Professional Documents
Culture Documents
To cite this article: Claudiu Lung, Daniel Marconi, Maria Toma & Aurel Pop (2016)
Characterization of the Aluminum Concentration upon the Properties of Aluminum Zinc Oxide
Thin Films, Analytical Letters, 49:8, 1278-1288, DOI: 10.1080/00032719.2015.1094663
Article views: 32
Download by: [INCDTIM Cluj-napoca], [Marconi Daniel] Date: 19 May 2016, At: 23:36
ANALYTICAL LETTERS
2016, VOL. 49, NO. 8, 12781288
http://dx.doi.org/10.1080/00032719.2015.1094663
NANOTECHNOLOGY
Introduction
Zinc oxide (ZnO) is one of the most important II-VI semiconductors with large exciton
binding energy (E 60 meV), known for its many applications such as thin film transistors,
window materials in solar cells, ultraviolet light emitting diodes, blue luminescent devices,
ultraviolet light lasers (Reynolds, Look, and Jogai 1996; Aoki, Hatanaka, and Look 2000),
transparent conductive contacts, optoelectronic, piezoelelectric applications, and spin-
photonic devices (H. W. Lee et al. 2005; S. Lee et al. 2005; Khomchenko et al. 2007). It
has a wide and direct band gap (Eg 3.37 eV) and good chemical and thermal stability.
ZnO is found in nature as a mineral named zincite. Its color may vary from yellow to
red, but due to its wide band gap, pure ZnO is colorless (Klingshirn 2007). Zinc oxide crys-
tal has mainly a hexagonal wurtzite structure. It belongs to the space group P63mc and the
ratio of translational vectors is close to the ratio for hexagonal cell (1.633). Zinc oxide has a
n-type electrical conductivity and is transparent to visible light. With a proper choice of
dopant atoms, the luminescence properties of ZnO films may be changed. By introducing
Al atoms as dopants, the defect environment is changed whether these atoms substitutes
the zinc atom or occupy interstitial sites. Aluminum doping is expected to change the
optical and electrical properties of ZnO films.
Several deposition techniques have been used to fabricate epitaxial and textured ZnO
and aluminum zinc oxide (AlZnO) films including magnetron sputtering and pulsed-laser
deposition (Pedarnig et al. 2008; Ciomos et al. 2011; Girbovan et al. 2011; Girbovan et al.
2012). For fabricating metal oxide thin films and related materials, radio-frequency mag-
netron sputtering is considered one of the best deposition methods, as it allows growth
of uniform thin films at low temperature with high reproducibility and with strong
adhesion to substrates over large area surfaces (Chen et al. 2001; J. Lee et al. 2007). Taking
Downloaded by [INCDTIM Cluj-napoca], [Marconi Daniel] at 23:36 19 May 2016
into account the practical use, the films should be deposited on amorphous substrates, such
as glass (Hwang et al. 2011). Many reports have already showed that the properties of
AlZnO thin films were influenced by processing parameters during sputtering, including
the substrate temperature (Girbovan et al. 2011; Girbovan et al. 2012), discharge power
(Chen et al. 2001; Kobayakawa, Tanaka, and Ide-Ektessabi 2006; Hwang et al. 2011), tar-
get-substrate distance (Ding et al. 2009; Kim et al. 2009; Hwang et al. 2011), and oxygen
flow content (Sui et al. 2013; Gupta, Mangal, and Singh 2014). Considering the latest stu-
dies, the novelties of this work consist in using glass as the substrate, increasing the dopant
concentration up to 5%, and evaluation of the changes in the properties of the thin films.
Experimental
The ZnO and AlZnO thin films were deposited by radio-frequency magnetron sputtering.
Ceramic circular targets with chemical formula ZnO and Al1-xZnxOy with 0 x 5 were
obtained by a solid state reaction, using mechanical mixed powders of 99.99% purity
ZnO and 99.97% purity aluminum oxide. The films were deposited on the glass substrate
by using the oxygen-argon atmosphere as sputtering gas. The deposition pressure in the
chamber was 2.1 10 2 mbar and the target-substrate distance was 6 cm. The reactive
gas is formed from argon and oxygen, having the mass flows dAr and dO2. The introduction
of the reactive gases to the sputtering chamber was independently measured using two
mass flow controllers. The flux ratio fO2 dO2/ (dArdO2) used was 0.375, while the
substrate temperature was 150C. Using a quartz monitor, the films thicknesses were
measured and it was around 900 nm.
The film structure and the preferred orientation of crystallites were determined by X-ray
diffraction analysis, using a Bruker D8 X-ray diffractometer with a CrK radiation. The 2
range of 4560 was recorded at the rate of 0.02 and 2/0.5 s. The crystal phases were
identified by comparing the 2 values and intensities of reflection on X-ray diffractograms
with JCP data base using Diffraction AT-Bruker program. Scanning electron microscopy
technique was used to illustrate the formation of crystallites on the film surface using a
FEI Quanta 3D FEG 200/600 microscope.
Optical transmission measurements were done with a Carry 500 Spectrometer (300
1300 nm range). From the transmission spectra, the optical constants were calculated using
the program PARAV-V2.0 (Ganjoo and Golovchak 2008). This program calculates the film
thickness, the refractive index as a function of wavelength, and estimates the transmission
1280 C. LUNG ET AL.
and the absorption coefficient as a function of energy by fitting the Cauchys dispersion
formula. The dispersion of refractive index was calculated from fringe data (experimentally
observed peaks and valleys of T() spectrum) in the fully transmitting region and the weak/
medium absorption regions using Swanepoels theory (Swanepoel 1983).
Figure 1. X-ray diffraction patterns of thin films composed of (a) ZnO, (b) 1% AlZnO, (c) 2% AlZnO, (d)
3% AlZnO, and (e) 5% AlZnO.
ANALYTICAL LETTERS 1281
The dislocation density (), defined as the length of dislocation lines per unit volume
represents the amount of defects in the films and was estimated by:
1
d 2
D2
while the strain () of the thin films was estimated by:
B cos h
e 3
4
The evaluated structural parameters of the thin films are presented in Table 1. The small
values of the strain and the dislocation density were observed for ZnO doped with 2% Al.
Consequently, this material presents the best crystalline quality. For a more precise deter-
Downloaded by [INCDTIM Cluj-napoca], [Marconi Daniel] at 23:36 19 May 2016
mination of the position and the full width at half maximum of the (002) peak, fitting of the
data with a Lorentz-type function was performed. Using Scherrers equation, the average
grain size for ZnO film was 37.4 nm. After substitution of Zn by 1% Al, the average grain
size increased to 39.7 nm, so the increase of the dopant concentration led to a slight
enlargement of the grain size. With 2% Al substitution, the average grain size increased
to 42.3 nm (Table 1). After this optimal Al concentration, the mean grain size slightly
decreased.
Scanning electron microscopy was used for characterizing the microstructure and sur-
face of the thin films. The measurements showed that the microstructural properties of
AlZnO thin films were improved by increasing the dopant concentration. The polycrystal-
line and porous nature is shown in Figures 2, 3, 4, 5, and 6. The incorporation of aluminum
in the lattice affected the morphology. The microstructure consisted of many round clearly
interconnected and defined grains covering the substrate surface more or less uniformly,
regardless of the substrate type (J. Lee et al. 2007). Thus, incorporation of Al led to a more
continuous film having higher density compared to undoped ZnO films.
After reaching optimal 2% Al concentration, values of Al above this concentration
tended to segregate at the grain boundaries, hindering the development of longer grains,
as shown in AlZnO 3 and 5%. (Babu et al. 2015).
The optical transmittance measurements of the ZnO and Al1-xZnxOy (0 x 5) films
were carried out in air at room temperature from 300 to 1300 nm. The results are shown
in Figure 7. All films were transparent in the visible and near infrared. The undoped ZnO
films showed 85% optical transmission in the visible (Kobayakawa, Tanaka, and Ide-Ektes-
sabi 2006; Girbovan et al. 2012). The film transparency decreased when the dopant content
increased, probably due to the rise of average grain size of the films, in accordance with
scanning electron microscopy results. Similar results were reported for AlZnO films
obtained by radio-frequency sputtering (Sui et al. 2013; Gupta, Mangal, and Singh
Table 1. Variation of grain size, optical band gap, film thickness, and structural parameters, as a func-
tion of Al concentration for Zn1-xAlxOy thin films
ZnO 1% AlZnO 2% AlZnO 3% AlZnO 5% AlZnO
Grain size (nm) 37.4 39.7 42.3 35.4 25.7
Optical band gap (eV) 3.28 3.31 3.40 3.21 3.19
Film thickness (nm) 920 910 900 940 950
Dislocations density ( 1014) (lines/m2) 7.14 6.34 5.58 7.97 15.14
Strain ( 10 3) 1.37 1.29 1.21 1.45 2.00
1282 C. LUNG ET AL.
Downloaded by [INCDTIM Cluj-napoca], [Marconi Daniel] at 23:36 19 May 2016
2014). For concentrations greater than 3% Al, atoms were not incorporated in the matrix
only as dopants but also as interstitial atoms causing defects. The decrease in transmittance
with increasing Al doping may be attributed to scattering of photons on structural defects
determined from X-ray diffraction.
According to the MossBurstein theory (Swanepoel 1983), in heavily doped ZnO films,
the donor-electrons occupy states at the bottom of the conduction band. Therefore, with an
increase in Al concentration, the optical band gap (Eopt) broadens (Gupta, Mangal, and
Singh 2014). This behavior was expected as a result of increasing Al3 concentrations that
substitute Zn2 resulting in a shorter wavelengths for 2% and longer wavelengths for
higher concentration values.
At wavelengths above 500 nm, the optical interference in ZnO films doped with Al gen-
erated oscillations in the transmission spectra. Both minimum and maximum values of the
interference increased with wavelength.
Figure 8 shows the refractive index n() for AlZnO film with fO2 0.375. Also, a
decrease from n 1.94 to 1.915 was observed with increasing wavelength from 400 to
1000 nm. The variation of refractive index with wavelength was calculated from the results
of the transmission area and the areas of lower absorbing medium using Swanepoels
theory (Swanepoel 1983). The film thicknesses were calculated based on measurements
at wavelengths centered on two adjacent minimum m2 and m1 using the formula (Ganjoo
and Golovchak 2008):
km1 km2
h 4
2n1 km2 n2 km1
where n2 and n1 are the values corresponding to diffraction indices of m2 and m1.
Figure 7. Optical transmittance spectra of thin films composed of (a) ZnO, (b) 1% AlZnO, (c) 2%
AlZnO, (d) 3% AlZnO, and (e) 5% AlZnO.
ANALYTICAL LETTERS 1285
Figure 8. Refractive index as a function of wavelength for an AlZnO film with fO2 0.375. The solid line
was the calculated dependence using a second order polynomial fit.
Downloaded by [INCDTIM Cluj-napoca], [Marconi Daniel] at 23:36 19 May 2016
The values of thickness of the thin films are shown in Table 1. The results are close to
the values measured with the quartz sensor. The band gap energy for the Al doped ZnO
layers was calculated from the optical absorption coefficient, which was obtained from
measured transmission and layer thickness h:
lnTk
ak 5
h
The relationship between the absorption coefficient () and the incident photon energy
hv may be written as:
ahn Ahn Eg m 6
where A is a constant, h is Plancks constant, Eg is the optical band gap m 1/2 for the
direct transition, and m 2 for the indirect allowed transition (Hwang et al. 2011). The
well-known Tauc relation was employed:
ahn2 A2 hn Eg 7
Figure 9. Tauc plot of thin films composed of (a) ZnO, (b) 1% AlZnO, (c) 2% AlZnO, (d) 3% AlZnO,
and (e) 5% AlZnO.
Figure 10. Variation of grain size and band gap with the concentration of doped AlZnO thin film.
Conclusions
High quality transparent ZnO and Al doped ZnO thin films deposited on glass substrates
were obtained by radio-frequency reactive magnetron sputtering. The effect of Al doping
on the morphological, structural, and optical properties of the films was characterized.
Scanning electron microscopy characterization of the film surface revealed that the incor-
poration of aluminum into the lattice affects the morphology. The AlZnO films also appear
to be more uniform compared to undoped ZnO.
X-ray diffraction measurements showed that the average grain size of ZnO film was
37.4 nm. The increase of the dopant concentration led to a slight enlargement of the grain
size. With 2% Al substitution, the grain size increased to 42.3 nm, whereas dislocations of
the density and of the strain decreased, suggesting that Al substitutes more in the Zn pos-
ition. Also, with an increase of Al concentration to 2%, there appeared to be a shift in the
ANALYTICAL LETTERS 1287
optical band gap of the AlZnO films due to an enhancement of carrier concentration, as
described by Burstein-Moss theory. Above 2%, the decrease of grain boundary, the
increase of the density dislocations, and the same values for lattice height confirmed that
an important fraction of Al atoms segregated, probably at grain boundaries. The thin films
with higher Al concentrations had a wider optical band gap energies compared to undoped
ZnO, suggesting a decrease of carrier concentration. The increase of Al concentration to
2% positively affected the structural and optical properties of AlZnO that are essential
for optoelectrical and solar cell applications.
Funding
Downloaded by [INCDTIM Cluj-napoca], [Marconi Daniel] at 23:36 19 May 2016
The author D. Marconi would like to thank the National Plan for Research-Development and Inno-
vation 2015-2020 PN 16 30 01 for their funding of this research.
References
Aoki, T., Y. Hatanaka, and D. C. Look. 2000. ZnO diode fabricated by excimer-laser doping. Applied
Physics Letters 76: 325758. doi:10.1063/1.126599
Babu, B. J., S. Velumani, J. Arenas-Alatorre, A. Kassiba, J. Chavez, H. Park, S. Hussain, J. Yi, and R.
Asomoza. 2015. Structural Properties of Ultrasonically Sprayed Al-Doped ZnO (AZO) Thin Films:
Effect of ZnO Buffer Layer on AZO. Journal of Electronic Materials 44: 699705. doi:10.1007/
s11664-014-3541-3
Chen, M., Z. L. Pei, C. Sun, J. Gong, R. F. Huang, and L. S. Wen. 2001. ZAO: An attractive potential
substitute for ITO in flat display panels. Materials Science and Engineering: B 85: 21217.
doi:10.1016/s0921-5107(01)00584-0
Ciomos, D., D. Marconi, R. Redac, and A. V. Pop. 2011. Structural and microstructural character-
ization of Al and Gd doped ZnO thin films. Studia UBB Physica. 56: 7.
Ding, J. J., S. Y. Ma, H. X. Chen, X. F. Shi, T. T. Zhou, and L. M. Mao. 2009. Influence of Al-doping
on the structure and optical properties of ZnO films. Physica B: Condensed Matter 404: 243943.
doi:10.1016/j.physb.2009.05.006
Ganjoo, A., and R. Golovchak. 2008. Computer program PARAV for calculating optical constants of
thin films and bulk materials: Case study of amorphous semiconductors. Journal of Optoelectronics
and Advanced Materials 10: 132832.
Girbovan, D., M. A. Bodea, D. Marconi, J. D. Pedarnig, and A. Pop. 2011. Structure, morphology and
optical properties of Al - doped ZnO thin films. Studia UBB Chemia 56: 21320.
Girbovan, D., D. Marconi, R. Redac, and A. V. Pop. 2012. Influence of oxygen on structure and
optical properties of AZO films. Advanced Optical Materials 6: 85962.
Gupta, C. A., S. Mangal, and U. P. Singh. 2014. Impact of rapid thermal annealing on structural,
optical and electrical properties of DC sputtered doped and co-doped ZnO thin film. Applied
Surface Science 288: 41115. doi:10.1016/j.apsusc.2013.10.048
Hwang, D.-H., J.-H. Ahn, K.-N. Hui, K.-S. Hui, and Y.-G. Son. 2011. Effect of oxygen partial
pressure contents on the properties of Al-doped ZnO thin films prepared by radio frequency
sputtering. Journal of Ceramic Processing Research 12: 15054.
Khomchenko, V. S., T. G. Kryshtab, A. K. Savin, L. V. Zavyalova, N. N. Roshchina, V. E. Rodionov,
O. S. Lytvyn, V. I. Kushnirenko, V. B. Khachatryan, and J. A. Andraca-Adame. 2007. Fabrication
and properties of ZnO:Cu and ZnO:Ag thin films. Superlattices and Microstructures 42: 9498.
Kim, Y. H., K. S. Lee, T. S. Lee, B. Cheong, T. Y. Seong, and W. M. Kim. 2009. Effects of substrate
temperature and Zn addition on the properties of Al-doped ZnO films prepared by magnetron
sputtering. Applied Surface Science 255: 725156. doi:10.1016/j.apsusc.2009.03.075
Klingshirn, C. 2007. ZnO: Material, physics and applications. ChemPhysChem 8: 782803.
doi:10.1002/cphc.200700002
1288 C. LUNG ET AL.
Kobayakawa, S., Y. Tanaka, and A. Ide-Ektessabi. 2006. Characteristics of Al doped zinc oxide (ZAO)
thin films deposited by RF magnetron sputtering. Nuclear Instruments and Methods in Physics
Research Section B: Beam Interactions with Materials and Atoms 249: 53639. doi:10.1016/j.
nimb.2006.03.047
Lee, H. W., B. G. Choia, K. B. Shima, and Y.-J. Oh. 2005. Preparation of Ti-doped ZnO transparent
conductive thin films by PLD method. Journal of Ceramic Processing Research 6: 5256.
Lee, J., D. Lee, D. Lim, and K. Yang. 2007. Structural, electrical and optical properties of ZnO:Al
films deposited on flexible organic substrates for solar cell applications. Thin Solid Films 515:
609498. doi:10.1016/j.tsf.2006.12.099
Lee, S. J., H. S. Lee, D. Y. Kim, and T. W. Kim. 2005. Microstructural, optical, and magnetic
properties of (Zn1-xMnx)O thin films grown on (0 0 0 1) Al2O3 substrates. Journal of Crystal
Growth 276: 12127. doi:10.1016/j.jcrysgro.2004.11.300
Muiva, C. M., T. S. Sathiaraj, and K. Maabong. 2011. Effect of doping concentration on the
Downloaded by [INCDTIM Cluj-napoca], [Marconi Daniel] at 23:36 19 May 2016
properties of aluminium doped zinc oxide thin films prepared by spray pyrolysis for transparent
electrode applications. Ceramics International 37: 55560. doi:10.1016/j.ceramint.2010.09.042
Pedarnig, J. D., J. Heitz, T. Stehrer, B. Praher, R. Viskup, K. Siraj, A. Moser, et al. 2008.
Characterization of nano-composite oxide ceramics and monitoring of oxide thin film growth
by laser-induced breakdown spectroscopy. Spectrochimica Acta Part B: Atomic Spectroscopy 63:
111721. doi:10.1016/j.sab.2008.06.012
Reynolds, D. C., D. C. Look, and B. Jogai. 1996. Optically pumped ultraviolet lasing from ZnO. Solid
State Communications 99: 87375. doi:10.1016/0038-1098(96)00340-7
Sui, Y. R., B. Yao, L. Xiao, L. L. Yang, J. Cao, X. F. Li, G. Z. Xing, 2013. Fabrication and
characterization of PN dual acceptor doped p-type ZnO thin films. Applied Surface Science
287: 48489. doi:10.1016/j.apsusc.2013.10.010
Swanepoel, R. 1983. Determination of the thickness and optical constants of amorphous silicon.
Journal of Physics E: Scientific Instruments 16: 121422. doi:10.1088/0022-3735/16/12/023