Hindawi Publishing Corporation

Journal of Nanomaterials
Volume 2013, Article ID 196521, 9 pages
http://dx.doi.org/10.1155/2013/196521

Review Article
ZnO-Based Transparent Conductive Thin Films:
Doping, Performance, and Processing

Yanli Liu, Yufang Li, and Haibo Zeng

College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China

Correspondence should be addressed to Haibo Zeng; [email protected]

Received 21 December 2012; Accepted 2 February 2013

Academic Editor: Xijin Xu

Copyright © 2013 Yanli Liu et al. This is an open access article distributed under the Creative Commons Attribution License, which
permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

ZnO-based transparent conductive thin films have attracted much attention as a promising substitute material to the currently
used indium-tin-oxide thin films in transparent electrode applications. However, the detailed function of the dopants, acting
on the electrical and optical properties of ZnO-based transparent conductive thin films, is not clear yet, which has limited the
development and practical applications of ZnO transparent conductive thin films. Growth conditions such as substrate type, growth
temperature, and ambient atmosphere all play important roles in structural, electrical, and optical properties of films. This paper
takes a panoramic view on properties of ZnO thin films and reviews the very recent works on new, efficient, low-temperature, and
high-speed deposition technologies. In addition, we highlighted the methods of producing ZnO-based transparent conductive film
on flexible substrate, one of the most promising and rapidly emerging research areas. As optimum-processing-parameter conditions
are being obtained and their influencing mechanism is becoming clear, we can see that there will be a promising future for ZnO-
based transparent conductive films.

1. Introduction [12]. Nevertheless, many problems associated with substi-

tuting ZnO-based TCO films for ITO still exist. Figure 1
Transparent conductive oxides (TCOs), capable of transport- visually describes structural, optical, electrical properties of
ing electrical charge and transmitting visible photon, are nec- zinc oxide. In LCD applications, stability in various envi-
essary for use as transparent electrodes in flat panel displays ronments has to be improved when films become thinner.
such as liquid crystal displays (LCDs), plasma display panels, [13]. In OLEDs applications, preparation technology of low-
electronic paper displays, light-emitting-diodes (LEDs) [1], temperature and plasma damage-free films on flexible sub-
and touch panels [2, 3]. A carrier concentration on the order strate have to be optimized.
of 1020 cm−3 or higher and a band-gap energy above 3 eV are For the design and realization of ZnO-based devices, one
usually required for high conductivity and transmittance [4]. of the most significant issues is doping, which necessarily
Various TCO thin films consisting of impurity-doped SnO2 involves the heavy doping with trivalent elements from the
(SnO2 :Sb and SnO2 :F), In2 O3 (In2 O3 :Sn, or ITO), and ZnO group III (Al, Ga, In). Minami summed up the resistivity
(ZnO:Al and ZnO:Ga) films have been researched so far in of impurity-doped binary compound TCO films reported
this field [5, 6]. Among them, tin-doped indium-oxide (ITO) among thirty years and found that the obtained minimum
is the one in practical use [7, 8]. However, with the market resistivity of impurity-doped ZnO films is still decreasing,
of ITO expanding, a stable supply may be difficult to ensure while SnO2 and In2 O3 films have essentially remained
because of the high cost and scarcity of indium [9, 10]. unchanged [4]. Such trend indicates the possible significant
Fortunately, ZnO thin films are a promising alternative promotion of ZnO-based TCO films.
to the commonly used ITO, which are low cost, nontoxic, ZnO films have been prepared through various kinds of
highly durable against hydrogen plasma compared to ITO methods [14, 15] and each of them has its own advantages
[11]. Besides, it has a more proper work function for the and drawbacks. In this paper, sputtering, chemical vapor
transparent contact cathode electrodes of transparent OLEDs deposition (CVD), and pulsed laser deposition (PLD) are
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
2 Journal of Nanomaterials

Table 1: Properties of ZnO films with different dopants prepared by PLD.

Dopants Optimum content in target (%) Thickness (nm) Resistivity (Ω⋅cm) Transmittance (%) Reference
Al 2 500 4.5 × 10−4 88% [35]
Ga 5 200 8.12 × 10−4 >90% [22]
In 40 >1000 4.02 × 10−4 >85% [36]
F 2 200 4.83 × 10−4 >90% [25]
Si 2 ∼150 6.2 × 10−4 ∼80% [37]

Photons and all films were fabricated under optimum-processing-

parameter conditions to achieve lower resistivity and higher
transmittance.

Electrons Conductivity 2.1. Group III Elements Doping. The ionic radius of Al3+ is
0.54 Å, which is smaller than that of Zn2+ (0.74 Å). So the
Al3+ can occupy the place of Zn2+ in lattice easily, leading
to a reduction of the lattice parameter. In comparison with
Al3+ , Ga3+ has similar ionic radius to Zn2+ ions, which
Transmittance minimizes the ZnO lattice deformations even at higher
doping concentrations [18, 21]. This may explain the reason
Figure 1: A picture visually describing structural, optical, electrical why the best electrical properties of ZnO-based films are
properties of zinc oxide. Revised from [38]. Copyright 2012, Amer- observed in Ga-doped ZnO thin films [22].
ican Chemistry Society. The conductive property of ZnO thin films is primarily
dominated by electrons generated by oxygen vacancies and
charge donation. Geng and his coworkers [23] investigated
the effect of Al concentration on the electrical properties
described in details, since ZnO-based TCO films based on of ZnO:Al thin films grown on Si(100) substrate by atomic
these methods can get the highest quality. The first two layer deposition. The crystallinity of the film degenerated
methods allowing large area deposition make them the most while resistivity was found to decrease with increasing Al
advanced and efficient deposition techniques for ZnO film. doping concentration (9.36 × 10−4 Ω⋅cm at maximal doping
Even if the films are prepared by the same method, thickness, concentration 2.7 at.%).
substrate, growth temperature, dopant, and their content Al is incorporated beyond the thermodynamic solubility
will play a crucial role in structural, electrical, and optical limit, even within the limit, the relationship between Al
properties of films. Therefore, whether we can optimize the content and resistivity is not monotonous [24]. The resistivity
fabrication of high-quality doped zinc oxide thin films at low of the AZO film decreased with an increase of the Al content
cost determines the future of ZnO-based TCO films. The up to 7 at.% and then increased at a high Al content of
structural, optical, electrical properties of doped ZnO are 8 at.% (Figure 2). At high Al concentration, Al exists in
summarized with particular emphasis on influence of doping the form of Al2 O3 , resulting in deleterious effects to the
on the properties of ZnO thin films, which are responsible for electrical properties of the films. According to many other
the properties of films. In addition, recent progress on film reports, the relationship between conduction characteristics
preparation is introduced. and concentration of other elements doping is similar to that
of Al doping.
Fluorine is another dopant to improve the conductivity
2. Different Dopant Elements of the films [19]. Unlike aluminum and other elements in
group III, effect of fluorine in ZnO is less discussed. Fluorine
Several elements are doped in ZnO films, such as B [16, 17],
incorporates into the lattice by substituting oxygen atoms due
Al, Ga, In (from group III elements) [18], F (from group VII
element) [19], and so forth. Among them the most studied are to the comparability of ionic radius (F-: 1.17 Å, O2− : 1.22 Å).
Al-doped ZnO and Ga-doped ZnO. In Section 2, we focus on Actually, ZnO:F films have good combination properties.
recent research on Al, Ga doping, and codoping. The position Cao et al. [25] prepared FZO films via pulsed laser deposition,
of the dopant atoms and solubility limit can be related to the getting a resistivity of 4.8 × 10−4 Ω⋅cm, carrier concentration
film preparation methods. For example, in the spray pyrolysis of 5.43 × 1020 cm−3 , and Hall mobility of 23.8 cm2 V−1 s−1 ,
technique, In and Ga is more efficient than Al since the Al respectively. The average optical transmittance in the entire
atoms are preferably at interstitial sites of the ZnO lattice and visible wavelength region was higher than 90%.
decrease the mobility [20].
Some reported electrical and optical properties of ZnO 2.2. Codoping. Difference of radii between doping ions and
films with different dopants prepared by PLD are summarized Zn2+ ions or O2− ions will result in variation of lattice
in Table 1. Each dopant was at its appropriate content constant and degeneration of crystallinity in zinc oxide.
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Journal of Nanomaterials 3

transmission, there is the potential to achieve both through

improving the microstructure of the films and increasing the
carrier mobility. Obviously, it is important to deconstruct the
10−1 influence of intentionally introduced impurities on electrical
Resistivity (Ω·cm)

properties of ZnO to realize any type of device applications.

3.2. Concentration-Dependent Optical Gap Shift. The optical-

gap shift is contributed by two competing effects, Burstein-
Moss (B-M) band-filling effect and band-gap narrowing
10−2 (BGN) effect (Figure 4). The well-known optical band-gap
(𝐸𝑔 op ) blue shift [32, 33] in heavily doped semiconductors
occurs because the lower states in the conduction band
0 2 4 6 8 10 are blocked. Conversely, band-gap narrowing is caused by
Al contents (at %) exchange interactions in the free-electron gas and elec-
trostatic interactions between free electrons and ionized
Figure 2: Resistivity as a function of Al contents from 0 to 8.4 at.% impurities. The fact that BGN effect is largely compensated
achieved by Hall measurement at room temperature [24]. Copyright by B-M effect and temperature or doping are two influence
2011, The Electrochemical Society. factors in the 𝐸𝑔 op behavior makes it difficult to separate these
two effects by means of current experiments.
Lu and coworkers [34] found that 𝐸𝑔 op , evaluated from
This issue could be partially resolved by codoping, which optical absorption spectra, was mainly related to the carrier
has led to an upsurge study in recent years [26–28]. High concentrations and so intrinsic to Al content. The optical
quality of films deposited by Shin et al. has confirmed the gap increased with the electron concentration when 𝑛𝑒 ≤
advantages of codoping [29]. As Ga concentration increased 4.2 × 1019 cm−3 , which could be fully interpreted by a
from 0.5 to 2 at%, the peak intensity of the (0002) plane and modified Burstein-Moss effect; A sudden decrease in energy
carrier concentration for Mg and Ga codoped ZnO thin films gap occurred at 5.4−8.4 × 1019 cm−3 , consistent with the Mott
(MGZO) increase compared with that of pure ZnO and Mg- criterion for a SMT. Above the critical values, the band gap
doped ZnO thin films, as shown in Figure 3 [29], implying the increased again (see Figure 5). Further exploration in this
substitution of Ga3+ ions with Zn2+ ions (ionic radius of Ga3+ , issue is needed to promote energy band engineering in ZnO-
Mg2+ , and Zn2+ is 0.062 nm, 0.057 nm, and 0.060 nm, resp.). based TCO films.
What is more, the MGZO structure was stabilized greatly in
this method. The low electrical resistivity and wide band gap
energy of MGZO thin films can be ascribed to the dopant of 4. Effect of Growth Conditions
Ga and Mg, respectively.
4.1. Preparation Methods. Among various preparation meth-
ods, pulsed laser deposition (PLD) is more appropriate for
3. Doping Concentration precise controlling of morphology and composition of the
grown materials. Park et al. and Agura et al. [22, 39] prepared
3.1. Concentration-Dependent Conductivity. Zinc oxide, as a
AZO and GZO thin films on glass substrates with a low
transparent oxide with band-gap energy of 3.37 eV [30], can
resistivity on the order of 10−5 Ω⋅cm by PLD, respectively.
satisfy the optical properties requirement of TCO without
Resistivity on the order of 10−5 Ω⋅cm is the best result for
doping. However, the carrier concentration of intrinsic ZnO
ZnO films ever reported and there is a general agreement
is roughly 106 cm−3 at room temperature [31], which is much on the better performances in terms of conductivity for
lower than that of TCO films for practical application. In ZnO films grown by PLD than those obtained via other
general, an introduction of dopants affords an increase in techniques. However, the problems of stability and cost most
carrier concentration, that is, probably constrained the future development of this method
𝑛0 ⋅ 𝑝0 = 𝑛𝑖2 , (1) in manufacture on a large scale.
Magnetron sputtering is one of the deposition methods
where 𝑛0 is the concentration of conductive electrons, 𝑝0 in practical use. It was found that the lowest resistivity
is the concentration of hole, and 𝑛𝑖 is s intrinsic carrier prepared by this method is still on the order of 10−4 Ω⋅cm,
concentration in ZnO. Doping directly affects carrier con- higher than the resistivities obtain by PLD several years
centration and influences conductivity in turn. Although ago. Chemical-vapor-deposition is another industrially most
introduced impurities are necessary, but not more is better. advanced deposition techniques. How to increase growth
Its concentration must have a limitation; otherwise, very rate and applied to continuous, in-line manufacturing is a
high doping levels will result in high free carrier absorption, vital issue. Illiberi et al. deposited ZnO:Al films on glass
high plasma resonance reflectivity, and low visible wavelength by an industrially scalable metal organic chemical-vapor-
transparency (Figure 2). Even though it seems difficult to deposition (MOCVD) technique at atmospheric pressure
improve electrical conduction while maintaining the optical [40, 41]. In view of an industrial up-scale, the vaporized
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
4 Journal of Nanomaterials

1021

Carrier concentration (cm−3 )

Intensity (a.u.)

1019

1017

1015
32 33 34 35 36 Pure ZnO 0 0.5 1 2
2𝜃(∘ ) Ga concentration (at %)
Pure ZnO Mg0.05 Ga0.01 Zn0.94 O
Mg0.05 Zn0.95 O × 5 Mg0.05 Ga0.02 Zn0.93 O
Mg0.05 Ga0.005 Zn0.945 O
(a) (b)

Figure 3: XRD patterns (a) and variation of the carrier concentration (b) of the pure ZnO, MZO, and MGZO thin films deposited at different
Ga concentration [29]. Copyright 2011, American Chemistry Society.

3.8
CB CB
Band-gap shift (eV)

0.4
3.7 0.3

0.2
Band-gap energy (eV)

Δ𝐸𝐹 3.6
0.1
𝐸𝑔 op
𝐸𝑔 op BGN effect BM effect 0
3.5 1019 1020 1021
Electron concentration (cm−3 )
VB
VB
3.4
ZnO ZnO:M

Figure 4: Band-gap renormalization and Burstein-Moss (B-M) 3.3

band-filling effect contributions to the 𝐸𝑔 op .
1019 1020 1021
−3
Electron concentration (cm )
Mist CVD
precursors, that is, diethylzinc (DEZ), Tertiary-butanol (t- Magnetron sputtering
BUT), and trimethylaluminum (TMA), can be injected in
different deposition zones, where each layer is deposited. Figure 5: Band-gap energy as a function of electron concentration
in AZO [34]. Copyright 2007, American Institute of Physics.
Then, each zone installed along the same production line
continuous, realizing in-line manufacturing. Schematic of an
industrial atmospheric-pressure MOCVD system is shown in
Figure 6. A maximum growth rate was found at a deposition obtained films was a little high (minimum resistivity is 2.35 ×
temperature of 480∘ C, for which ZnO𝑥 :Al films show good
10−2 Ω⋅cm) but their results are still promising on the way
crystalline quality, high conductivity (𝑅 < 10 Ω/◻ for film
to the development of liquid-phase routes. To produce TCO
thicknesses above 1050 nm), and good transmittance (>85%
films of good quality, every step of sol-gel method, including
in the visible range).
synthesis of nanoparticles, preparation of dispersions, thin-
Sol-gel method is an attractive liquid-phase routes for
film processing, and postannealing, has to be optimized.
obtaining thin films due to its advantages of easy control
of the film composition and fabrication of a large area thin
film with low cost. Luo et al. [45] developed a versatile 4.2. Substrate Type. Up to now, transparent conductive
film-deposition process combining microwave-assisted non- films have been prepared on plenty of different substrates,
aqueous sol-gel process with dip-coating. The resistivity of such as glass, sapphire, and polymer. Polymeric substrates,
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Journal of Nanomaterials 5

Injector investigated the temperature dependence of electrical resis-

tivity and optical band gap of GZO thin films. The resistivity
of films decreases from 9.61 × 10−3 to 4.50 × 10−4 Ω⋅cm with
Exhaust

the increases of deposition temperature from 100 to 500∘ C

(Figure 8), and this can be attributed to substitutional doping
increase and the grain boundary density decrease as the
Glass growth temperature rose.
Low growth temperature is required for the flexible
substrates in OLEDs. However, the films always show poor
Heating properties at low growth temperature. This relationship does
Figure 6: Schematic of an industrial atmospheric-pressure
not mean all hope for low-temperature growth lost. In recent
MOCVD system. Films have been deposited by using one injector. years, the growth of high quality films at low temperature on
The system can be upscaled for industrial production by installing flexible substrates has attracted extensive attention owing to
multiples injectors [40]. Copyright 2011, Elsevier. the rather low cost with many unique applications [51, 52].
Clatot et al. successfully deposited Si-doped zinc oxide (SZO,
Si 3%) thin films at a relatively low temperature (≤150∘ C) by
pulsed laser deposition (PLD). The SZO films deposited on
polyethylene-terephthalate (PET) [46], polycarbonate (PC) PET substrates at 100∘ C exhibit a very promising resistivity of
[47], aspolyphthalamide (PPA) are drawing increasing atten-
9.0 × 10−4 Ω⋅cm [46]. Reference [44, 53] introduced a process
tion due to their merits of light weight, low cost, ability to
combining room-temperature PLD and direct pulsed laser
flex, curve, roll, fold small volume and promising application
recrystallization (DPLR). During DPLR, the AZO thin film
in organic light-emitting diodes (OLEDs) [48, 49].
undergoes recrystallization and growth while the underlying
Substrates nature alone may still affect microstructures
flexible substrate is retained at low temperature. Schematic of
(crystallization, morphology) and electrical properties of
DPLR technique and temperature evolution of AZO film on
films. Esmaili-Sardari et al. have a research on conductivity
different substrates carried out by multiphysics EM-HT simu-
type dependent on different substrates [50]. All films grown
lation is shown in Figures 9(a) and 9(b), respectively. Recrys-
on boron doped p-Si have n-type conductivity at low Hall
tallization and growth of films reduce internal imperfections,
Effect temperatures and p-type conductivity at high Hall
resulting in higher conductivity, Hall mobility (increases
Effect temperatures but films grown n-type substrate show n-
type behavior for the entire Hall temperatures range from 80 from 6.56 to 10.12 cm2 /Vs), and higher transmittance. It is
to 350 K, suggesting that the differences in nearly substrates also worthy to note that the merit of no damaging on the
surfaces could affect intrinsic defects and concentrations as underlying substrates makes this technology promising in
well as the ZnO (0001) surface termination. various low temperature applications.
Shin et al. prepared thin films of Ga-doped ZnO (GZO)
on glass and Al2 O3 (0001) substrates by using RF mag- 4.4. Ambient Atmosphere. In deposit technique, ablated
netron sputtering under the same processing conditions species will loss kinetic energy due to collisions with the
and found that individual grains with columnar shape are background gas molecules, resulting in different film density
clearly observed in the GZO film on the glass substrate, as and morphology. Gas pressure, especially oxygen partial
shown in Figure 7(a). However, it is difficult to distinguish pressure, has received a lot of attention [24, 25]. Gondoni et al.
individual grains in the GZO film on the Al2 O3 substrate [35] found that when the background gas (O2 ) pressure
(Figure 7(b)). The superior crystal quality of the epitaxially changed from 0.01 Pa to 10 Pa, resistivity remains the same
grown GZO films on Al2 O3 substrates compared to the and increases to a magnitude of 10−1 Ω⋅cm upon reaching
polycrystalline GZO films on glass substrates afforded better 10 Pa abruptly (black squares in Figure 10). The increasing
electrical characteristics. resistivity at higher pressures derived from a lower concen-
Clatot et al. measured the film crystallinity and stoi- tration of oxygen vacancy, which reduces the number of free
chiometry, resistivity, and transmittance curves of Si-doped electrons in turn. In addition, the annealing treatment in
ZnO thin films deposited both on glass and PET substrates. air was observed to cause resistivity to increase (red dots in
Their results confirmed the strong dependence of the elec- Figure 10), diminishing residual dependence on deposition
trical and optical properties on substrate nature [46]. As conditions because oxygen vacancies are saturated. This
the theoretical and experimental studies of the impact of variation relation has been also observed in other preparation
hydroxylation, vacancies, interstitials, and extrinsic doping methods [5, 54].
on the electronic properties of the polar ZnO (0002) surface In CVD processing, the precursor pressure in CVD
done by Li et al. [38], we can have a study on the influence processing also showed strong influence on resistivity. Kim
of substrate type on growth, defects, and the electronic et al. [24] prepared AZO layers on glass substrates by LP-
properties of the ZnO thin films. CVD and found Al precursor, (Trimethylaluminum) showed
strong influence on Al contents and resistivity of AZO.
4.3. Growth Temperature. At high temperature, films exhib-
ited higher doping efficiency, higher carrier concentration, 4.5. Film Thickness. Film thickness is another factor for the
lower resistivity, and higher Hall mobility. Lee et al. [43] electrical and optical properties in ZnO-based TCO films,
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
6 Journal of Nanomaterials

(a) (b)

(c) (d)

Figure 7: Cross-sectional FE-SEM images of (a) 200 nm thick GZO thin films on glass; (b) 200 nm-thick GZO thin films on Al2 O3 (0001)
substrates; (c) 1000 nm thick GZO thin films on glass; (d) 1000 nm thick GZO thin films on Al2 O3 (0001) substrates [42]. Copyright 2009
Materials Research Society.

×10−3 time, temperature, and power [42, 55]. In sol-gel spin coating,
3.5 7 films with various thicknesses are obtained with different
22
Carrier concentration (1020 /cm3 )

3 repeating times of coating procedure [26, 45, 56].

20 6 As we all know that electrical conductivity becomes better
Mobility (cm2 /Vs)
Resistivity (Ω·cm)

2.5 18 while transmittance may become poorer as the film thickness

2
16 5 increases [55]. Shin et al. [42] investigated the effect of film
14 thickness on the structural and electrical properties of Ga-
1.5
12
4 doped ZnO thin films. It was also found that the electrical
1
resistivity difference between the films on the two substrates
10
3 decreased from 9.48 × 10−4 Ω⋅cm to 1.45 × 10−4 Ω⋅cm with
0.5 8 increasing the film thickness from 100 nm to 1000 nm. In
0 6 2 Figure 7, the conductivity increases because of both the
100 200 300 400 500
increase of grain size and the decrease of grain boundary
Temperature (∘ C)
scattering. On the other hand, more photons are adsorbed
Resistivity when the thickness increases according to the following:
Mobility
Concentration
𝐼 = 𝐼0 e−𝛼𝑥 . (2)
Figure 8: Resistivity, carrier concentration, and Hall mobility of
GZO thin films as a function of deposition temperature in the range
of RT to 500∘ C [43]. Copyright 2011, Elsevier. Here 𝐼 is the intensity of transmitted light, 𝐼0 is the
intensity of incident light, 𝛼 is absorption coefficient, and 𝑥
can be treated as the film thickness. Due to these two opposite
trends, it is difficult to balance the need for high conductivity
which change from ∼50 nm to ∼2000 nm. In magnetron with the need for high transparency. How to get thinner films
sputtering and other deposition technique, ZnO films with with both excellent electrical and optical property is one of
various thicknesses are obtained by varying the deposition the main research tasks.
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Journal of Nanomaterials 7

1100
248 nm Scan AZO on Kapton
pulsed
laser 80%
900

Temperature (K)
AZO on SLG
AZO
700
AZO on Al-foil 60%
SLG
i-ZnO
Motorized 𝑋/𝑌 stage 500
Substract
300 25%
0 100 200 300 400 500 600
Time (ns)
(a) (b)

Figure 9: (a) Schematic of DPLR technique. (b) Temperature evolution of AZO film on different substrates carried out by multiphysics EM-
HT simulation. To reach 1100 K (peak temperature), laser fluence used is 50, 60, and 65 mJ/cm2 for AZO film on Kapton, SLG, and Al-foil
substrates, respectively [44]. Copyright 2012 American Institute of Physics.

Opened Fund of the State Key Laboratory on Integrated

Optoelectronics No. 20∗∗∗∗∗∗∗∗ .
Annealed
0.1
References
Resistivity (Ω·cm)

[1] J. Song, Y. He, J. Chen et al., “Bicolor light-emitting diode based

0.01 on zinc oxide nanorod arrays and poly(2-methoxy,5-octoxy)-
1,4-phenylenevinylene,” Journal of Electronic Materials, vol. 41,
no. 3, pp. 431–436, 2012.
[2] D. J. Rogers, F. H. Teherani, V. E. Sandana, and M. Razeghi,
1𝐸−3 As-dep “ZnO thin films and nanostructures for emerging optoelec-
tronic applications,” in Proceedings of the 12th Optoelectronic
Integrated Circuits, L. A. Eldada and E. H. Lee, Eds., January
2010.
0.01 0.1 1 10
[3] H. Zeng, X. Xu, Y. Bando et al., “Template deformation-
Deposition pressure (Pa)
tailored ZnO nanorod/nanowire arrays: full growth control and
Figure 10: Resistivity as a function of deposition pressure for optimization of field-emission,” Advanced Functional Materials,
as-deposited (black squares) and annealed films (red dots) [35]. vol. 19, no. 19, pp. 3165–3172, 2009.
Copyright 2012, Elsevier. [4] T. Minami, “Transparent conducting oxide semiconductors for
transparent electrodes,” Semiconductor Science and Technology,
vol. 20, no. 4, pp. S35–S44, 2005.
5. Summary [5] D. B. Buchholz, J. Liu, T. J. Marks, M. Zhang, and R. P. H. Chang,
“Control and characterization of the structural, electrical, and
In this paper, how dopants and growth conditions, such as optical properties of amorphous zinc-indium-tin oxide thin
substrate type, growth temperature, influence electrical and films,” ACS Applied Materials & Interfaces, vol. 1, no. 10, pp.
2147–2153, 2009.
optical properties of ZnO-based TCO films were discussed
in a panoramic view. we reviewed recently published work [6] C. A. Hoel, T. O. Mason, J. F. Gaillard, and K. R. Poeppelmeier,
“Transparent conducting oxides in the ZnO-In2O 3-SnO2
on new, cheap, low-temperature, and high-speed deposition
system,” Chemistry of Materials, vol. 22, no. 12, pp. 3569–3579,
technology, highlighting methods of producing film on 2010.
flexible substrate, the most promising and rapidly emerg-
[7] A. Stadler, “Transparent conducting oxides-an up-to-date
ing research areas. However, more experimental works are overview,” Materials, vol. 5, no. 4, pp. 661–683, 2012.
needed to clarify the relationship between doping, process-
[8] C. G. Granqvist, “Transparent conductors as solar energy
ing, and property of ZnO thin films. materials: a panoramic review,” Solar Energy Materials and Solar
Cells, vol. 91, no. 17, pp. 1529–1598, 2007.
Acknowledgments [9] U.S.G. Survey, “Mineral Commodity Summaries,” 2012.
[10] K. Ellmer, “Past achievements and future challenges in the
This work was supported by the Natural Science Foundation development of optically transparent electrodes,” Nature Pho-
of China (Nos. 61222403), the Jiangsu Introduction Pro- tonics, vol. 6, no. 12, pp. 809–817, 2012.
gram of High-Level Innovative and Pioneering Talents, the [11] T. Minami, “Substitution of transparent conducting oxide thin
Fundamental Research Funds for the Central Universities films for indium tin oxide transparent electrode applications,”
(Nos. 4015-56XIA12004 and 4015-56YAH11047), and by the Thin Solid Films, vol. 516, no. 7, pp. 1314–1321, 2008.
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
8 Journal of Nanomaterials

[12] T. W. Kim, D. C. Choo, Y. S. No, W. K. Choi, and E. H. [27] D.-W. Kang, J.-Y. Kwon, D.-J. Lee, and M.-K. Han, “Boron and
Choi, “High work function of Al-doped zinc-oxide thin films aluminum codoped ZnO transparent conducting films with
as transparent conductive anodes in organic light-emitting high electrical stability,” Journal of the Electrochemical Society,
devices,” Applied Surface Science, vol. 253, no. 4, pp. 1917–1920, vol. 159, no. 2, p. H61, 2012.
2006. [28] S. W. Shin, G. L. Agawane, I. Y. Kim et al., “Development of
[13] T. Minami, “Present status of transparent conducting oxide transparent conductive Mg and Ga co-doped ZnO thin films:
thin-film development for Indium-Tin-Oxide (ITO) substi- effect of Mg concentration,” Surface and Coatings Technology,
tutes,” Thin Solid Films, vol. 516, no. 17, pp. 5822–5828, 2008. 2012.
[14] H. Zeng, S. Yang, and W. Cai, “Reshaping formation and [29] S. W. Shin, I. Y. Kim, G. H. Lee et al., “Design and growth of
luminescence evolution of ZnO quantum dots by laser-induced quaternary Mg and Ga codoped ZnO thin films with transpar-
fragmentation in liquid,” Journal of Physical Chemistry C, vol. ent conductive characteristics,” Crystal Growth & Design, vol. 11,
115, no. 12, pp. 5038–5043, 2011. no. 11, pp. 4819–4824, 2011.
[15] H. B. Zeng, X.-W. Du, S. C. Singh, S. A. Kulinich, S. Yang, and [30] H. Zeng, W. Cai, P. Liu et al., “ZnO-based hollow nanoparticles
J. He, “Nanomaterials via laser ablation/irradiation in liquid: a by selective etching: elimination and reconstruction of metal—
review,” Advanced Functional Materials, vol. 22, no. 7, pp. 1333– semiconductor interface, improvement of blue emission and
1353, 2012. photocatalysis,” ACS Nano, vol. 2, no. 8, pp. 1661–1670, 2008.
[16] A. Favier, D. Muñoz, S. Martı́n De Nicolás, and P. J. Ribeyron, [31] D. P. Norton, Y. W. Heo, M. P. Ivill et al., “ZnO: growth, doping
“Boron-doped zinc oxide layers grown by metal-organic CVD & processing,” Materials Today, vol. 7, no. 6, pp. 34–40, 2004.
for silicon heterojunction solar cells applications,” Solar Energy
[32] H. Zeng, W. Cai, J. Hu, G. Duan, P. Liu, and Y. Li, “Violet
Materials and Solar Cells, vol. 95, no. 4, pp. 1057–1061, 2011.
photoluminescence from shell layer of Zn/ZnO core-shell
[17] Q. Huang, Y. Wang, S. Wang, D. Zhang, Y. Zhao, and X. Zhang, nanoparticles induced by laser ablation,” Applied Physics Letters,
“Transparent conductive ZnO:B films deposited by magnetron vol. 88, no. 17, Article ID 171910, 2006.
sputtering,” Thin Solid Films, vol. 520, no. 18, pp. 5960–5964,
[33] H. Zeng, G. Duan, Y. Li, S. Yang, X. Xu, and W. Cai, “Blue
2012.
luminescence of ZnO nanoparticles based on non-equilibrium
[18] J. A. Sans, J. F. Sánchez-Royo, A. Segura, G. Tobias, and E. processes: defect origins and emission controls,” Advanced
Canadell, “Chemical effects on the optical band-gap of heavily Functional Materials, vol. 20, no. 4, pp. 561–572, 2010.
doped ZnO: MIII (M=Al,Ga,In): an investigation by means
[34] J. G. Lu, S. Fujita, T. Kawaharamura et al., “Carrier concentra-
of photoelectron spectroscopy, optical measurements under
tion dependence of band gap shift in n -type ZnO:Al films,”
pressure, and band structure calculations,” Physical Review B,
Journal of Applied Physics, vol. 101, no. 8, Article ID 083705, 2007.
vol. 79, no. 19, Article ID 195105, 2009.
[19] D. S. Bhachu, I. P. Parkin, and G. Sankar, “Aerosol assisted [35] P. Gondoni, M. Ghidelli, F. Di Fonzo et al., “Structural and
chemical vapour deposition of transparent conductive Zinc functional properties of Al:ZnO thin films grown by Pulsed
oxide films,” Chemistry of Materials, vol. 24, no. 24, pp. 4704– Laser Deposition at room temperature,” Thin Solid Films, vol.
4710, 2012. 520, no. 14, pp. 4707–4711, 2012.
[20] P. Nunes, E. Fortunato, P. Tonello, F. Braz Fernandes, P. Vilar- [36] G. Socol, D. Craciun, I. N. Mihailescu et al., “High quality
inho, and R. Martins, “Effect of different dopant elements on amorphous indium zinc oxide thin films synthesized by pulsed
the properties of ZnO thin films,” Vacuum, vol. 64, no. 3-4, pp. laser deposition,” Thin Solid Films, vol. 520, no. 4, pp. 1274–1277,
281–285, 2002. 2011.
[21] J. L. Zhao, X. W. Sun, H. Ryu, and Y. B. Moon, “Thermally stable [37] A. K. Das, P. Misra, and L. M. Kukreja, “Effect of Si doping on
transparent conducting and highly infrared reflective Ga-doped electrical and optical properties of ZnO thin films grown by
ZnO thin films by metal organic chemical vapor deposition,” sequential pulsed laser deposition,” Journal of Physics D, vol. 42,
Optical Materials, vol. 33, no. 6, pp. 768–772, 2011. no. 16, Article ID 165405, 2009.
[22] S. M. Park, T. Ikegami, and K. Ebihara, “Effects of substrate [38] H. Li, L. K. Schirra, J. Shim et al., “Zinc oxide as a model
temperature on the properties of Ga-doped ZnO by pulsed laser transparent conducting oxide: a theoretical and experimental
deposition,” Thin Solid Films, vol. 513, no. 1-2, pp. 90–94, 2006. study of the impact of hydroxylation, bacancies, interstitials,
[23] Y. Geng, L. Guo, S. S. Xu et al., “Influence of Al doping on the and extrinsic doping on the electronic properties of the polar
properties of ZnO thin films grown by atomic layer deposition,” ZnO (0002) surface,” Chemistry of Materials, vol. 24, no. 15, pp.
Journal of Physical Chemistry C, vol. 115, no. 25, pp. 12317–12321, 3044–3055, 2012.
2011. [39] H. Agura, A. Suzuki, T. Matsushita, T. Aoki, and M. Okuda,
[24] D. Kim, H. Kim, K. Jang, S. Park, K. Pillai, and J. Yi, “Electrical “Low resistivity transparent conducting Al-doped ZnO films
and optical properties of low pressure chemical vapor deposited prepared by pulsed laser deposition,” Thin Solid Films, vol. 445,
Al-doped ZnO transparent conductive oxide for thin film solar no. 2, pp. 263–267, 2003.
cell,” Journal of the Electrochemical Society, vol. 158, no. 4, pp. [40] A. Illiberi, B. Kniknie, J. van Deelen et al., “Industrial high-rate
D191–D195, 2011. (∼14 nm/s) deposition of low resistive and transparent ZnOx:Al
[25] L. Cao, L. Zhu, J. Jiang, R. Zhao, Z. Ye, and B. Zhao, “Highly films on glass,” Solar Energy Materials and Solar Cells, vol. 95,
transparent and conducting fluorine-doped ZnO thin films no. 7, pp. 1955–1959, 2011.
prepared by pulsed laser deposition,” Solar Energy Materials and [41] A. Illiberi, P. J. P. M. Simons, B. Kniknie et al., “Growth of
Solar Cells, vol. 95, no. 3, pp. 894–898, 2011. ZnOx:Al by high-throughput CVD at atmospheric pressure,”
[26] T. Wang, Y. Liu, Q. Fang, M. Wu, X. Sun, and F. Lu, “Low Journal of Crystal Growth, vol. 347, no. 1, pp. 56–61, 2012.
temperature synthesis wide optical band gap Al and (Al, Na) [42] S. W. Shin, S. M. Pawar, T. W. Kim, J. H. Moon, and J. H.
co-doped ZnO thin films,” Applied Surface Science, vol. 257, no. Kim, “Effect of film thickness on the structural and electrical
6, pp. 2341–2345, 2011. properties of Ga-dopped ZnO thin films prepared on glass and
 9182, 2013, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2013/196521 by Istanbul Technical University, Wiley Online Library on [10/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Journal of Nanomaterials 9

Al2O3 (0001) substrates by RF magnetron sputtering method,”

Journal of Materials Research, vol. 24, no. 2, pp. 441–447, 2009.
[43] D.-H. Lee, K. Kim, Y. S. Chun, S. Kim, and S. Y. Lee,
“Substitution mechanism of Ga for Zn site depending on
deposition temperature for transparent conducting oxides,”
Current Applied Physics, vol. 12, no. 6, pp. 1586–1590, 2012.
[44] M. Y. Zhang, Q. Nian, and G. J. Cheng, “Room temperature
deposition of alumina-doped zinc oxide on flexible substrates
by direct pulsed laser recrystallization,” Applied Physics Letters,
vol. 100, no. 15, 2012.
[45] L. Luo, M. D. Rossell, D. Xie, R. Erni, and M. Nieder-
berger, “Microwave-assisted nonaqueous Sol-Gel synthesis:
from Al:ZnO nanoparticles to transparent conducting films,”
ACS Sustainable Chemistry & Engineering, vol. 1, no. 1, pp. 152–
160, 2013.
[46] J. Clatot, G. Campet, A. Zeinert, C. Labrugère, M. Nistor, and
A. Rougier, “Low temperature Si doped ZnO thin films for
transparent conducting oxides,” Solar Energy Materials and
Solar Cells, vol. 95, no. 8, pp. 2357–2362, 2011.
[47] L. Gong, J. Lu, and Z. Ye, “Transparent and conductive Ga-
doped ZnO films grown by RF magnetron sputtering on
polycarbonate substrates,” Solar Energy Materials and Solar
Cells, vol. 94, no. 6, pp. 937–941, 2010.
[48] L. Ficke and M. Cahay, “The bright future of organic LEDs,”
IEEE Potentials, vol. 22, no. 5, pp. 31–34, 2003.
[49] J. Z. Song, Y. He, D. Zhu, J. Chen, C. L. Pei, and J. A. Wang,
“Polymer/ZnO micro-nano array composites for light-emitting
layer of flexible optoelectronic devices,” Acta Physico-Chimica
Sinica, vol. 27, no. 5, pp. 1207–1213, 2011.
[50] S. Esmaili-Sardari, A. Berkovich, and A. A. Iliadis, “Observation
of conductivity type conversion in undoped ZnO films grown
by pulsed laser deposition on silicon (100) substrates,” Applied
Physics Letters, vol. 100, no. 5, Article ID 053505, 2012.
[51] K. Kim, S. Y. Park, K.-H. Lim, C. Shin, J.-M. Myoung, and
Y. S. Kim, “Low temperature and solution-processed Na-
doped zinc oxide transparent thin film transistors with reliable
electrical performance using methanol developing and surface
engineering,” Journal of Materials Chemistry, vol. 22, no. 43, pp.
23120–23128, 2012.
[52] W.-J. Yang, C.-C. Tsao, C.-Y. Hsu, H.-C. Chang, C.-P. Chou,
and J.-Y. Kao, “Fabrication and characterization of transpar-
ent conductive ZnO:Al thin films deposited on polyethylene
terephthalate substrates,” Journal of the American Ceramic
Society, vol. 95, no. 7, pp. 2140–2147, 2012.
[53] M. Y. Zhang and G. J. Cheng, “Highly conductive and transpar-
ent alumina-doped ZnO films processed by direct pulsed laser
recrystallization at room temperature,” Applied Physics Letters,
vol. 99, no. 5, 2011.
[54] T. Moon, W. Yoon, K. S. Ji et al., “Enhancement of crystallinity
in ZnO:Al films using a two-step process involving the control
of the oxygen pressure,” in Proceedings of the 35th IEEE
Photovoltaic Specialists Conference (PVSC ’10), pp. 3709–3712,
June 2010.
[55] T. Prasada Rao and M. C. Santhoshkumar, “Effect of thickness
on structural, optical and electrical properties of nanostruc-
tured ZnO thin films by spray pyrolysis,” Applied Surface
Science, vol. 255, no. 8, pp. 4579–4584, 2009.
[56] J. Z. Song, Y. He, Z. D. Pan, D. Zhu, J. Chen, and J. A. Wang,
“PANI/nano-ZnO composites prepared by in-situ polymeriza-
tion under magnetic field,” Acta Chimica Sinica, vol. 69, no. 13,
pp. 1582–1588, 2011.