PROGRESS IN PHOTOVOLTAICS: RESEARCH AND APPLICATIONS

Prog. Photovolt: Res. Appl. 2011; 19:149–154

Published online 23 July 2010 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/pip.999

RESEARCH ARTICLE

Comparative study of ZnO thin films prepared by

plasma deposition and electron beam evaporation
for use in photovoltaic devices
V. D. Falcão1,2*, D. O. Miranda2,3, M. E. L. Sabino2,3, T. D. O. Moura2,3, A. S. A. C Diniz4,
L. R. Cruz5 and J. R. T. Branco2,3
1
Instituto Federal de Educação Ciência e Tecnologia de Minas Gerais – IFMG Campus Congonhas, Congonhas/MG, Brazil
2
Rede Temática em Engenharia de Materiais – REDEMAT, Ouro Preto/MG, Brazil
3
Fundação Centro Tecnológico de Minas Gerais – CETEC, Belo Horizonte/MG, Brazil
4
Companhia Energética de Minas Gerais – CEMIG, Belo Horizonte/MG, Brazil
5
Instituto Militar de Engenharia - IME, Rio de Janeiro/RJ, Brazil

ABSTRACT
Undoped zinc oxide thin films were grown at room temperature using two techniques: plasma deposition (PD) and electron
beam evaporation in an argon atmosphere. PD offers some advantages, such as low ion damage and low deposition
temperature. The optical transmittance of the films deposited by both methods was higher than 80% in the near UV–VIS
range; the energy band gap and index of refraction agree with values reported in the literature. The resistivity of films grown
by PD was 3.1
102 V cm, lower than the value of 1.2
101 V cm found for plasma assisted e-beam evaporated films.
Copyright # 2010 John Wiley & Sons, Ltd.
KEYWORDS
zinc oxide; plasma deposition; transparent conductive oxide; photovoltaic devices
*Correspondence
V. D. Falcão, Instituto Federal de Educação, Ciência e Tecnologia de Minas Gerais – IFMG Campus Congonhas, Congonhas/MG,
Brazil.
E-mail: vivienne.falcao@ifmg.edu.br

Received 29 October 2009; Revised 5 March 2010

1. INTRODUCTION used, such as chemical spray pyrolysis [10], sputtering [11],

Nowadays zinc oxide (ZnO) thin films are investigated as
transparent conductive electrodes for use in optoelectronic
devices including flat displays, thin films transistors, and
solar cells because of their unique optical and electrical
properties [1]. This material, which is a wide direct band gap
semiconductor with the hexagonal crystal structure of
wurtzite [2–5], is one of the most promising materials for the
production of new generation photovoltaic devices, and has
gained great commercial and scientific interest compared
with other TCO films, such as indium tin oxide [5–7]. Some
of its numerous advantages include: electrical conductivity
modified by appropriate doping or post-annealing, high
absorption in the ultraviolet range, compatibility with large
scale processes, low cost, abundance, non-toxicity, and easy
fabrication [8,9].
The technology for growing ZnO thin films on a variety of
substrates has been improved, and a lot of method has been
metal–organic chemical vapor deposition [12], electron
beam evaporation [13], and the sol–gel process [14].
In this work, we propose a new method for growing ZnO
thin films, which we called plasma deposition (PD). In this
process, a film is deposited by means of plasma, which
is used to sublimate the source material. This method offers
the advantages of low ion damage, low deposition
temperature, and large area deposition, which allows high
throughput manufacturing. Besides, this method provides
economical and efficient usage of the raw material. We also
grew ZnO films by electron beam evaporation with plasma
assistance (EBPA) and compared the optical and electrical
properties of the films obtained by the two techniques.
2. EXPERIMENTAL
The ZnO thin films were deposited at room temperature
onto sodalime glass substrates by PD and EBPA in a

Copyright ß 2010 John Wiley & Sons, Ltd. 149

Comparative study of ZnO thin films
Balzers BAI 640 R system whose schematic is shown in
Figure 1. Before deposition, the 1.2 mm thick glass
substrates were cleaned using a standard procedure [15]. In
both processes, argon gas was used to form the plasma and
a ZnO target was used as material source. This target was
prepared in our laboratory from ZnO powder (99%)
supplied by ‘‘Votorantim Metais,’’ a Brazilian company of
the Votorantim group. The powder was pressed as small
tablets and sintered at 1400 8C for 1 h. While the PD
process consists of depositing the film from plasma, the
EBPA uses an e-beam source to sublimate the target in the
presence of plasma. The plasma is generated inside an
ionization chamber (plasma source in Figure 1) by means
of a hot tungsten filament. It is then expelled out of the
chamber by the action of a magnetic field. In both process,
the electrons of the plasma are attracted by the positively
biased crucible, establishing plasma current, which is used
to sublimate the target material. On the other hand, the
acceleration of the argon positive ions occurs in the electric
field developed between the anode and the negative
floating potential on the substrate holder. These ions
activate the vaporized neutral atoms prior to the deposition,
providing them enough energy on the surface of the
substrate. The two processes are quite similar, the only
difference lying on the fact that, in addition to the plasma
current, the EBPA uses an extra electron beam to sublimate
the material. The deposition parameters of ZnO films
grown by both techniques are shown in Table I.
Film thicknesses were measured in a Veeco Dektak8
step-height profilometer. To produce a step in the films,
slurry of boron nitrate and distilled water was applied to a
small area of the substrate before deposition. The slurry
was easily removed with isopropyl alcohol after the
deposition to reveal a step in the film down to the substrate.
Resistivity and Hall measurements were performed at
room temperature in a four-probe van der Pauw
configuration, using an Accent HL5500PC system.
X-ray diffraction (XRD) analyses were made on a
Siemens D500 diffractometer with a Cu anode. Cu Ka
radiation was selected by a graphite monochromator.
Typical symmetric u2u scans were taken between 208 and
808 using 0.028 steps.
Figure 1. Schematic of the EBPA and PD techniques.
150 Prog. Photovolt: Res. Appl. 2011; 19:149–154 ß 2010 John Wiley & Sons, Ltd.
V. D. Falcão et al.
Table I. Deposition parameters of ZnO films grown by EBPA
and PD.
Deposition parameters EBPA PD
Background pressure 6
9
10 mbar 9
106 mbar
Beam current 0.07 A —
Plasma current 30 A 75 A
Deposition time 20 min 60 min
Gas Argon Argon
Substrate to target distance 23 cm 23 cm
Optical spectra were obtained in the 190–1000 nm range
using an n&k Technology, Inc. Nkt 1280 spectropho-
tometer. Glass and silicon polished wafers were used as
references for transmittance and reflectance measure-
ments, respectively. The thickness, index of refraction, and
band gap energy data were determined from the optical
spectra using a software based on n&k Method [16–18].
Determination of the optical constants is not a trivial
problem. The refraction index, n, and the extinction
coefficient, k, depend on wavelength and cannot be
measured directly; they must be computed from optical
parameters such as reflectance, R, and transmittance, T.
The n&k method incorporates the Forouhi–Bloomer
formulation [16–18] for the optical constants, n and k,
along with a parameterized model for interface roughness
[19], into the Fresnel coefficients, associated with multi-
layer films on a substrate to generate an algorithm, Rt, that
describes the theoretical reflectance:
 
Rt ¼ Rt l; u; d; nf ðlÞ; kf ðlÞ; ns ðlÞ; ks ðlÞ; Eg ; s 1 ; s 2 (1)
where Rt is the theoretical reflectance, l the wavelength, u
the angle of incidence, d the film thickness, nf(l) and ns(l)
the refraction indexes of the film and substrate, respect-
ively, kf(l) and ks(l) the extinction coefficients of the film
and substrate, respectively, Eg the band gap energy, and s1
and s2 are the interface roughness on top and bottom,
respectively. By comparing the theoretical reflectance with
the measured one, the required parameters of the film [d,
nf(l), kf(l)] can be determined.
DOI: 10.1002/pip.999
V. D. Falcão et al.
The band gap of ZnO films was also obtained from the
experimental transmittance data and from:
a2 ¼ cðhn  Eg Þ
which relates the absorption coefficient (a) to the energy of
the incident photon for direct transitions. In this equation h
is the Planck constant and n is the frequency of incident
radiation. The band gap energy can be determined from the
intercept of the linear portion of the a2 versus hn graph with
the energy axis. The band gap of both EBAP and PD films
was obtained in order to compare them with the values
calculated by n&k method.
3. RESULTS AND DISCUSSION
The optical transmittance and reflectance spectra of ZnO
thin films deposited by EBPA and PD are shown in
Figures 2 and 3, respectively. The solid lines represent
experimental data and the dotted lines represent the n&k
Figure 2. Optical transmittance and reflectance spectra of ZnO
film grown by EBPA.
Figure 3. Optical transmittance and reflectance spectra of ZnO
film grown by PD.
Prog. Photovolt: Res. Appl. 2011; 19:149–154 ß 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/pip.999
Comparative study of ZnO thin films
calculated data. Both films exhibit high transmittances –
above 80% – in visible region, which means that film
stoichiometry has been achieved even for depositions
(2)
carried out in the absence of a reactive oxygen atmosphere.
Sharp fundamental absorption edges are also observed in
both spectra, indicating that films with high quality crystal
structure were obtained even for depositions onto unheated
substrates. The explanation is that the plasma indeed
assists the deposition, playing the same role of the substrate
heating, that is, to increase the mobility of the depositing
atoms and lead to films with better crystallinity. The
absorption edge in the EBPA spectrum is not as sharp as in
PD spectrum, suggesting that defect electronic states such
as oxygen vacancies and/or Zn interstitials [7] within the
band gap of EBPA films may be more active.
Table II summarizes the thickness of ZnO thin films,
as measured in the profilometer, and the parameters
determined using the n&k method. The good-of-fitness
(GOF) between the theoretical and measured reflectance
data (0  GOF  1) is also shown and indicates the fitting
is quite good. The thickness values calculated by the n&k
method are close to the ones measured with the
profilometer. The small difference between calculated
and measured data may be due to the quality of the step
produced on the film surface for profilometer measure-
ments. The optical band gap energies given by n&k
software were 3.15 and 3.10 eV for the films deposited by
EBPA and PD, respectively, and are in good agreement
with the values reported for polycrystalline ZnO films [20].
The literature has ascribed this small difference to
variations in the composition of ZnOx films [21]. The
index of refraction calculated for both films by n&k
method is also in good agreement with the reported values
for ZnO thin films [22]. The value of 2.07 for PD films is
close to that of bulk wurtzite ZnO, which is 2.0 [23] and
indicates the good quality of the film. For films deposited
by EBPA, the value is smaller than that of pore-free
wurtzite, meaning that they are less dense than PD films
[24]. The squared absorption coefficient (a2) versus the
photon energy, near the fundamental absorption region, for
films deposited by EBPA and PD, was plotted in Figure 4 in
order to determine the optical gap, Eg. ZnO, being a direct
band gap semiconductor, has an absorption coefficient
which obeys Equation (2) for high photon energies. The
band gap values are quite similar and close to the values
calculated by the n&k method.
Figure 5 shows the XRD profiles of ZnO films deposited
by EBPA and PD. The result confirms our previous
hypothesis about the excellent crystallinity of the films
grown by both techniques. Both films show the hexagonal
wurtzite structure with the presence of high intensity (002)
peaks indicating a strong orientation along c(002)-axis
normal to the surface of the substrate. This result can be
attributed to the low temperature of the substrate that
favored the spontaneous growth of crystal planes with low
surface energy, such as the (002) plane. By comparing the
two profiles, one can also observe that the uniformity of the
lattice constant along the sample in PD films is higher than
151
Comparative study of ZnO thin films V. D. Falcão et al.

Table II. Thickness and optical constants of ZnO thin films grown by EBPA and PD.

Profilometer Parameters determined using the n&k method

Deposition Thickness (nm) Thickness (nm) GOF Refraction Band gap

method index energy (eV)

EBPA 530.0 459.3 0.9851 1.87 3.15

PD 522.5 553.4 0.9934 2.07 3.10

in EBPA films, as shown by the smaller full width at half
maximum (FWHM) of the (002) peak. This is attributed to
the lower deposition rate used for growing PD films.
The Hall measurement results of ZnO thin films
deposited by EBPA and PD are shown in the Table III.
The films are n-type, as indicated by the sign of the Hall
coefficient. The carrier concentration in PD samples is one
order of magnitude larger than in EBPA samples. Since
carrier density in undoped ZnO films is controlled by
oxygen vacancies and/or interstitial Zn ions, this result
indicates that the density of these defects is larger in PD
films. On the other hand, the XRD results suggest that the
lattice constant in PD samples is more uniform. This
apparently facilitates the activation of interstitials Zn ions
and oxygen vacancies, leading to a greater carrier
concentration. The mobility in PD films is smaller than
in EBPA films, despite the better crystallinity. The reason
for this is the higher carrier concentration, which is one

Figure 4. Typical plots of squared absorption coefficient versus photon energy for ZnO films grown by EBPA and PD.

Figure 5. XRD patterns of ZnO films prepared on glass substrates by EBPA and PD.

152 Prog. Photovolt: Res. Appl. 2011; 19:149–154 ß 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/pip.999
V. D. Falcão et al.
Table III. Hall measurements results of ZnO thin films deposited by EBPA and PD.
Sample Resistivity (V cm)
EBPA 1.22
101
PD 3.16
102
order of magnitude greater in PD than in EBPA samples.
Carrier mobility is proportional to the time between
collisions, which is reduced not only by electron–phonon
and electron-defect scattering, but also by electron–
electron scattering. In the present case, with carrier
concentration values as high as 1019 cm3, this effect
should be relevant. The overall result is that resistivity of
PD-ZnO films is smaller than that of EBPA-ZnO films.
The resistivity of 3
102 V cm is an excellent value
for films deposited at room temperature [25] and may
be further improved in order to achieve the values reported
for aluminum-doped sputtered ZnO films, which are
of the order of 103 to 104 V cm, a resistivity range
which is considered to be appropriate for photovoltaic
applications [26].
4. CONCLUSIONS
Highly oriented, transparent, and conducting ZnO films
have been deposited at room temperature by EBPA and PD.
Optical constants obtained using the n&k method closely
agreed with the values reported in the literature. Both films
presented excellent crystallinity favored by the presence of
the plasma. The films grown by PD had better crystallinity
and electrical properties, probably due to the low
deposition rate used in the process. Although the optical
properties of the films obtained in these works are quite
acceptable, the electrical resistivity must to be lowered
somewhat for photovoltaic applications. However, con-
sidering that the films are undoped, the resistivity can be
considerably improved by proper doping the films.
ACKNOWLEDGEMENTS
This work was supported by CAPES, FAPEMIG, and
CEMIG. The authors would like to thank Dr. Yueqin
Xu, Dr. Helio Moutinho, and Dr. Ramesh Dhere from
NREL for helpful discussions.
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DOI: 10.1002/pip.999