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Materials Today: Proceedings 5 (2018) 9965–9971 www.materialstoday.com/proceedings
IC-FNM 2016
Photoluminescence of Atomic Layer Deposition Grown ZnO
Nanostructures
Dipayan Pala, Aakash Mathura, Ajaib Singha, Jaya Singhalb, Sudeshna
Chattopadhyaya,b,c,*
a
Discipline of Metallurgy Engineering and Materials Science, Indian Institute of Technology Indore, Indore 453552, India
b
Centre for Biosciences and Biomedical Engineering, Indian Institute of Technology Indore, Indore 453552, India
c
Discipline of Physics, Indian Institute of Technology Indore, Indore 453552, India
Abstract
Atomic Layer Deposition (ALD) technique was used to grow crystalline, nanostructured Zinc Oxide (ZnO) thin films, having
very low surface roughness, on silicon (Si) and fused quartz (SiO2) substrates. The film thickness and structural properties were
characterized by using X-ray reflectivity and X-ray diffraction techniques. The excitonic light emission of ZnO thin films
wasstudied by means of photoluminescence (PL) measurements in the ultraviolet-visible spectral region. Characteristic near band
edge emission (NBE) of the ZnO thin films corresponding to free excitonic recombination shows strong signal in the UV range at
room temperature. Visible region of the PL spectra of ZnO nanostructures shows that there is no defect related deep level
emission (DLE), suggesting the absence of defect states. The results confirm the growth of ZnO thin films of a high quality
crystalline structure by ALD technique.
© 2017 Elsevier Ltd. All rights reserved.
Selection and/or Peer-review under responsibility of International Conference on Functional Nano-Materials, 2016.
Keywords:Atomic Layer Deposition; Zinc Oxide thin film; Photoluminescence, optical property
1. Introduction
During the past few years, wide band gap semiconductors have garnered immense interest, because of the
increasing commercial demand for short wavelength light-emitting devices [1, 2]. ZnO is a direct and wide bandgap
semiconductor with Eg = 3.37 eV at room temperature and a large exciton binding energy of 60 meV, which
* Corresponding author. Tel.:+0-731-2438-959 .
E-mail address:
[email protected]2214-7853© 2017 Elsevier Ltd. All rights reserved.
Selection and/or Peer-review under responsibility of International Conference on Functional Nano-Materials, 2016.
9966 Pal et al. / Materials Today: Proceedings 5 (2018) 9965–9971
expedites more efficient excitonic emission at higher temperatures, compared to other semiconductors, such as GaN
(28 meV) and ZnSe (19 meV) [3-5]. Due to these outstanding properties, ZnO has received enormous interest as an
important contender for use in optoelectronics applications in the UV and visible regions. It has also become an
attractive choice for application in various technological domains, e , such as solar cells [6], transparent conducting
oxide thin film electrodes [7], light-emitting diodes [8], laser diodes [9] and acoustic optical devices [10] due to its
good optical quality, extreme stability of excitons and excellent piezoelectric properties [11]. Therefore, control over
their structural and consequently the optical properties is the key to designing of the next-generation optoelectronic
devices.
So far, a number of deposition techniques have been explored to grow ZnO thin films, for example, molecular
beam epitaxy (MBE)[12, 13], pulsed laser deposition (PLD)[13, 14], radio-frequency magnetron sputtering[15,
16]and sol-gel method[17, 18]. But, the precise control of film thickness and conformality is the present day
technology need. In the recent years, atomic layer deposition (ALD) technique has drawn a significant interest to
grow ZnO thin films[19-23]. Over other thin film deposition techniques, ALD offers several advantages such as
precise thickness control down to atomic level, excellent conformality, high uniformity over a large area, dense and
pinhole-free films and a high degree of reproducibility[24-26].
Recently, ZnO research in the optoelectronics field has been increasing and it is mainly focused on improving the
ZnO free exciton emission in the UV region, taking advantages of its large exciton binding energy and efficient
radiative recombination even at room temperature [27, 28]. Photoluminescence (PL) in the UV region is due to the
free electron-hole recombination near the band edge. In the visible region, PL is due to the presence of native point
defects such as oxygen and zinc vacancies; oxygen and zinc interstitials; and antisite oxygen [29]. Free excitons are
bound electron-hole pairs which can move together throughout the crystal [30]and play an important role in
photovoltaic, optoelectronics and solar cell devices [31-33].
In this study, we have investigated the structural and optical properties in Atomic Layer Deposition (ALD) grown
ZnO thin films with the film thickness ranging from ~20nm to ~70 nm. The structural properties have been explored
by x-ray reflectivity (XRR) and x-ray diffraction (XRD) techniques. The excitonic light emission of ZnO thin films
has been studied by means of Photoluminescence (PL) measurements. The strong UV PL emission and complete
absence of defect-related broadband emission confirm the growth of ZnO thin films of high quality crystal structure
with negligible defect states irrespective of the used substrates, like Si (100) and fused quartz (SiO2).
2. Experimental
A BENEQ TFS-200 ALD setup was used for deposition of thin ZnO films on two different substrates Si (100) and
fused quartz (SiO2). The substrates were pre-cleaned by ultrasonication in acetone and ethanol in sequence for 2 min
each, and then keeping them in DI water, and finally drying up in nitrogen (N2, 99.999% purity). Diethyl zinc (DEZ,
Zn(C2H5)2, Sigma-Aldrich) and deionized (DI) water were used as precursors for zinc and oxygen respectively. The
ZnO ALD films were grown using an alternating pulse of the precursors into the reactor chamber. ALD was carried
out at 200ºCand the reactor pressure during the growth was kept at 1.75 mbar.One ALD reaction cycle consisted of a
0.2 s exposure to DEZ, followed by a 0.75 s for N2 purge, a 0.2 s exposure to H2O, and then another 0.75 s N2
purgewith a growth rate of about 1.6 Å per cycle which is in agreement with the growth rate reported by the other
groups[34, 35].ZnO films with different thickness (~ 20 nm and ~ 70 nm) were grown on Si (100) and fused quartz
(SiO2) substrates, by varying the number of ALD cycles.
The crystalline structures and thickness of the ZnO thin films were examined by X-ray diffraction (XRD) and X-ray
reflectivity (XRR) respectively. A Rigaku SmartLab automated multipurpose X-ray diffractometer with CuKα
radiation ( = 1.54 Å) and a vertical scattering plane was usedto collect x-ray scatteringdata.
In x-ray reflectivity studies under specular conditions the momentum transfer vector q = ks-ki(ks and ki being the
scattered and incident X-ray wave vector respectively) has vanishing inplane components (qx = qy = 0) with only
nonvanishing component, qz (= (4π/λ) sinθ) along surface normal direction, where θis the angle of incident which is
equal to the scattering angle.Specular reflectivity scans were performed with θvarying from 0º to 3º,
correspondingly qz varies from 0 to 0.4 Å-1.
Pal et al./ Materials Today: Proceedings 5 (2018) 9965–9971 9967
The X-ray reflectivity, R(qz), is relatedtoρ(z)via[36]:
( )
( )= ( ) exp( ) (1)
∆
Where, RF is the Fresnel reflectivity from a single ideal step-function interface, Δρ is the total change in electron
density across the interface. The Eq. (1) can be used to calculate R(qz) from a given analytic function ρ(z), but, the
reverse is not simple. The general procedure, which is commonly used to analyze all the inverse problems, was
employed to study and evaluate the XRR data. A model ρ(z), specifically a slab model, is assumed, and following
the Parratt formalism theparameters of the model were adjusted until good fits to the data were achieved[37-41]. The
extracted values of film thickness, electron density and interface width or roughness from the best fit of reflectivity
data, were used to construct the electron density profiles (EDPs), i.e., the electron density as a function of film depth
from the top for ZnO films, after convoluting the profile with the interface widths.
The PL emission from the ZnO films was measured at room temperature using a PL spectrometer (Dongwoo Optron
DM 500i) having an excitation source consisting of a continuous wave He-Cd laser (excitation wavelength, 325 nm,
PMT detector).
3. Results and discussion
X-ray reflectivity (XRR) technique provides the overall information of film thickness, electron density
profile and the surface and interface roughness of the system. Fig. 1(a) shows specular reflectivity (R) normalized
with Fresnel reflectivity (RF), for ZnO films on two different substrates, Si and SiO2. XRR of two representatives
ZnO film thickness, 69 nm and 19 nm, are shown. Circles and lines represent the experimental data and theoretical
fit respectively. XRR data analysis using well-known Parratt formalism [37-41],provides the information on depth
profile of the ALD grown ZnO films, as shown in Fig. 1(b). Fig. 1(a) and (b) show the electron density () profiles
(EDPs) of the respective films extracted from XRR fits, for four ZnO films with two different film thickness, which
were deposited on two different substrates, Si and SiO2.
XRR results indicate that for ZnO/Si and ZnO/SiO2 systems, the electron density of ZnO films are close
to its bulk electron density and remain constant down to ~ 19 nm thickness. Clear strong Kiessig fringes in XRR
data (Fig. 1(a)) along with the extracted electron density profile (Fig. 1(b)) indicate the formation of high quality
ALD grown ZnO thin films on both Si and SiO2 substrates, with very low surface and interface roughness. This
signifies the growth of pinhole free with ~100% coverage high quality ZnO thin films by atomic layer deposition
technique.
Fig. 2(a) and 2(b) show the X-ray diffraction pattern of ZnO films grown at 200ºC on Si and SiO2 substrates
respectively. The diffraction peak positions were well matched with the standard diffraction pattern of hexagonal
wurtzite ZnO with a space group of P63mc (JCPDS PDF card number: 01-079-2205). From Fig. 2(a), XRD patterns
of ZnO films grown on Si show much stronger ZnO (002) peak with respect to ZnO (101), whereas standard powder
XRD pattern of hexagonal wurtzite bulk ZnO shows maximum intensity at ZnO (101) peak (JCPDS PDF card
number: 01-079-2205).
The results suggest the growth of textured ZnO films with a preferential orientation along <0002> direction with c
axis perpendicular to the substrate surface. For ZnO/SiO2 system, as shown in Fig. 2(b), the observation is similar
with that of ZnO/Si system, i.e. a dominant (002) peak of hexagonal wurtzite is observed.
9968 Pal et al. / Materials Today: Proceedings 5 (2018) 9965–9971
Fig. 1.(a) Reflectivity profiles, i.e., specular reflectivity (R) normalized with Fresnel reflectivity (RF), (R/RF) vs. normal momentum transfer qz (in
Å-1) for different ZnO film thickness, grown at 200ºC. (i) and (ii): ~19 nm ZnO deposited on Si and SiO2 substrates respectively; (iii) and (iv):
~69 nm ZnO deposited on Si and SiO2 substratesrespectively. RF is the theoretical reflectivity from an ideal surface. Circles and lines represent
the experimental data and theoretical fit respectively; and (b) corresponding extracted electron density () profile from XRR fits.
Pal et al./ Materials Today: Proceedings 5 (2018) 9965–9971 9969
Fig. 2.XRD patterns of ZnO thin films grown on (a) Si and (b) SiO2 at 200ºC. Corresponding film thicknesses are marked in the figure.
The excitonic light emission of ZnO films has been investigated by means of photoluminescencemeasurements in
the wavelength (λ) range of 300-800 nm UV-Vis region. Photoluminescence (PL) analysis is a very effective tool
for characterizationand evaluation ofluminescent materials[42]. Fig. 3 shows the room temperature
photoluminescence (RT-PL) spectra of the ZnO films grown on Si and SiO2. From Fig. 3, it can be clearly seen that
for both the ~ 69 nm film grown on Si and SiO2, the RT-PL spectra is dominated by strong near band edge (NBE)
UV-emission originating from free exciton emission at room temperature. This free excitonic PL (also called ‘edge’
PL) can only be seen in films of good structural quality, in which nonradiative processes are inefficient and in which
carriers are not dominantly trapped by some defect centers[43].In the PL spectra, no prominent defect related deep
level emission (DLE) in the visible spectral region is observed for all the samples. The strong NBE and absence of
DLE indicate the very low density of defect states and correspondingly a growth of ZnO thin films, in ~19 nm to ~
69 nm length scale, with high quality crystalline structure [43, 44]. Additionally, there is a clear blue shift in thinner
ZnO film (~19 nm), when the film was grown on Si substrate, which can be attributed to the confinement effect, as
observed in other studies on ZnO thin films, at and below 20 nm film thickness[23, 27, 45] .
9970 Pal et al. / Materials Today: Proceedings 5 (2018) 9965–9971
Fig. 3.Photoluminescence (PL) spectra of ZnO films grown on (a) Si and (b) SiO2 at 200ºC. Theinset displays the near band edge (NBE) UV
emission peaks in log scale.
4. Conclusions
We have clearly shown that by using ALD technique high quality crystalline textured ZnO thin films with very low
surface roughness can be grown, where film thickness can be controlled very precisely in nm scale. The system
shows strong near band edge (NBE) UV emission in PL spectra whereas there is no signal of defect related deep
level emission (DLE) in the visible spectral region. This phenomenon indicates that ZnO thin films prepared in this
manner may serve as a key component in the design and fabrication of short wavelength light-emitting devices.
Acknowledgements
We would like to acknowledge IIT Indore for all kinds of support to this work. We would also like to thank
Department of Science and Technology (DST), Government of India. This work is partially supported by
Department of Science and Technology (DST), India, Project No. SB/S2/CMP-077/2013 and Council of Scientific
and Industrial Research (CSIR), India, Project No. 03 (1310)/14/EMR-II.
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