectively. As a refer-
175–177; PyFnNPh, n = 1–3, 178–180) to modulate the electrical ence, even after the first cycle, the ASE threshold of PFO
properties. For OLED devices, PyFnCN (n = 1–3, 175–177) and substantially increased with nearly 140-fold from 7.7 mJ cm2
PyFnNPh (n = 1–3, 178–180) manifested enhanced electrical to 1.06 mJ cm2. Therefore, PyFPy (183) and SpFPy (184)
properties with lower turn-on voltages, superior current effi- exhibited outstanding optical stabilities under both air and
ciencies and brightness in comparison with the electrolumi- water conditions. The tunable lasing region of 30 nm (PyFPy
nescent properties of their starburst counterparts Py-n (157 and (183): 476–505 nm; SpFPy (184): 442–472 nm) were achieved
158) without electro-active end-cappers. Without sacrificing in DFB resonates by varying grating periods and emission
the optical properties, they showed comparable ASE/lasing layer thicknesses. The minimum lasing threshold values of
thresholds and optical gain properties as summarized in 3.85 mJ cm2 (24 nJ per pulse) and 6.0 mJ cm2 (16 nJ per pulse)
Table 4. for PyFPy (183) and SpFPy (184) were obtained, respectively.
Pyrenyl-capped dendritic starbursts were also synthesized Correspondingly, the DFB lasers based on PyFPy (183) and
and designed for lasing applications. For example, Lai et al. SpFPy (184) showed good ambient stabilities even under water
reported a set of novel trigonal starbursts with a truxene core conditions.
and three end-capped pyrene units (TrF1Py and TrF2Py,
181 and 182).300 Due to the well-defined and restricted [Link] Other dendritic starbursts. Generally, solid-state
p-delocalization of truxene core, the fluorescence emission of molecules suffer from concentration quenching, induced by
TrF1Py (181) and TrF2Py (182) were blue-shifted compared with intermolecular interactions. To address this challenge, multi-
the pyrene-cored starbursts. The ASE thresholds for TrF1Py dimensional steric conformation based on spirobifluorene core
(181) and TrF2Py (182) films were recorded as 11.2 mJ cm2 was constructed to effectively prevent the molecular aggrega-
and 6.3 mJ cm2, with the corresponding stimulated peak at tion and improve the processability as well as the morpho-
449 nm and 445 nm. TrF1Py (181) exhibited relatively stable logical stability. In 1998, Johansson et al. presented the spectral
ASE performance with only 4.5-fold Eth increment during narrowing of blue-emitting spiro-linked oligophenylenes, named
the subsequent thermal annealing from room temperature to as Sp-P1 (185) and Sp-P2 (186),302 in amorphous films. The
250 1C. In comparison, Eth of TrF2Py (182) film increased spectral narrowing with dramatic collapse (linewidths to
seriously with 17.6-fold annealing up to 200 1C. For TrF2Py 2.2–2.9 nm) were observed in Sp-P1 (185) and Sp-P2 (186) with
(182) film, green fluorescent emission band ranging from an increase of pump fluence. The narrowing emission were
500 nm to 600 nm appeared after annealing at 250 1C; while associated with the 0–0 vibronic transition for Sp-P1 (185) and
the PL spectrum remained almost unchanged without green the 0–1 vibronic transition for Sp-P2 (186) in their emission
emission band for TrF1Py (181) after annealing. The existence spectra. Spehr et al. selected additional substitutions with four
of green emission band, originated from the excimer formation methoxy groups or two biphenyl groups attached onto spiro-
(from the p–p stacking fluorene units), explains the different sexiphenyl, named as Sp-P1 (185), Sp-P3 (187) and Sp-P4 (188).232
ASE behaviors of TrF1Py (181) and TrF2Py (182) after annealing. Four-carbazole-armed spiro-compound (Sp-Cz, 190) was also
The key data obtained from DFB lasers with TrF1Py (181) reported with ASE threshold down to 3 mJ cm2 for the thin film pre-
and TrF2Py (182) as the emitters are summarized in Table 4. pared by vacuum vapor deposition. In 2005, Schneider et al. reported

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Scheme 14 Conjugated starbursts with pyrene as the central core and/or the end-capper.

a spiro-material, 2,20 ,7,70 -tetrakis(p-fluoro-phenyl)-9,90 -spirobifluorene 191) as an emitter doping in another spiro molecule, 2,7-
(Sp-F, 189), as the emitter for thin-film UV OSSLs with a spectral bis(biphenyl-4-yl)-2 0 w,7 0 -di-tert-butyl-9,9 0 -spirobi-fluorene, at a
range from 378 nm to 395 nm.303 DFB lasers based on this sample concentration of 1.1%.304
exhibited a minimum threshold of 62 mJ cm2 at 382 nm. Output In 2015, Ma et al. reported a set of truxene-cored starburst
energy up to 6.8 W from the fabricated UV DFB laser was observed, molecules linked with different p-conjugated arms (TrSp,
rendering the resulting OSSL an efficient light source for biomarker TrTSp, and TrCSp, 192–194).305 Scheme 15 shows the molecular
spectroscopy. Minimum DFB lasing threshold was recorded as structures of these starburst compounds. The truxene core and
0.32 J cm2 at 478 nm from a guest–host optical gain system using spirobifluorene end-cappers were linked through single bonds
2,20 ,7,70 -tetrakis(2,2-diphenylvinyl)spiro-9,90 -bi-fluorene (Sp-DPVBi, (TrSp, 192), or thiophene units (TrTSp, 193), or N-ethylcarbazole

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Scheme 15 Other dendritic starbursts as organic gain media.

units (TrCSp, 194). Truxene-cored starburst with spirobifluorene 83 mJ cm2 for TrTSp (193) with thiophene linking truxene core
substituents (TrSp, 192) showed an optical gain with lasing and spirobifluorene substituents. But ASE disappeared in TrCSp
fluence above 156 mJ cm2. The ASE threshold came down to (194) with thiophene replaced by N-ethylcarbazole. The improved

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intermolecular vibronic coupling and suppressed low-frequency in polyfluorenes, and the specific morphology greatly relies
vibrational modes via incorporating the thiophene units were on the fabrication process and/or the thermal history of the
presented with density functional theory (DFT) calculation. The molecular film layer. There are a number of studies on the
enhanced high-frequency modes and decreased low-frequency phases and photophysical properties of polyfluorenes with
modes are favorable for the formation of effective quasi four-level different side-substitutions. Among them, PFO (203) is one of
energy system for stimulated emission. On the contrary, the the most widely known conjugated polymers, demonstrating
embedded N-ethylcarbazole moieties induce abundant strongly particularly rich-phase behaviors. Among the fluorene-based
elongated low-frequency modes, which ruin the quasi four-level polymers, the lowest lasing thresholds by far were recorded for
energy system. those with b-phase morphology, in which individual oriented
A series of structural isomers of trigonal starburst mole- molecular chain had an extended p-conjugation without p–p
stacking.307 Recent studies on the refractive index deviation of
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cules, containing a truxene core and quarter-dialkylfluorene

arms with different locations of benzothiadiazole (BT) moiety b-phase and amorphous phase polyfluorenes showed that
(Tr-nBT, n = 1–5, 195–199), were presented by Skabara and attractive device geometries featuring with mixed morphologies
Bradley.306 The optical properties from absorption and PL can be constructed.308 In comparison to the amorphous
spectra could be adequately described in accordance with BT morphology, the b-phase PFO (203) demonstrated an additional
unit at the three different possible positions, corresponding to lower energy absorption shoulder (B430 nm), resulted in a
a Tr-1/4BT pair (195 and 198), a Tr-2/3BT pair (196 and 197) and 1–2% refractive index increase in this spectral region. DFB
Tr-5BT (199), rationalized on the basis of molecular symmetry. lasers based on PFO (203) in b-phase via spin-coating mani-
Dramatically, Tr-5BT (199) exhibited a very weak BT unit fested bathochromic shifts by a few nanometers compared with
absorption, weak BT Raman scattering intensities centered at the output lasing from the amorphous polymer counterpart
1360 and 1547 cm1, and a strong blue-shifted PL, as a direct integrating with the same period DFB gratings.309
consequence of the relatively weak amplitude of HOMO with PFO (203) with various morphologies could be induced via
occupied natural transition orbital (NTO) when BT unit is spin-coating from various solvents, thermal cycling, exposure
located at the arm end. It led to the formation of a fast relaxed to solvent vapors, etc. Liquid crystalline phases could be
excited state from the Franck–Condon (vertical transition) state processed by depositing PFO (203) onto the rubbed polyimide
created by photon absorption, which resulted in the absence of substrates.310 By nanoimprinting, DFB grating was imposed
ASE even having a pumping energy of up to 500 mJ cm2, and onto the PFO (203) layer. The wavelengths of lasing emission
the accompanying low PLQY (ca. 27%). For Tr-nBT (n = 1–4, and the lasing thresholds could be tuned by controlling the
195–198), the ASE thresholds were around 60 mJ cm2, and the PFO (203) chains orientation with respect to the nanoimprinted
ASE saturation were observed above 200 mJ cm2. The results 1D DFB grating direction. In this way, the effective refractive
indicated that any effect of changing the ground state polarization indexes of PFO (203) could be adjusted to the oscillation
gradient may affect the performance of gain media in ASE and geometry and lasing thresholds as low as 20 mJ cm2 could be
lasing. Recently, Lai et al. reported a novel set of monodisperse achieved. On the other hand, the polymer alignment could
ladder-type oligo(p-phenylene)s starbursts, named as TrL-n improve the charge carrier mobility. The combination of b-phase
(n = 1–3, 200–202).284 Compared with their linear counterparts, and amorphous-phase morphology of PFO (203) layer were
TrL-n (200–202) exhibited suppressed low-energy emission and achieved by spin-coating hot solution and then exposing in
enhanced optical stabilities. The rather low ASE thresholds, toluene vapor. Side-by-side PFO (203) layer with various
i.e., threshold of 1.60 mJ cm2 for TrL-3 (202), were recorded for morphologies were induced onto the grating.311 The metastable
TrL-n, suggesting their promising prospects for use as organic morphology could be eliminated by heating up to the transition
gain media. temperature under the subsequent solvent exposure. Alexander
3.2.4 Conjugated polymers. Fluorescent polymers with et al. reported a novel polyfluorene with vinyl-ether-functionalized
p-conjugation are yielded from various monomers, ranging aliphatic side-chains (VE-PFO, 204).307,312 An extraordinary
from randomly composed chains to highly oriented and advantage of this polyfluorene was that the induced b-phase
defined chains. Polymers can possess various morphologies morphology could be fixed by cross-linking. The crosslinked
varying from disorderly amorphous to highly oriented crystalline. VE-PFO (204) film don’t dissolve in the subsequent solvent
As far as we are concerned, the amorphous polymers usually processing without affecting the morphology patterns. With
exhibit good optical properties, while the crystalline polymers this strategy, a b-phase cross-linkable VE-PFO (204) layer was
often manifest superior charge transport properties. imposed with a DFB grating by using electron beam litho-
Particularly, polymers exhibit excellent film-forming abili- graphy. As followed, an amorphous layer of VE-PFO (204) on
ties and attractive mechanical properties, thus rendering them top was formed by spin-coating, resulting in a double-layered
highly attractive for flexible optoelectronic devices via solution device with a stack of b-phase and amorphous morphologies.
processing. Both layers emitted laser radiation at the same time in such a
layered device with mixed morphologies when the excitation
[Link] Polyfluorenes. Polyfluorenes and their derivatives energy densities exceeded these two thresholds. A lasing thresh-
have been served as a significant kind of polymers for applica- old as low as 0.4 mJ cm2 was achieved from the b-phase cross-
tion in OSSLs. Various metastable morphologies are observed linkable VE-PFO (204) film. Recently, Lin et al. synthesized a

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model polyfluorene, namely, poly[4-(octyloxy)-9,9-diphenylfluorene- The increased mobilities were resulted from improved inter-
2,7-diyl]-co-[5-(octyloxy)-9,9-diphenylfluoren-2,7-diyl] (PODPF, 205), chain charge hopping at the sites of diethylhexylfluorene mono-
in which the octyloxy unit lied at 4-position of fluorene and mer, where the distance between intermolecular polyfluorene
diphenyl moieties substituted at the 9-position of fluorene skeletons was improved, compared with those with octyl-
units.313 The b-phase morphology of PODPF (205) film was substituents that might isolate the polyfluorene chains. With
achieved by spin-coating from toluene solution, and erased by 1D DFB grating, a lasing threshold (0.3 mJ cm2) with a slope
the annealing process. The thin film of PODPF (205) exhibited efficiency of 11% (Fig. 12d) was obtained for PFO-ET-1 (206) as
outstanding spectral stability without obviously green fluores- gain media. Organic lasers with a 45 nm spectral window from
cent emission band even annealing at 200 1C for 12 h under 434 nm to 479 nm were achieved by varying the film thicknesses
ambient conditions. The ASE threshold of b-phase PODPF (205) (45–160 nm) (Fig. 12e).
for 461 nm was 15.7 mJ cm2, and the lasing peak at 462 nm
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For blue-color-emitting polyfluorene polymers, one serious

with a threshold of 42 nJ per pulse was achieved. issue is their poor spectral stabilities caused by interchain
Modulating the lengths of side flexible chain has been interactions or the oxidative instabilities with fluorenone
proved to be an effective strategy to finely modulate the charge defects. Great efforts, such as constructing copolymer con-
carrier mobilities of polyfluorenes. For example, dioctylfluorene figuration, the introduction of other functional groups, spiro
was copolymerized with diethylhexylfluorene to improve the hole linkages, etc., have been made to overcome this challenge.
mobility of polyfluorene, and thus a homopolymer involving Xia et al. reported a copolymer, poly(9,9-dioctyl-fluorene-co-
only dioctylfluorene (PFO, 203), and copolymers consisting 9,9-di(4-methoxy)phenylfluorene) (PF8DP, 208) as gain medium,314
of dioctylfluorene and diethylhexyl-fluorene with ratios of 4 : 1 which exhibited similar PL spectrum, lower ASE threshold
(PFO-EH-1, 206) and 1 : 1 (PFO-EH-2, 207) were synthesized.11 (6.25 mJ cm2), and similar gain value (66 cm1) compared
The molecular structures of these polymers are depicted in with PFO (203). A novel polymer with spiroanthracenefluorene
Fig. 12a and Scheme 16. Decreasing the length of substituted monomer, namely poly(9-spiro(10,10-bis(2-ethylhexyl)-10H-
flexible chain from octyl to butyl, the interchain distance was anthracene)-fluorene) (PEHSAF, 209), was reported as gain
reduced with increased mobility and favorable light emission medium, which exhibited thermally stable stimulated emission
characteristic. The ASE wavelengths were around 450 nm for in vacuum upon annealing up to 250 1C with moderate gain
all polymers (Fig. 12b). As shown in Fig. 12c, the resulting coefficient (38 cm1) and ASE threshold (131 mJ cm2).315
copolymer materials exhibited enhanced hole mobilities (deter- Functional groups, such as carbazole,316 bi-naphthalene,317
mined by time-of-flight (TOF)) (mhole E 3–6  104 cm2 V1 s1), solfonyl,50 and dibenzothiophene-S,S-dioxide spacer units,318
which were more than 100-fold higher than that of PFO (203). were selected to construct statistical copolymers of polyfluorenes.

Fig. 12 (a) Polymer chemical structures of PFO-EH-1, PFO-EH-2 and PFO. (b) Absorbance (solid line, left), PL (dash line, right) and ASE (filled area, right)
spectra for PFO-EH-1 (red), PFO-EH-2 (green) and PFO (black). (c) Field dependence of the mobility for PFO-EH-1 (red), PFO-EH-2 (green) and PFO
(black). (d) Input–output characteristics for a 1D DFB laser with covered PFO-EH-1 film. The right inset shows output emission spectra with the increase
of pump energy. (e) Top panel: The spectral window of organic lasers. Bottom panel: Corresponding threshold variation of the output lasing wavelength
for the PFO-EH-1 DFB lasers. Reproduced with permission from ref. 11. Copyright 2008 Nature Publishing Group.

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Scheme 16 Polyfluorene derivatives as gain media.

The polymer structures of PFC (210), PFBN (211), PFSO (212) and In 2008, Laquai et al. demonstrated the ASE performance of
PPFSO-n (n = 1–3) (213–215) are shown in Scheme 16. The a number of blue-emitting LPPPs, namely, LPPP-1/2/3 (218–
corresponding data of ASE/lasing performance are shown in 220).46 Carbazole was introduced to construct ladder-type poly-
Table 5. Polyspirobifluorenes cross-linked with the use of oxetane mers (PLC-1/2, 221 and 222). A fully arylated polyfluorene
functional groups were also explored and investigated, which (PFP8, 216, as shown in Scheme 16) was selected as a reference
exhibited mediocre ASE performance.319–321 for the comparison with the ladder-type polymers. The
chemical structures of LPPP-1/2/3 (218–220) and PLC-1/2 (221
[Link] LPPPs. The low carrier mobilities and poor oxidative and 222) are depicted in Scheme 17. The ASE thresholds of
stabilities in polyfluorene derivatives, which is generally caused carbazole-containing LPPPs (PLC-1/2, 221 and 222) were much
by interchain-aggregation-induced energy transfer to fluore- higher, and no meaningful gain coefficient was recorded for the
none defects, have inevitably impeded their potential applica- resulting carbazole-containing polymers. LPPP-1 (218), whose
tions in electrically driven OSSLs. To overcome this problem, monomer with 3 bridged phenyl rings, demonstrated a low ASE
LPPPs with the design concept to fuse the conjugated backbone threshold of 3 mJ cm2 and a relatively high optical gain of
architectures have been proposed to explore organic emitters 21 cm1. As to indenofluorene copolymers, ASE thresholds
with great thermal and electrochemical stability, and promi- close to that of LPPP-1 (218) were observed for poly(indeno-
nent charge-carrier mobility. The investigation of synthesis and fluorene-cophenanthrene)s (4.5 mJ cm2 and 17.5 mJ cm2 for
photophysical property of LPPP was firstly reported by Scherf PIF-1 and PIF-2, respectively; 223 and 224).48 However, PIF-1
and Müllen in 1991.322 Since then, a large number of ladder- (223) demonstrated a very high gain value of 154 cm1. More
type polymers have been designed and synthesized for organic impressively, a TOF hole mobility of 102 cm2 V1 s1 was
electronics.323,324 Among them, the most well-known ladder- obtained for PIF-1 (223). In an OFET architecture, hole mobility
type polymer is MeLPPP (217), which has aroused intense up to 0.5 cm2 V1 s1 was achieved. Simultaneous optimization
photophysical investigations.46,60,322,325–327 It showed an ASE of stimulated emission and charge carrier mobility is generally
threshold of 20 mJ cm2 at the peak of 489 nm. The required towards electrically pumped organic lasers.
bathochromic-shifted ASE peak, compared with PFO (203),
was mainly due to the large planar rigid ladder-type conjugated [Link] Polymers contain BT units. As for other polyfluorene
backbone structure. A moderate gain coefficient of 16 cm1 was copolymers, poly(dioctylfluorene-co-benzothiadiazole) (F8BT,
detected by using VSL method in MeLPPP (217). Kallinger et al. 225) is a popular conjugated polymer with yellow-green stimu-
reported the lasing performance based on MeLPPP (217) as the lated emission and moderate ASE threshold (28 mJ cm2).314
emitter. A low lasing threshold (4.8 mJ cm2) was demonstrated.325 By modulating the ratio of fluorene (F8) to BT units from 1 : 1 to

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Table 5 Physical and amplified emission properties of conjugated polymers

ASE Lasing
Threshold Threshold
Threshold [mJ cm2] Threshold [mJ cm2] Slope
lema PLQYa lASE FWHMb Gain [nJ per (at pulse Feedback FWHMb [nJ per (at pulse efficiency
Chem Soc Rev

Compd [nm] [%] [nm] [nm] [cm1] pulse] length) structurec llaser [nm] pulse] length) [%] Ref.
Glassy-PFO 423, 450 50 452 4 74 350 29 DFB 437–477 — 6 1@449 2 11 and 49
Amorphous VE-PFO 422, 445 — 445 — — — — DFB 445, 449 0.2 5.8 3.6@445 1.84 307
b-phase VE-PFO 438, 467 — 467 — — — — DFB 468 0.2 4  102 0.4 1.93 307
PODPF 445, 465 46 461 4.6 — 251 15.7 DFB 462 — 41.9 — — 313
PFO-ET-1 421, 448 70 448 — 87 — — DFB 434–479 — 0.1 0.3@447 11 11
PFO-ET-2 424, 451 60 451 — 87 — — DFB 437–476 — 0.14 0.5@451 10 11
PEHSAF 423, 447 55 445 38 2.1  103 1.31  102 DFB 433–449 — 18.5 68.5@446 5 314
PF8DP 427, 449 50 452 5 66 100 6.25 DFB 455–465 — 4 16@460 — 315
PFC 453 450 5 8 — 200 — — — — — — 316
PFBN 428, 454 — 446 — — — — DFB 435–465 — — 3@455 — 317
PFSO 419 — 423 9 20 2.56  103 32 — — — — — — 50

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PPFSO-1 450, 478 53 Ca. 475 — — 390 24.4 — — — — — — 318
PPFSO-2 450, 478 44 Ca. 475 — — 250 15.6 — — — — — — 318
PPFSO-3 450, 478 51 475 — — 250 15.6 DFB 467–487 — 18 66.7@485 — 318
PFP8 423, 450 57 449 18 1.92  103 24 — — — — — — 46
MeLPPP 461, 492 26 489 16 1.6  103 20 DFB 490 0.3 1.5 4.8 — 46 and 325
LPPP-1 437, 466 45 468 — 21 240 3 — — — — — — 46
LPPP-2 — 23 475 — 15 800 10 — — — — — — 46
LPPP-3 — 35 479 — 6 8  103 100 — — — — — — 46
PLC-1 — 15 480 — — 8.8  103 110 — — — — — — 46
PLC-2 — 14 492 — — 1.2  104 150 — — — — — — 46
PIF-1 426, 448 55 451 — 154 360 4.5 — — — — — — 48
PIF-2 425, 452 56 453 — 59 1.4  103 17.5 — — — — — — 48
F8BT 561 58 576 8 22 450 28.1 314
9F8–1BTd 545, 568 — 560 20 — 200 2 DFB 568 — 190 8.46 — 19 and 328
20F1/4F8BTe — 52 552 14 32 62 2.8 — — — — — — 330
15F1/4F8BTe — 40 552 13 — 112 5.1 — — — — — — 330
10F1/4F8BTe — 34 551 15 — 138 6.3 — — — — — — 330
F1/4BTe — 30 549 14 — 308 14 — — — — — — 330
LPBT-1 545 36 552 8 66 1.18  103 65.8 — — — — — — 331
LPBT-2 548 49 560 12 77 131 7.3 — — — — — — 331
LPBT-3 551 55 568 13 84 108 6.0 DFB 543–563 0.3 7.2 3.0@543 — 331
Red F 662 40 685 10 24 450 28.1 DFB 627–702 0.55 1.1@698 314 and 333
PPV 520, 555 8 — — — — — DBR 545 4 250 — — 17
BuEH-PPV 520, 560 — 563 9 62 — 15 — — — — — — 17 and 55
BBEHP-PPV 496, 528 86 538 6 19 193 1.2 DFB 535 1 0.3 0.04 — 336 and 337
MEH-PPV 585, 625 10 627 8 Ca. 70 500 62.5 DFB 636 1 4 15.9 6.8 343–345
BEHP-co-MEH-PPV 550, 625 — — — — — — MC 607 1 0.71 9 — 340
TN-RxGyf 430, 452, 520 — 448 4 — 1.13  103 63 — — — — — — 350
TM-RxGyf 431, 453, 518 — 448 4 — 1.56  103 86.8 — — — — — — 351
PDOPT 616, 655 — — — — — — MC 655 1.3 — 2.4 — 352 and 353
P3HTg 613, 665 25 661 20 50 1.0  103 62.5 DFB 640–673 1–2 8 26@653 2.4 355
In-MOF 482, 522 — 472 18 — — 3.6  104 — — — — — — 103
Zn-MOF 473 — 473 19 — — 2.7  104 — — — — — — 103
a
Measured in films. b Full width at half maximum (FWHM). c DFB: distributed feedback, DBR: distributed Bragg reflector; MC: microcavity. d InGaN light-emitting diode (LED) pumped laser.
e
‘‘10/15/20’’ represents the ratio of 9,9-di(2-methyl)butyl (F1/4) in the copolymers; the ASE measurements are tested in the blended samples with PFO. f ‘‘x/y’’ means the ratio of green or red
emission unit in the single polymers, respectively; the ASE threshold is the lowest result. g The ASE and lasing measurements are tested in the blended samples with F8BT.
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Scheme 17 Ladder-type poly(p-phenylene)s as gain media.

9 : 1, the ASE threshold of this novel material, named as

9F8–1BT (226), was significantly decreased with a value of
2 mJ cm2.328 This improvement might originate from the
isolation of polymer chains by the octyl side chains, leading Scheme 18 Polymeric gain media with BT units.
to the efficiently suppressed exciton annihilation. With using
9F8–1BT (226) as the emitter, the first LED pumped OSSL was
demonstrated by Samuel’s group.19 The schematic diagram of nF1/4F8BT (227–230) blends exhibited superior optical gain
the hybrid InGaN-semiconducting polymer laser is depicted in properties. The branched F1/4 substitution in the copolymers
Fig. 1. The onset of DFB laser at 568 nm was achieved when the hindered exciton annihilation. Ladder-type oligophenylenes
InGaN LED driving current above 144 A, corresponding to were introduced to construct ladder-type poly(indenofluorene-
a lasing threshold of 6.5 mJ cm2 (180 W cm2). This work co-benzothiadiazole)s to explore light amplified application.331,332
opened the gate of indirect electrically pumped organic Ladder-type oligo(indenofluorene)s were incorporated with BT
lasers.18,26,27,125–127 With using F8BT (225) and 9F8–1BT (226) units and various indenofluorene chains with different lengths,
as gain media, Karl et al. recently reported the membrane- denoted as LPBT-n (n = 1–3) (231–233). Compared with 9,9-
based, substrate-less and extremely thin DFB lasers for portable dioctylfluorene units, the indenofluorene chains exhibited much
security tags application.329 more efficient energy transfer to BT units. Without blending, a
Recently, Yu et al. developed a series of fluorene-based low ASE threshold of 6.0 mJ cm2 was achieved for LPBT-3 (233),
copolymers with yellow-green emission composed of the branched with a high net gain value (84 cm1).
2-methyl-butyl substituted fluorene-co-benzothiadiazole and F8BT Lasing can also be observed in ternary copolymers. Ternary
monomer in different ratios (namely, nF1/4F8BT, 227–230, with copolymer poly(fluorene-co-benzothiadiazole-co-thiophene-co-
n representing the ratio of 9,9-di(2-methyl)butyl (F1/4) in the tri-phenylamine), known as Red F (234), was reported as a
copolymer).330 The chemical structures of nF1/4F8BT are gain medium.314,333,334 A very broad tunable wavelength range
depicted in Scheme 18. Doping nF1/4F8BT (227–230) copolymers (627–702 nm) was demonstrated in the resulting optically
into PFO (203), a systematic increase in PLQY was observed by pumped 2D DFB lasers.333 The lowest lasing threshold was
increasing the ratio of the F1/4 monomers. Manifested as reduced recorded of 1.1 mJ cm2 for the operation at 698 nm. Optical
ASE thresholds (2.8 mJ cm2 vs. 4.3 mJ cm2) and increased gain switching in DFB lasers based on Red F (234) with red lasing
values (32 cm1 vs. 22 cm1) with respect to F8BT blends, emission was demonstrated by Xia et al., using optical control

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pulses (1.28 mm, 4 ps, 5 kHz).334 As a response to the optical BBEHP-PPV (237) down to 0.04 mJ cm2 (Fig. 13a–c), and
control pulse, the reduction of the lasing output by more demonstrated the sensing application to detect explosives
than 30 times can be used a new switch to provide effective based on the resulting organic laser device.336 The results
wavelength conversion from silica to polymer optical fiber to showed that the resulting optically pumped attenuated laser
regulate the communication wavelengths. device based on BBEHP-PPV (237) film displayed excellent
sensitivity to the explosive vapors over 30 times higher, com-
[Link] PPV derivatives. Besides the fluorene-based polymers, pared with the observation from PL emission (Fig. 13d and f).
another important class of linear polymers are PPVs. The first As sketched in Fig. 13e, in the existence of explosive vapors, the
polymer light-emitting diode (PLED) was reported based on PPV DFB lasing threshold increased and the chemical sensitivity
(235) by Friend and co-authors in 1990.5 Lasing emission from was determined. Non-radiative deactivation pathways were
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the polymer film was reported in 1996 by optically pumping PPV induced by trace amount of explosive vapors of 2,4,6-trinitro-
(235).17 Due to the insoluble nature of PPV (235), PPV (235) films toluene (TNT) and 2,4-dinitrotoluene (DNT), leading to the
were usually fabricated from the solution-processable precursor competition with stimulated emission. In other work, by
polymer. The precursor polymer converted into PPV (235) in mixing BBEHP-PPV (237) with 1,4-cyclohexanedimethanol divi-
films after thermal conversion.5,335 Various flexible chains were nyl ether (CHDV) and spin-coating onto a DFB grating, the
then added onto the phenylene units to enhance the polymeric diluted BBEHP-PPV (237) film exhibited a high threshold of
solubility. Various PPV derivatives were reported with promising 1.1 mJ cm2.337
ASE/lasing performance, including poly(2-butyl-5-(2 0 -ethylhexyl)- Park et al. investigated the ASE performance of MEH-PPV
1,4-phenylenevinylene) (BuEH-PPV, 236),17 poly(2,5-bis(2 0 ,50 - (238) in 1999.343 Narrowed spectrum was recorded with an ASE
bis(200 -ethylhexyloxy)phenyl)-1,4-phenylenevinylene) (BBEHP- threshold of 62.5 mJ cm2 and emission center at 638 nm. The
PPV, 237),336,337 poly(2-methoxy-5-(20 -ethylhexyloxy)-1,4-phenylene- net gain of doped MEH-PPV film is ca. 70 cm1.344 Since then,
vinylene) (MEH-PPV, 238),338 poly((2-(2 0 ,5 0 -bis(200 -ethylhexyloxy)- MEH-PPV (238) has been widely used as a standard red-color
phenyl)-1,4-phenylene-vinylene)-co-(2-methoxy-5-(2 0 -ethyl-hexyl- gain medium in organic laser physics. For example, a 2D DFB
oxy)-1,4-phenylenevinylene)) (BEHP-co-MEH-PPV, 239),339,340 laser based on MEH-PPV (238) was demonstrated by Samuel
etc. The polymer structures are depicted in Scheme 19. and co-authors.345 A pumping energy threshold of 5.9 mJ cm2
‘‘Super Yellow’’ (240) is one of the most popular PPV was recorded by the observation of the band-edge lasing at
derivatives as yellow emitters in PLEDs.341,342 PPV derivatives 636 nm. The laser exhibited an energy slope efficiency of 6.8%,
BBEHP-PPV (237) and MEH-PPV (238) have been extensively with maximum output energy of 1.12 nJ per pulse at pumping
studied for green and red polymer lasers, because of their very energy of 20.4 nJ per pulse. A novel copolymer, named as BEHP-
low ASE/lasing thresholds and high optical gain values. co-MEH-PPV (239), consisting of the monomers of BEHP-PPV
For example, Rose et al. recorded the low lasing threshold of and MEH-PPV, was found to be resistant to photodegradation
with good solubility at room temperature. PL spectrum of
BEHP-co-MEH-PPV (239) covered broad emission ranging from
550 nm to 625 nm, corresponding to the yellow-red emission
characteristic of MEH-PPV, indicating efficient intramolecular
energy transfer in the polymer skeletons. A low lasing threshold
was achieved (9 mJ cm2) in a single-defect microcavity structure,
with emission peak at 607 nm.340

[Link] Other polymeric gain media. Hyperbranched polymers

have been employed as efficient emitters in OLEDs,346,347
especially in white PLEDs.348,349 The molecular design provides
a valuable platform to achieve high-quality white EL. As a part
of the efforts, Lai et al. explored the fine modulation of the
energy transfer process in different emission species of two
novel star-shaped single-polymer systems.350,351 Two star-shaped
models, tris(4-(3-hexyl-5-(7-(4-hexylthiophen-2-yl)-benzo[c][1,2,5]-
thiadiazol-4-yl)thiophen-2-yl)phenyl)amine (TN) and 7,7 0 -(5,5 0 -(9-
(4-(3-hexyl-5-(7-(4-hexyl-thiophen-2-yl)benzo[c][1,2,5]thiadiazol-4-
yl)thiophen-2-yl)phenyl)-H-carbazole-3,6-diyl)bis(4-hexylthio-
phene-5,2-diyl))bis(4-(4-hexylthiophen-2-yl)benzo[c][1,2,5]thiadiazole)
(TM), were chosen as the central cores for saturated red emission.
Star-shaped single polymers were framed by introducing BT units as
green emissive dopants and polyfluorene as blue emissive moieties
onto the red TN/TM cores. The chemical structures of star-shaped
Scheme 19 PPV derivatives for polymer lasers. single-polymers (241–250) with different ratios of TN/TM and BT

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Fig. 13 (a) Chemical structures of BBEHP-PPV, TNT and DNT. (b) DFB grating structure fabricated from polydimethylsiloxane. (c) Lasing spectra of
BBEHP-PPV atop a DFB structure. (d and f) Spectral sensitivity of optically pumping BBEHP-PPV thin film before and after exposure to DNT under
different pulse energies (0.39 mJ cm2, d; 0.96 mJ cm2, f). (e) Schematic representation of ASE increase in gain medium after exposure to quencher.
Reproduced with permission from ref. 336. Copyright 2005 Nature Publishing Group.

units are depicted in Scheme 20. Interestingly, ASE could be As discussed in Section 2.4.3, MOFs were selected as feed-
observed in these white emissive single-polymers. Due to the back structures for organic dye lasers because of their quasi-
trace amounts of green and red emission units, the incomplete periodic configurations. However, the device stability is a key
energy transfers could be achieved by ICT in these white emissive issue because of the short-term stability of the encapsulated
single-polymers. The ASE peaks were located at 448 nm, which dye. Chemically bridging the metal-nodes with chromophore-
were assigned to the stimulated emission of polyfluorenes. The linkers would enhance the thermal stability compared to the
large optical losses induced by abundant vibronic bands from the physically doping strategy. Recently, Medishetty et al. reported
broad PL emission in these polymers led to much higher ASE two novel 3D MOFs, In-MOF (253) and Zn-MOF (254), which
thresholds (410 fold) as compared with PFO (203). were derived from a well-established AIE dye, tetrakis[4-(4-
Generally, physical blending strategy is an effective method carboxyphenyl)phenyl]ethane (H4TCPE), acting as a linker coor-
to improve the optical gain properties. Mixing two different dinating with In3+ and Zn2+ nodes (Fig. 14a and b).103 Pumped
chromophores could effectively prevent concentration quenching. by femtosecond pulse laser, these MOF single crystals gener-
With this strategy, some less emissive materials could achieve ated intrinsic blue stimulated emission with resulted ASE
relatively low ASE/lasing thresholds. For example, for thiophene- thresholds of 36 mJ cm2 and 27 mJ cm2 for In-MOF (253)
based polymers, lasing was recorded in microcavity resonator and Zn-MOF (254), respectively (Fig. 14c, d and f). Besides, the
containing poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT, 251) with emission lifetime of In-MOF (253) decreased from 900 ns to
relatively high lasing threshold of 2.4 mJ cm2 (24 mW cm2).352,353 500 ns for stimulated emission (Fig. 14e). Similarly, the
But no lasing action was observed for poly(3-hexylthiophene) decreased fluorescence lifetime from 1.2 ms to 380 ns was also
(P3HT, 252) even in high Q resonator configuration.354 By blending shown in Zn-MOF (254) (Fig. 14g). It should be noted that there was
10–20 wt% P3HT (252) with F8BT (225) films, efficient lasing from no lasing occurring during the optical pumping, though in some
P3HT (252) with attractive optical gain properties were achieved.355 cases, the MOF quasi-periodic structure could act as a Fabry–Perot
A threshold of ca. 60 mJ cm2 with a corresponding high gain cavity to realize lasing.100–102 The ASE thresholds were relatively
(50 cm1) was recorded for the blended film with 15 wt% P3HT higher compared with other organic materials. But still, this work
(252). The resulting 1D DFB lasers exhibited thresholds as low as proved that coordination network materials, such as MOFs, could
26 mJ cm2, much lower than other thiophene-based polymers. act as novel optical gain media for lasing applications.

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Scheme 20 Polyfluorene derivatives as gain media.

3.3 Triplet gain media and triplet sensitizers and Fig. 15a). Compared with the non-substituted compound,
Generally, there are mainly three emission mechanisms for (E)-2-(((4-nitrophenyl)vimino)methyl)-naphthalen-1-olateBF2 (C-BF2)
organic light sources: fluorescence, phosphorescence,356 and (Fig. 15a), S-BF2 (255) reversed the lowest singlet p–p* electronic
TADF,2 currently available for achieving efficient light output. The transition by n–p* transition. In sharp contrast to the forbiddance of
existing organic gain media are dominated by fluorescent materials. ISC from S1(p,p*) to T1(p,p*) in C-BF2, T1(p,p*) ’ S1(n,p*) ISC was
According to spin statistics, a 1 : 3 ratio for singlet and triplet found with 100% efficiency in S-BF2 (255). ICT character was
excitons is expected in carrier recombination,357,358 indicating introduced in S-BF2 (255) with the assistance of the nitro moiety,
that 75% formed excitons are prevented for the contribution of leading to a moderate phosphorescence efficiency of 10%. S-BF2
the singlet population in fluorescent emitters. As a result, a (255) single-crystalline nanowires were fabricated via solution
maximum of 25% for internal electroluminescence (EL) quantum self-assembly method. As shown in Fig. 15b and c, the nanowires
efficiency (IQE) would be limited in organic light-emitting devices, manifested strong yellow-red emission and acted as effective
such as OLEDs, under current injection. Phosphorescent and optical waveguide with bright PL from the end tips. A fast decay
TADF materials are particularly interesting, in which theoretically lifetime of 2.3 ns was monitored with PL peak at 510 nm
all of the formed excitons, including singlet and triplet excitons, (Fig. 15d), corresponding to fluorescence emission. Another
could be harvested as EL. As discussed in Section 4, extremely high emission peak of S-BF2 (255) nanowire was at 610 nm with a
current density (a few kA cm2) is necessary for achieving decayed lifetime of 9.3 ms (Fig. 15d), which was assigned to
electrically pumped OSSLs. Therefore, if the 75% triplet excitons phosphorescence emission. Lasing output at 650 nm was
could be effectively utilized, it would be much helpful to reduce the recorded in the 30 mm length nanowire, mainly because of
injected current density above lasing threshold for electrically the construction of Fabry–Perot microcavity in the nanowire
pumped OSSLs. In most common cases, since the value of the (Fig. 15e). The evolution from phosphorescence radiation to
excited-state absorption cross-section (sex, T1 - Tn) for phosphor- narrowed spontaneous emission started at 10.4 mJ cm2, and
escent (or TADF) emitter is much larger than the maximum further increasing the pumping energy above 12.8 mJ cm2,
stimulated emission cross-section (sem, T1 - S0), no ASE occurs lasing oscillation occurred (Fig. 15f and Table 6). FWHM of
in the pumping process.44 individual cavity mode was ca. 0.76 nm with lasing peak at
The only one example of phosphorescence laser was reported 650 nm, obtaining a cavity quality factor Q E 850. More modes
by Yu et al.40 Unlike most phosphorescent metal-complex in the nanowire lasing spectra were observed by increasing the
molecules, the phosphorescence was achieved from a sulfide- nanowire lengths (Fig. 15g). A linear relationship was demon-
substituted difluoroboron compound, (E)-3-(((4-nitrophenyl)- strated in the value of mode spacing dependent on 1/L (L is the
imino)methyl)-2H-thiochroman-4-olateBF2 (S-BF2, 255) (Scheme 21 twice fold of nanowire length). This work made a big leap by

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Fig. 14 (a and b) Perspective views of In-MOF (a) and Zn-MOF (b) molecular structures. (c) PL and ASE optical images of Zn-MOF crystals with the scale
bar of 100 mm. (d and f) Dependence of emission spectrum on pumping laser energy for In-MOF (d) and Zn-MOF (f). (e and g) Transient PL with pumping
energy below and above ASE threshold in In-MOF (e) and Zn-MOF (g). Reproduced with permission from ref. 103. Copyright 2017 Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim.

exploring phosphorescence gain media for addressing the narrow PL emission with FWHM less than 30 nm. The
challenges towards OSL diodes (OSLDs). co-evaporated film of 6 wt% DABNA-2 (257) in CBP showed a
Another type of triplet gain media were achieved in TADF rapid decrease of FWHM, corresponding to a nonlinear
emitters reported by Adachi’s group.22,41–43 The first reported increase of output intensity, with increasing the excitation
TADF examples as gain media are 5,9-diphenyl-5,9-diaza-13b- intensity, which clearly indicated the achievement of light
boranaphtho [3,2,1-de]anthracene (DABNA-1, 256) and 9-([1,1 0 - amplification. ASE threshold of 1.6 mJ cm2 with emission
biphenyl]-3-yl)-N,N,5,11-tetraphenyl-5,9-dihydro-5,9-diaza-13b- peak at 494 nm was recorded. Similar ASE characteristic was
boranaphtho[3,2,1-de]anthracen-3-amine (DABNA-2, 257).41 observed for DABNA-1 (256). Rigid core of DABNA maintained
Unlike typical TADF materials, DABNA-2 (257) held the strong a small energy band gap between S1 and T1 (DEST), which
p–p* characteristic, leading to a high PLQY (74%) and a quite appeared as the key to the gain for light amplification. But the

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Scheme 21 The triplet gain media.

Fig. 15 (a) Chemical structures and energy level diagrams of S-BF2 and C-BF2. (b) PL microscopy image of S-BF2 nanowires. (c) Absorption and PL
spectra of S-BF2 nanowire. (d) Transient PL of S-BF2 nanowire monitored at the fluorescence region (red, inset) and the phosphorescence region (black).
(e) Emission spectra under different pump densities in a single 38 mm length S-BF2 nanowire. (f) Dependence of output intensity on pumping density in
the fluorescence band and the phosphorescence band, monitored at 510 nm and 650 nm, respectively. (g) High-resolution lasing spectra for S-BF2
nanowires with lengths of 20, 30, and 50 mm. Reproduced with permission from ref. 40. Copyright 2017 American Chemical Society.

rate of reverse intersystem crossing (RISC) in DABNA-2 was difluoride curcuminoid derivatives, named as BDFC-1 (258) and
very low (kRISC = 3.1  103 s1), which significantly restricted BDFC-2 (259), contained triphenylamine donor and acetyl-
the contribution of converted singlet excitons from triplet acetonate boron difluoride acceptor. Compared with the one
excitons to light amplification process. branch derivative BDFC-1 (258), BDFC-2 (259) possessed larger
NIR TADF emitters, boron difluoride curcuminoid deriva- p-conjugated system and stronger charge transfer character with
tives, were then investigated as gain media.22,42,43 The boron efficient NIR emission.22 As described in Fig. 16a, by increasing

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Table 6 Physical and amplified emission properties of triplet gain media

ASE Lasing
Threshold Threshold
Threshold [mJ cm2] Threshold [mJ cm2]
lema PLQYa lASE FWHMb Gain [nJ per (at pulse Feedback FWHMb [nJ per (at pulse Slope
Compd [nm] [%] [nm] [nm] [cm1] pulse] length) structurec llaser [nm] pulse] length) efficiency Ref.
C-BF2 510, 610 10 650 — — — 10.4 NW (850) 650 0.76 — 12.8@650 — 40
DBANA-1d — — 479 7.2 — 140 2.8 — — — — — — 41
DBANA-2d 467, 490 74 494 6 — 80 1.6 — — — — — — 41
BDFC-1e 686 30 697 8.7 — 760 19 — — — — — — 42
BDFC-2d 722 70 747 10 — 280 7 — — — — — — 22
BDFC-3f
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760 45 801 16 — 300 7.5 — — — — — — 43

BDFC-4f — 58 738 — — 80 Ca. 2 — — — — — — 43
a
Measured in films. b Full width at half maximum (FWHM). c NW: nanowire (Q-factor). d
Blending concentration: 6 wt%. e Blending concen-
tration: 15 wt%. f Blending concentration: 2 wt%.

Fig. 16 (a) Photographs under UV light of CBP blended samples (wt%: BDFC-2 concentration). (b) PLQYs of BDFC-2 blended films at various doping
concentrations. (c) Streak camera image of the 6 wt% BDFC-2 blended film. (d) Jablonski diagram shows two RISC processes in the NIR-emitting BDFC-2
blends. (e) NIR OLED structure, including schematic and energy diagram. (f and g) EQE vs. current density (f) and EL spectra (g) in OLEDs. (h) Emission
spectra measured in the 6 wt% BDFC-2 doped film at different excitation densities. (i) FWHM (right) and the corresponding output intensity (left) for the
6 wt% BDFC-2 blend as a function of excitation density. (j) Dependence of ASE threshold and ASE wavelength on doping concentration in BDFC-2
blends. Reproduced with permission from ref. 22. Copyright 2018 Nature Publishing Group.

the BDFC-2 (259) concentration from 2 to 60 wt%, the blended the BDFC-2 (259) blends gradually increased, and a maximum
samples (with CBP as a host) showed substantial spectral bath- value of 70% was achieved for the 6 wt% BDFC-2 (259) blended
ochromic shifts in NIR region, corresponding with PL peak from sample (Fig. 16b). The streak camera image of 6 wt% CBP
706 to 782 nm. The PLQY of neat BDFC-2 (259) film was only ca. blended sample with BDFC-2 (259) exhibited prompt NIR and
3.2%. Decreasing the doping concentrations, the PLQY values of delayed fluorescence (Fig. 16c), which mainly originated from

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the emissive monomer states (with shorter-lived emission, at to pass its triplet and singlet energy to the laser dye (C545T) for
higher energy) and dimer states (with longer-lived emission, radiative decay. A decreased ASE threshold of 0.8 mJ cm2 was
at lower energy) (Fig. 16d). NIR-TADF OLED devices were fabri- demonstrated in this three-component blend, compared with
cated. The OLED architecture, including the schematic and the sample without ACRXTN (262) with a value of 1.2 mJ cm2.
energy-level diagram, is shown in Fig. 16e. The device with Unlike the OLED device without ACRXTN (262), the efficiency
doping concentration of 6 wt% BDFC-2 (259) exhibited a maxi- (maximum EQE of over 10%) increased significantly by adding
mum external quantum efficiency (EQE) approaching 10% with TADF molecules. More importantly, the device with ACRXTN
EL peak at 721 nm (Fig. 16f and g). This outstanding EQE value is revealed the excellent efficiency stability with low EQE roll-off.
well above the theoretical upper limit for conventional fluores- The estimated threshold current density for lasing collapsed
cent OLEDs. A clear narrowed spontaneous emission was from ca. 2500 A cm2 to ca. 200 A cm2 in the device with triplet
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observed in the 6 wt% BDFC-2 (259) blended sample at high sensitizer, indicating the attractive application of this method
pumping intensity (Fig. 16h). The ASE threshold was 7 mJ cm2, towards OSLDs.
and FWHM of ASE spectrum was found to drop to ca. 10 nm Recently, Lai et al. presented a novel concept by comprising
(Fig. 16i). With increasing the BDFC-2 (259) concentration up to iridium complexes as triplet sensitizers and a fluorescent
10 wt%, the ASE thresholds quickly increased, mainly due to the conjugated polymer (F8BT) as gain medium to construct tri-
concomitant decrease of PLQY values in this process (Fig. 16j). plet–singlet guest–host gain systems for light amplification.364
By appending acetylacetone borondifluoride or carboxylate Fig. 17a shows the proposed FRET diagram from a phosphor-
in the meso position of boron difluoride curcuminoid, another escent sensitizer to a laser fluorophor. The selected three iridium
two different boron difluoride curcuminoid derivatives, named complexes were named as (Dfpypy)2Ir(pic) (263), (Dfpypy)2Ir(dpm)
as BDFC-3 (appended acetylacetone borondifluoride in the meso (264) and (Dfpypy)2Ir(acac) (265) (as shown in Scheme 22). The PL
position, 260) and BDFC-4 (appended carboxylate in the meso spectrum of (Dfpypy)2Ir(pic) (263) overlapped well with the
position, 261), were designed and synthesized.43 The chemical absorption spectrum of F8BT, indicating the expected efficient
structures are depicted at Scheme 21. The two branched difluoride energy transfer from (Dfpypy)2Ir(pic) (263) to F8BT (Fig. 17b). Note
curcuminoid compound (BDFC-3, 260) exhibited bathochromic- that, in the blended systems possessing a phosphor as a host and
shifted NIR emission exceeding 800 nm while keep high NIR PL a fluorophore as a guest, the energy transfer processes were Dexter
property. A maximum EQE of 5.1% was achieved in NIR TADF transfer in most cases,365,366 occurring at short distances (typically
OLEDs, with emission peak above 760 nm. ASE with thresholds within 1 nm). However, the long aryl-flexible chains (ca. 1.1 nm) in
lower than 100 mJ cm2 were demonstrated in the doped films, iridium complexes played important roles to eliminate the
keeping ASE spectral region between 801 nm and 860 nm. These exchange interactions by the wavefunction overlaps of electron
studies represented important advances in NIR OLEDs and clouds between iridium complexes and F8BT (Fig. 17d). From a
demonstrated the possibility of TADF emitters as gain media series of measurements, including PIA spectroscopy, PL excitation
with broad spectral range for photonic and telecommunication (PLE) spectra, and fluorescence transients (Fig. 17c), the direct
applications. triplet–singlet energy transfer process was confirmed and Dexter
Another strategy, i.e., adding ‘‘triplet sensitizer’’ into the energy transfer was forbidden in these blended systems.
fluorophore, is widely used to utilize the triplet excitons in Successful light amplification were demonstrated with lower
OLED field. The management of triplet energy could be ASE threshold and much better lasing performance for the
achieved by the conversion from triplet excitons to singlet resulting triplet–singlet guest–host system compared with F8BT
excitons through energy transfer via FRET, which was firstly sample without triplet sensitizers. The lowest ASE threshold of
proved by Baldo and Forrest in 2000.147 Fluorescent OLEDs 7.1 mJ cm2 was recorded for (Dfpypy)2Ir(pic) blended sample
based on a triplet sensitizer (a phosphor or TADF) and a (263) with 90% F8BT fraction, which was three-fold lower than
conventional fluorescent emitter were reported recently.359–363 that of F8BT itself (Fig. 17e and f). Similar phenomena were
The achievement of the ‘‘triplet sensitizers’’ in constructing observed in blended films with (Dfpypy)2Ir(dpm) (264) and
efficient fluorescent OLEDs also suggested their potentials for (Dfpypy)2Ir(acac) (265) as ‘‘triplet sensitizers’’(Fig. 17g). For
light amplification. comparison, a blended system with confirmed Dexter energy
Adachi et al. demonstrated this feasible method in light transfer, containing Iridium [bis(4,6-difluoro-phenypyridinato-
amplification by using TADF molecule as ‘‘triplet sensitizer’’, N,C2 0 )picolinate] (FIrpic) (with no flexible chain) and F8BT,365
which harnessed the triplet energy for population inversion by was selected to understand the dependence of Dexter energy
converting triplet excitons to singlet excitons and subsequently transfer process on light amplification. As shown in Fig. 17g,
transferring the singlet energy to the laser dye.146 3-(9,9-Dimethyl- the FIrpic blended samples showed much higher ASE thresh-
acridin-10(9H)-yl)-9H-xanthen-9-one (ACRXTN, 262) was selected olds than F8BT itself. The narrowed spectral emission were
as the triplet sensitizer, and 2,3,6,7-tetrahydro-1,1,7,7,-tetra- only observed in FIrpic blended samples with F8BT fractions of
methyl-1H,5H,11H-10-(2-benzothiazolyl)quinolizino-[9,9a,1gh]- 85%, 90% and 95%, while no ASE was recorded for FIrpic
coumarin (C545T) was used as the laser dye. The host material blended samples with F8BT fraction less than 85%. The results
was CBP. The PL emission of the triplet blended film fitted well proved that the triplet–triplet annihilation in Dexter energy
with the emission of C545T:CBP co-deposited film, indicating transfer provided exciton quenching, and was adverse to light
that the triplet sensitizer (ACRXTN, 262) just acted as a medium amplification. At the same time, the fluorescent OLEDs with

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Fig. 17 (a) The proposed FRETdiagram from a phosphorescent sensitizer to a laser fluorophor. (b) Absorbance and PL spectra of (Dfpypy)2Ir(pic) and
F8BT in neat films. (c) PL decay curves of (Dfpypy)2Ir(pic) blended samples in film monitored in F8BT emission. (d) The view of molecular simulation model
of (Dfpypy)2Ir(pic) by DFT calculation. (e) Output intensity vs. pump energy for (Dfpypy)2Ir(pic) blended film with 90% F8BT. (f) Emission spectra of
(Dfpypy)2Ir(pic) blended film with 90% F8BT at different pump energies. Inset: FWHM as a function of pump energy in F8BT (hollow circle) and
(Dfpypy)2Ir(pic) blended film with 90% F8BT (solid circle). (g) Dependence of ASE threshold on F8BT fraction in (Dfpypy)2Ir(dpm) blended samples,
(Dfpypy)2Ir(acac) blended samples, PFO blended samples and FIrpic blended samples. (h) The current efficiency and EQE as a function of driving voltage
in OLED devices. (i) Input–output characteristics for a 1D DFB laser with covered (Dfpypy)2Ir(pic) blended film with 90% F8BT fraction, compared with that
covered with F8BT neat film. (j) Top panel: The tunable lasing spectra (from varying the grating periods) monitored from 1D DFB laser devices with
covered (Dfpypy)2Ir(pic) blended film with 90% F8BT fraction. Bottom panel: corresponding threshold variation of the output lasing wavelength for the 1D
DFB lasers. Reproduced with permission from ref. 364. Copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Scheme 22 The triplet sensitizers.

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‘‘triplet sensitizers’’ demonstrated with enhanced electro- Fluorescent proteins represent a series of biologic fluoro-
luminescent performance relative to those without ‘‘triplet phores, whose fluorescence phenomenon can be traced back to
sensitizer’’ (Fig. 17h). By integrating DFB into the blended film, 1962.381 The fluorescent proteins also find potential applica-
a very low lasing threshold of 1.86 mJ cm2 (0.37 kW cm2) was tion as laser gain media. Gather and Yun firstly observed the
manifested for (Dfpypy)2Ir(pic) blended film (263) with lasing action in a living system.20 The gain medium, which was
90% F8BT fraction. For comparison, the DFB laser with F8BT composed of a single mammalian cell with a diameter of
as gain medium recorded a much higher lasing threshold of 15 mm, transfected with a mutant form of GFP. Lasing was
8.66 mJ cm2 (1.73 kW cm2) at 566.1 nm (Fig. 17i). A ca. 30 nm recorded by placing the cell suspension in a DBR resonator. The
tunable lasing spectral window from 561 to 590 nm was operational lasing threshold was around 1 nJ per pulse with
enabled in the blended film by varying the grating periods tunable lasing wavelength region of 516–520 nm. The cells
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from 320 to 360 nm (Fig. 17j). The work suggests a general and remained alive under lasing excitation, providing great
effective methodology to utilize both triplet and singlet excitons potential of fluorescent proteins for biological imaging in the
for the contribution of light amplification, accompanying with future.382
excellent electroluminescent performance, providing an alter- Deoxyribonucleic acid (DNA) biopolymers doped with fluoro-
native route for electrically pumped OSLs. phores have been previously demonstrated as efficient lumi-
nescent polymers. ASE were recorded in double-layer systems,
3.4 Others consisting of a biopolymer based matrix loaded with organic
Perovskites have emerged as promising candidates for next- dyes and photochromic polymers.383,384 The lasing action was
generation solar cell materials due to their tunable bandgaps, achieved via DFB configuration in photochromic polymers. The
low-temperature processabilities, low recombination rates, and exponential gain coefficient was over 10 cm1. The results
long electron–hole diffusion lengths.367 The archetypical semi- showed that low threshold could be realized by the utilization
conductors with nearly 100% defect free and crystalline films of of suitable surfactant in the DNA biopolymer system to form an
perovskites yielded solar cells with over 20% efficiency, rivaling efficient energy transfer system. Together with the enhanced
the performance of industry-standard silicon, due to the long- fluorescence in DNA, this strategy could further endow the
range charge transport and efficient charge collection.368,369 biopolymer gain media with promising lasing properties.
Definitive strides have also been made by perovskites as
promising light-emitting materials in applications of LEDs,370,371 3.5 Summary
and tunable ASE and lasing.94,372 In this section, we have comprehensively summarized the
Strictly speaking, perovskites are inorganic materials; never- recent advances in the field of organic gain media, including
theless, some of their qualities are similar to organic molecules organic dyes, fluorescent semiconductor emitters, triplet gain
and can be conveniently incorporated into organic opto- media, biological materials, etc. fluorescent semiconductor
electronic devices. The rapid advances in perovskite LEDs and emitters constitute the vast majority of gain media. Promising
lasers, including materials development, device fabrication, optical properties including low ASE/lasing thresholds have
operational stability, have been comprehensively reviewed by been demonstrated based on some specific building blocks,
Veldhuis et al.373 Here we emphasize that perovskites are such as fluorene units, ladder-type (p-phenylene)s, p-phenylene
important gain candidates for electrically pumped lasers, vinylenes, etc. However, there is by far no general principle
mainly due to their high charge carrier mobilities and large available to tell whether a particular organic material is suitable
crystalline domains that resulted from their crystalline nature as organic gain media for lasing applications. It is still highly
in perovskite films,374,375 low thresholds (ASE threshold of desirable yet greatly challenging to develop effective strategies
10 mJ cm2 for MeNH3PbI3 perovskite),372 and broadly tunable to explore robust gain media for OSSLs, especially for electri-
emission (almost the entire visible spectrum).376 Recently, the cally pumped OSLs.
perovskite nanowire lasers94,95 and perovskite WGM nanolasers Essentially, stimulated emission is based on the construc-
were also reported.377–379 tion of quasi four-level lasing system. The fundamental mecha-
Recently, some new types of organic materials are used in nism for stimulated emission could be studied by theoretical
the field of lasers, e.g., liquid crystal materials with high degree calculation.244,245,305 The vibrational levels of the electronic
of self-arrangement.81,380 Liquid crystals represent a kind of ground states are simulated to get insights into ASE phenom-
soft matter that combines fluid-like behavior with crystalline- ena. The low-frequency modes result in uncontinuous energy
like solid ordering. Liquid lasers possess many remarkable levels, corresponding to distinct sideband, which is disadvan-
features, such as large coherence area, wideband tunability, tageous to the formation of the quasi four-level energy system.
and multidirectional emission under some conditions. Most Enhanced vibration strength and vibronic peak intensity of
importantly, they have the potential of combining large output high-frequency modes benefit for population inversion and
power with miniature laser oscillation dimension, even these the decreased ASE threshold, resulted from the distinct quasi
two characteristics are contradictory in most cases. Addition- four-level energy system. The ratio of high-frequency modes to
ally, they have diverse potential applications such as large-area low-frequency modes would provide a new insight into organic
holographic laser displays and miniature medical diagnostic gain media. Another parameter to assess the gain media is
tools.81 radiative decay rate (kr), which is calculated from PLQY and

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transient lifetime.248,249 Usually, high kr in the gain media is higher than 30% in OLED devices have been reported in recent
expected to achieve low ASE threshold, which is beneficial for years.389,390 The challenge of OLED as laser diode structure
the fast four-level transition cycle in lasing. However, this is that the excitons would suffer from many paths for non-
method can hardly explain why no ASE phenomenon exists in radiative transition under the condition of high current
some highly efficient fluorescent emitters. injection.391 The excitons might be annihilated in the high
Gain coefficient is another important parameter to evaluate electric field by polaron interactions, and can diffuse and
gain media. As we summarized, VSL method has been widely quench in the presence of nearby metal electrodes. Also the
used to evaluate the optical gains of organic semiconductors. OLED structure gives high potential for absorbing the emitted
In most cases, net gains are around 50 cm1 for fluorescent photons by the opaque metal electrode layer. The efficiency
emitters. Over 90 cm1 net gain values have been achieved in roll-off is observed in the OLEDs at high excitation density,
ladder-type emitters.48,235,236 High gain would be much helpful contributed by all of these factors.392,393 Estimating the excita-
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to compensate the optical losses in the integrated semiconductor tion density to reach the lasing threshold, injected current
devices. As a result, gain media holding high gain coefficients are density as high as 1 kA cm2 is required.35,391 However, the
extremely desired for realizing high-performance organic lasers. operational current density of most OLEDs is still far below
For the application in electrically pumped organic lasers, 1 A cm2. Due to the relatively low conductivity of organic
there are several critical demands required for the gain media, semiconductors, OLED devices generate strong Joule self-
i.e., very low threshold that means low current density is needed heating under high current densities, which would lead to
under electrically pumped conditions; high thermal/optical stabi- thermal breakdown of devices. The self-heating as well as the
lity to ensure long-time device operation; high optical gain efficiency roll-off could be relieved by using high thermal
coefficient that compensates the optical losses in electrical pump- conductive substrates, such as sapphire,394 or patterning of the
ing device; high PLQY; high charge carrier mobility, etc. but it still OLEDs.393,395 Recently, Solwik et al. introduced a new OLED
remains rather challenging to simultaneously achieve all of the concept with restructured layer sequence to concentrate and
requirements in one emitter. The greatest difficulty is to simulta- maximize the current flow in the metal-free emission area.396
neously achieve low threshold, high PLQY and high charge carrier Thus, the parasitic absorption by the metal electrodes is
mobility in organic gain media, which not only exists for organic avoided and the drastically reduced dissipation power is
amorphous films, but also for organic crystals. Typically, ambi- achieved. High current density over 1 kA cm2 is reached,
polar OLETs based on organic single crystals and thin films and the operation voltage up to 75 V is achieved with Alq3:DCM
exhibit high PLQYs (410%) but quite low carrier mobilities as the emitter. However, the potentials of this new concept still
o103 cm2 V1 s1.34,385 In contrast, high mobility ambipolar needs to be further investigated in resonator geometries, such
OLETs based on organic single crystals and thin films as microcavities, and the feasibility of this device structure for
(41 cm2 V1 s1) are able to reach current density over electrically driven OSLs remains yet to be explored.
1 kA cm2, but they generally show very low PLQYs.386,387 Another widely studied device for lighting is OLETs, which
New molecular design strategies are required to address this combine the capability of light generation and the high charge
challenge. The development of efficient triplet gain media and carrier mobility of a field-effect transistor in a single device.385,397
triplet harvesters may be helpful for achieving electrically Compared with OLED structure, the OLET geometry holds a
pumped organic lasers, since 75% triplet excitons could be variety of advantages, such as higher channel conductivity, planar
utilized for stimulated emission theoretically. architecture that allows micrometer-size emission, minimized
exciton losses, gate-tunable emission-zone positions and charge-
carrier balance, and even higher EQE.398
4. The challenges towards electrically The conductivity of the ambipolar OLET is several orders of
pumping organic lasers magnitudes higher than that of OLED. Therefore, the signifi-
cantly enhanced population of the injected charge carriers
Since the first OSLs discovered by Friend and Heeger in occur in the active channel for recombination. Indeed, the
1996,17,18 intense efforts have been made in this field, including current density values of OLET have reached kA cm2 order
gain media design, the high-quality feedback structures, the of magnitude.386,399–401 Extremely high current density of
encapsulation technologies, CW lasers, etc. Although optically 128 kA cm2 was reported in thin films of copper phthalo-
pumped OSLs have been dramatically improved in the last cyanine.400 The accumulated holes and electrons are balanced
twenty years, it is still a challenge to develop electrically driven during operation in ambipolar regime, and the recombination
OSLs. In 2019, Adachi’s group claimed the achievement of zone is driven in the transistor channel, separated from the
electrically pumped OSLs.23 In the following section, we will metal electrodes. The distance between the recombination zone
discuss the challenges and highlight breakthroughs in the recent and the metal electrodes is more than 300 nm, even in the
efforts in electrically-driven OSLs. carrier imbalance condition. It means the diffusion of the
formed fluorescence excitons to the metal electrode will not
4.1 Device design and the effect of metal electrode happen. Therefore, the exciton annihilation resulted from the
OLED is by far a state-of-the-art technology, and active matrix electronic device structure can be resolved. Moreover, OLETs
OLED displays are entering the lighting market.388 The EQE hold the capabilities of operating at high current density while

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maintaining the luminescence EQE, indicating their minimum In order to eliminate the influence of triplet excitons, the
exciton loss paths.398,402 general strategy is to remove the triplet excitons by adding triplet
quenchers, e.g., small molecule triplet scavengers (e.g., cyclo-
4.2 The impact of dipoles and charge absorption octatetraene412 and anthracene derivatives),145 and metal nano-
particles embedded in the gain media.413 Alternatively, triplet gain
Carriers (dipoles) themselves are critical sources of loss for
media and triplet sensitizers may provide an alternative pathway to
electrically pumped organic lasers. Because of their broad
resolve this problem, as discussed in Section 3.3.
absorption band, which could cover the emission, laser photons
could be absorbed or singlet excitons could be quenched.391 4.4 The demonstration of electrically pumped OSLs
Quantified explanation about dipole absorption is still rare. Rabe
An electrically pumped OSL has been most recently demonstrated
et al. used the spiro-bifluorene as the hole-transporting material
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in an electroluminescent device, which incorporates a mixed-order

to precisely measure the dipole absorption cross-sections. They
DFB grating into an OLED device with BSBCz (124) as gain
found that the value of dipole absorption cross-section was very
medium.23 As introduced in Section [Link], BSBCz (124) is one
low: from 560 nm to 660 nm, s o 2.6  1018 cm2.403 The results
of the best candidates for electrically pumped OSLs due to its nearly
demonstrated the interactions between dipoles were mainly
100% PLQY, extremely weak production of triplet excitons, and
dipole-exciton quenching rather than direct absorption of
negligible triplet–triplet absorption.21,248,251 Mixed-order DFB
photons.404 The existence of electrodes and dipoles lead to low
grating was selected with an alternation of the first- and second-
mobilities of organic semiconductors. As for the amorphous
order Bragg scatting regions to provide a sufficient vertical
organic semiconductors, the carrier mobility is approximately
out-coupling of the laser radiation. The architecture of OSLD is
within the range of 105–102 cm2 V1 s1, which means that a
presented in Fig. 18a. The engraved DFB gratings on SiO2 layer,
large number of dipoles must be removed in order to obtain
which was sputtered on indium tin oxide (ITO), were fabricated
high current density. The influence of dipoles can be minimized
with electron beam lithography and reactive ion etching. The
by using OLET devices, in which the accumulated holes and
fabricated OSLD held an inverted OLED structure with ITO
electrons are recombined in a long distance.
(100 nm)/20 wt% Cs:BSBCz (60 nm)/BSBCz (124) (150 nm)/MoO3
Another serious optical loss combined with electrical pumping
(10 nm)/Ag (10 nm)/Al (90 nm). MoO3 layer was used for hole
is the charge-induced absorption (polaron absorption) (see
injection, and doping BSBCz with Cs promoted electron injection
Section 2.2). The absorption from charge excited states could
into the emission layer. The ZEQE–current density of an OLED and
prejudice the stimulated emission and gain, due to the long
OSLD under pulsed condition (voltage pulse width: 400 ns;
lifetimes of the charges benefitting for significant population
repetition rate: 1 kHz) at room temperature is shown in Fig. 18b.
build-up, and the region overlapping of the charge-induced
The efficiency roll-off was suppressed in the OSLD under pulse
absorption and the stimulated emission.32,39,405 This process
operation, and a maximum value of 2.9% of ZEQE was achieved with
can be neglected in a short-pulse optically pumped device, but
pulse current density increasing above 200 A cm2 (Fig. 18b). Related
in an electrically-driven device, the carrier-induced absorption
to the thermal degradation, ZEQE of the OSLD device decreased
would make it much less effective. Tessler estimated 1000 times
rapidly when the pulse current density was above 2.2 kA cm2.
as many polarons as singlets for a material with a mobility of
The narrowed EL spectra of OSLD were recorded by increasing
104 cm2 V1 s1.406 In the well-designed experiments with either
current density (Fig. 18c and d). A definite threshold from the
optical or electrical excitation, the study of charge absorption
slope efficiency of the lasing output was determined at a current
shows that the polaron absorption with a typically broad region is
of 600 A cm2. Meanwhile, strong spectral narrowing with FWHM
a critical issue for lasing.407–409
less than 0.2 nm occurred at 480.3 nm, suggesting the emergence
of lasing (Fig. 18c–e), when the current density increased up to
4.3 Effects of triplet excitons 600 A cm2. The dependence of output power on current density
The greatest challenge to realize organic laser diodes is prob- is depicted in Fig. 18f. A maximum output energy of 5.0 mW was
ably the existence of triplet excitons. Due to the spin statistics, achieved with current density at 3.3 kA cm2. As we emphasized
the 75% formed excitons are triplets.357,358 The long-lived and summarized, three aspects significantly contribute to the
triplet excitons result in the quenching of light amplification achievement of OSLD, i.e., the separation of the lasing output
through triplet–triplet absorption and the reduction of the S1 wavelength region from triplet–triplet absorption and charge
population via STA resulting from the overlapping of the broad absorption; the low lasing threshold which allows the relatively
triplet–triplet absorption band and the singlet fluorescence low current-injection for lasing observation in BSBCz (124) gain
emission band.32 The problem caused by triplet excitons can medium; and the optimized DFB architecture. Nevertheless, the
be studied with long pulse optical excitation. The experiments manufacturing success rate of OSLD devices claimed by the
by Giebink and Lehnhardt showed that, lasing was completely authors was only 5% (in 500 devices). And also the output energy
inhibited within tens of nanoseconds after the optical pumping and operational lifetime still need to be optimized.
began in the guest–host systems (Alq3:DCM and F8BT:MEH-
PPV), suggesting that the triplet-singlet annihilation and triplet– 4.5 Summary
triplet absorption were the dominant factors to optical losses in Since the first OSL was realized two decades ago, the researches
the electrically-driven devices.410,411 and the attempts to realize electrically pumped organic lasers

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Fig. 18 (a) Schematic representation of OSLD. (b) ZEQE–current (Z–J) characteristics of the OLED and OSLD under pulse condition. (c) Output intensity
and FWHM in OSLD device as a function of the current and current density. (d) Emission spectra of the OSLD at different current densities. (e) Emission
spectra around the lasing threshold. (f) Dependence of output power on injected current and current density. Reproduced with permission from ref. 23.
Copyright 2019 Japan Society of Applied Physics.

have attracted extensive interest. With the aim to attempt MEH-PPV (238), and so on. Great achievements have been made
electrically pumped organic lasers, several aspects should be in the field of organic gain media, including high PLQYs, low
taken into consideration, i.e., it is necessary to optimize the ASE/lasing thresholds, good thermal/optical stabilities, high gain
device structure, to reduce the electrode absorption, to reduce values, and improved charge carrier mobilities. The optically
(or recycle) the triplet state, to select the appropriate feedback pumped OSSLs have shown a number of applications, e.g.,
structure and the gain media with outstanding stability, and to on-chip spectroscopy, information and communication techno-
achieve low lasing threshold, high gain, high carrier mobility logy, biomedicine, and low-cost sensing.
and so on. Although the first optically pumped OSL was reported in
1996, the electrically-pumped OLSD was not realized until 2019.
Despite prominent device structures and the potential feasibili-
5. Conclusion and outlook ties for direct integration on flexible substrates, efficient and
robust organic gain media for achieving electrically driven OSLs
To conclude, we have comprehensively summarized the are still extremely scarce. For the development of OSLDs, the
research in the field of organic solid-state gain media. A variety gain media should possess the important characteristics,
of gain materials have been reported, including organic dyes, i.e., low lasing threshold, high gain, excellent stability, and high
fluorescent semiconductor emitters, triplet gain media, and charge carrier mobility. All these issues require a more thorough
biological materials, covering a wide spectrum from UV to understanding of the roles of the chemical structures on the optical
NIR. Some gain media are already commercial available, and electrical properties. Some design strategies, such as incorpo-
including some laser dyes, i.e. TDAF-1 (79), PFO (203), F8BT (225), rating specific functional groups (e.g., ladder-type (p-phenylene)s

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and bis-styrylbenzene), introducing branched flexible chains, MPP Multi-photon pumped

constructing triplet gain media and triplet harvesters, may be PS Polystyrene
beneficial to the development of robust organic gain media for UV Ultraviolet
OSLDs. We hope that in the future, intense efforts will be paid to DCM 4-(Dicyanomethylene)-2-methyl-6-(4-
explore various successful ways to realize electrically pumped dimethylaminostryl)-4H-pyran
organic lasers and promote their practical application, inspired FRET Förster energy transfer
by the recent advancements. CBP 4,4 0 -Bis(9-carbazolyl)-2,2 0 -biphenyl
FWHM Full width at half maximum
TPCO Thiophene-phenylene co-oligomer
Abbreviations nPV Oligophenylene vinylene
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DSB trans-Distyrylbenzene
OLED Organic light-emitting diode PIA Photoinduced absorption
OSC Organic solar cell ESIPT Excited-state intramolecular proton transfer
OTFT Organic thin-film transistors D–p–A Donor–p–acceptor
OSSL Organic solid-state laser 2D Two dimensional
OSL Organic semiconductor laser tASE
1/2 ASE photostability half-lifetimes
PMMA Polymethylmethacrylate TDAF Ter(9,9-diarylfluorene)
Alq3 Tris(8-quinolinolato) aluminum(III) COPV Carbon-bridged oligo(p-phenylenevinylene)
PPV Poly(p-phenylenevinylene) LPPP Ladder-type poly(p-phenylene)
LED Light-emitting diode ICT Intramolecular charge transfer
GFP Green fluorescent protein ACQ Aggregation-caused quenching
CW Continuous-wave AIE Aggregation-induced emission
BSBCz 4,4 0 -Bis[(N-carbazole)styryl]biphenyl SAMIM Solvent assisted micromoulding
NIR Near-infrared CLC Cholesteric liquid crystal
TADF Thermally activated delayed fluorescent OD Optical density
S0 The electronic ground state HOMO Highest occupied molecular orbital
S1 The first electronic excited state DFT Density functional theory
T1 The lowest triplet excitation state BT Benzothiadiazole
ISC Intersystem crossing NTO Natural transition orbital
STA Singlet–triplet annihilation TOF Time-of-flight
sex The cross-section of the excited-state absorption F8BT Poly-(dioctylfluorene-co-benzothiadiazole)
sem The maximum cross-section of stimulated PLED Polymer-light-emitting-diode
emission EL Electroluminescence
ASE Amplified spontaneous emission IQE Internal EL quantum efficiency
VSL Variable stripe length OSLD Organic semiconductor laser diode
MeLPPP Methyl-substituted ladder-type RISC Reverse intersystem crossing
poly(paraphenylene) kRISC The rate of reverse intersystem crossing
PFO Poly(9,9-dioctylfluorene) EQE External quantum efficiency
WGM Whispering gallery mode PLE Photoluminescence excitation
DBR Distributed Bragg reflectors DNA Deoxyribonucleic acid
DFB Distributed feedback ITO Indium tin oxide
ONW Organic nanowire
1D One dimensional
ES Electrospinning Conflicts of interest
PVD Physical vapor deposition
There are no conflicts to declare.
PL Photoluminescence
TPP Two-photon-pumped
NIL Nanoimprint lithography Acknowledgements
vs. versus
MOF Metal organic framework We acknowledge financial support from the National Natural
PLQY Photoluminescence quantum yield Science Foundation of China (21835003, 91833304, 21422402,
TPA Two-photon absorption 21674050), the National Key Basic Research Program of China
GM 1050 cm4 s photon1 molecule1 (973 Program, 2014CB648300, 2017YFB0404501), the Natural
3PP Three-photon-pumped Science Foundation of Jiangsu Province (BE2019120), Program
COF Covalent organic framework for Jiangsu Specially-Appointed Professor (RK030STP15001),
OLET Organic light-emitting transistor the Six Talent Peaks Project of Jiangsu Province (TD-XCL-009),

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the 333 Project of Jiangsu Province (BRA2017402), the NUPT 21 A. S. D. Sandanayaka, T. Matsushima, F. Bencheikh,
‘‘1311 Project’’ and Scientific Foundation (NY218164, K. Yoshida, M. Inoue, T. Fujihara, K. Goushi, J.-C.
NY217169), the Leading Talent of Technological Innovation of Ribierre and C. Adachi, Sci. Adv., 2017, 3, e1602570.
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Displays, and the Priority Academic Program Development of 23 A. S. D. Sandanayaka, T. Matsushima, F. Bencheikh,
Jiangsu Higher Education Institutions (PAPD, YX030003). S. Terakawa, W. J. Potscavage, C. Qin, T. Fujihara,
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