Materials Research Express

PAPER

A structural study of the growth of ZnOx thin films by thermal evaporation

in vacuum followed by heat treatment in air
To cite this article: D Bulut and M H Yükselici 2019 Mater. Res. Express 6 056408

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 Mater. Res. Express 6 (2019) 056408 https://doi.org/10.1088/2053-1591/ab0251

PAPER

A structural study of the growth of ZnOx thin films by thermal

RECEIVED
12 December 2018
evaporation in vacuum followed by heat treatment in air
REVISED
24 January 2019
ACCEPTED FOR PUBLICATION
D Bulut and M H Yükselici
28 January 2019 Yildiz Technical University, Davutpaşa Campus/Faculty of Art and Sciences, Department of Physics, Davutpasa Cad. PK: 34210 Esenler/
PUBLISHED Istanbul/Turkey
6 February 2019
E-mail: yukseli@yildiz.edu.tr

Keywords: thin films, ZnO, physical vapor deposition

Abstract
ZnO thin films were grown on glass slides by thermal evaporation of zinc powder in vacuum followed
by heat treatment in air. The films were characterized by x-ray diffraction (xrd), Raman scattering and
scanning electron microscopy (SEM). Xrd pattern for as-deposited thin film sample consists of
hexagonal Zn structure with slight wurtzite ZnO texture. It is observed that the heat-treatment at
between 450 and 600 °C for 1 to 3 h turns the xrd pattern almost completely to wurtzite ZnO structure.
SEM micrographs display flakes like hexagonal button shaped grains for as-deposited thin film which
turns to needle like nanometer size structures with heat treatment. The red shift of some vibrational
modes in Raman spectra for as-deposited thin film relative to the heat treated films and the
introduction of a line at around 582 cm−1 indicate that ZnO thin films have defects such as oxygen
vacancies or zinc interstitials. The most intense Raman mode due to high frequency oxygen vibration
for as-deposited zinc film is red-shifted by about 7 cm−1 relative to the Raman mode for the ZnO thin
film heat-treated.

1. Introduction

Organic, crystal or hybrid thin film structures have potential for technological applications such as light emitting
diodes (LED), gas, pressure and temperature sensing detectors and two or three dimensional imaging, and solar
cells. Most of the research has been conducted on CdSxSe1−x thin films and nanocrystals however the rise of
health consciousness against highly volatile and toxic heavy metals such as Cd forced scientist to develop devices
based on other compounds like pure ZnO or composite ZnO/CuO2 [1] for hazard free technology. ZnO is a
wide band gap energy semiconductor of 3.37 eV with large exciton binding energy of around 60 meV which
makes it stable against thermal disassociation of excitons and thus high intensity excitonic emission required for
LED applications becomes possible [2, 3]. ZnO thin film semi-conductor might be used as a detector which
precisely senses ethanol gas [4, 5] has catalytic properties [4, 6–9] and might replace expensive ITO layer in solar
cells [10]. Weijia et al synthesized ternary CdS/ZnO/graphene based catalysts and scrutinized photo-
electrochemical performance under radiation [11]. The effect of defects on device performance in ZnO thin film
electro-deposited on Fluorine doped Tin Oxide (FTO) glass based heterojunction and on the structure of ZnO
nanorods grown on glass prepared by sol-gel and hydrothermal method were studied by Jianguo et al [12, 13].
ZnO thin films have been studied for about a quarter century with the majority of research conducted in recent
years. Fujimura et al [14] developed mechanisms such as alteration of O2 percentage during deposition, sample
geometry, substrate temperature, rate of vaporization to control the texture formation in ZnOx films deposited
by radio frequency magnetron sputtering. Rusu et al [15] deposited zinc thin films on glass substrates by thermal
evaporation in vacuum and prepared ZnO thin films by thermal oxidation in air. They reported the results of
structural and optical measurements and characterized ZnO thin films in detail. Mihailova et al [16] studied
ZnO thin films deposited by magnetron sputtering followed by thermal oxidation. Their xrd and Raman results
show that the deposition rate has no significant effect on the crystallinity of the ZnO thin films. However heat-
treatment at 550 °C for 15 min was enough to oxidize zinc. Kumari et al [17] prepared ZnO and zinc rich ZnO

© 2019 IOP Publishing Ltd

Mater. Res. Express 6 (2019) 056408 D Bulut and M H Yükselici

Figure 1. Schematic view of vacuum chamber. Deposition geometry 1 (lower right corner) and 2 (upper right most corner). The angles
for geometries 1 and 2 are, in degree, q1 = 25.07, q2 = 18.06, j1 = 64.93, j2 = 71.94 and
q1 = 11.14, q2 = 10.36, j1 = 78.86, j2 = 68.5 respectively.

thin films by chemical vapor deposition and discussed the defect structure including anti-site defects and
interstitials with the help of x-ray diffraction (xrd) and Raman scattering. In this work we present the results of
xrd, Raman and scanning electron microscopy (SEM) for ZnOx thin films deposited by thermal evaporation in
vacuum followed by heat-treatment in air. We present a discussion to exploit the red-shift observed in the
vibrational frequencies of ZnO thin film using the results of xrd pattern and Raman spectra.

2. Experimental

2.1. Thermal evaporation

Thin films were deposited on glass substrates by vacuum evaporation of zinc powder of purity of 99.995%
supplied by Sigma Aldrich-324930. Glass slides were immersed in 1.85% HCl for 5 min and then washed with
methanol and distilled water and finally wiped with lens cleaning tissues before the deposition process. Thin
films were grown on glass slides by resistive heating of zinc powder in tungsten boat (source) in vacuum chamber
unit (PVD-HANDY/25-TE) produced by VAKSIS. Films were deposited under an ultimate pressure acting on
the vapor on the order of 10−5 Torr when the current passing through the boat was 70 A. In figure 1 a schematic
view of vacuum chamber is shown. We note that the deposition of zinc on glass slide strongly depended on the
distance (h) between the source and the glass substrate (target). The deposition rate which depends on
vaporization rate varies with geometry. The Hertz-Knudsen vaporization rate is proportional to the difference
between vapor pressure of the evaporant (Pvp) and the pressure (P) in the vacuum chamber at a given
temperature (T): dN dt µ (Pvp - P ) T [18]. We expect quite high rate of vaporization as P→0 due to the
relatively high equilibrium vapor pressure of ∼10−2 torr of zinc at melting point of ∼415 °C which makes Zinc
vapour quite volatile [19]. However, we observe no deposition on the glass substrate at distances above 12 cm
between the source and the target although the metal walls of the vacuum chamber around the sample and the
quartz sensor were deposited well with zinc which turned greyish. The cosine deposition distribution equation
relates mass per unit area to the angular distribution of the depositing flux and the source-target distance (r):
dm dA µ cos q cos j r 2 where the angles were shown in figure 1. While the ratio of mass per unit area for
geometry 2 to geometry 1 is 4.4 for the first set of angles, the same ratio is 11.4 for the second set of angles. A
number of zinc thin films were deposited on glass slides using geometry 2 with second set of angles to maximize
the deposition and heat-treated in air at temperatures between 450 and 600 °C for time intervals from 1 to 3 h to
grow ZnO. The samples were characterized by xrd, Raman scattering and SEM. The results show that heat-

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Figure 2. The XRD pattern of as-deposited Zn thin film (a), heat-treated for 2 h at 500 °C (b) and for 3 h at 600 °C (c) after deposition.
The solid lines through the data points are the result of a curve fit which consist of a Lorentzian line profile for each peak and a
polynomial background.

treated samples have similar properties regardless of heat-treatment temperature and time unlike as-deposited
thin films. Therefore we mainly concentrate on two thin film samples: (i) as-deposited zinc thin film and (ii) zinc
thin film heat-treated at 600 °C for 3 h.

2.2. XRD
X-ray diffraction (xrd) patterns of thin films were recorded on Bruker D8 Advance diffractometer. The
representative xrd spectra are presented in figure 2. Each peak was fitted by a Lorentzian function with a
polynomial background and the best fit parameters were determined for peak positions and full width at half
maximum (FWHM). We initially made use of literature values for hexagonal lattice constants for bulk ZnO
crystal to assign Miller Indices (h, k, l) to each diffraction peak in xrd spectra [20]. We then used h=0, k=0,
l≠0 and h≠0 or k≠0 and l=0 values along with the angular position of diffraction peaks to determine
lattice constants c and a respectively. The XRD spectrum for as-deposited Zn thin film in figure 2(a) displays
diffraction peaks at the angles of 38.95°, 43.19°, 54.32° and 70.11° attributed to the (100), (101), (102) and (110)
and/or (103) planes of hcp Zn structure respectively [21]. The most intense peak at 36.27° might be due to the
(101) plane of hcp Zn and/or the (002) plane of wurtzite ZnO. The low intensity peak at 34.72° is attributed to
the (002) plane of wurtzite ZnO which indicates partial oxidation during vacuum deposition. The ZnO peaks
grow at the expense of Zn with the heat treatment at temperatures between 450 and 600 °C. Figure 2(b) displays
the xrd spectrum for a thin film sample heat treated at 500 °C for 2 h and figure 2(c) at 600 °C for 3 h after
deposition. The peaks between 45° and 70° in figure b at angles 47.46°, 56.52°, 62.82° and 68.00° due to the
(102), (110), (103) and (112) planes of wurtzite ZnO respectively. The Zn peak at 43.19° after deposition
decreases in magnitude with heat treatment at 500 °C for 2 h as shown in figure 2(b) and finally disappears with
heat treatment at 600 °C for 3 h as shown in figure 2(c). We also note the rise of ZnO peak at 31.36° with heat
treatment. The most intense peak located at 36.27° prior to heat-treatment and at a slightly shifted position
36.14° after heat-treatment attributed to the (101) plane of wurtzite ZnO and/or the (002) plane of hcp Zn.

2.3. SEM
Zeiss EVO LS 10 scanning electron microscope (SEM) was employed for the surface morphological analysis.
SEM micrographs are given in figure 3 for as-deposited ZnO thin film (a) and for ZnO thin films heat-treated at
450 °C for 1 h (b) 500 °C for 1 h (c) 500 °C for 2 h (d) 500 °C for 2 h (high magnification image) (e) and 600 °C
for 3 h (f). The progression of as-deposited thin films from a zinc rich structure as shown in figure 3(a) to a zinc
oxide structure with heat-treatment in air is observed. Figure 4 shows energy dispersive x-ray spectrum (EDS)
for as-deposited ZnO films (a) and ZnO films heat-treated after deposition at 600 °C for 3 h (b). In the same plots

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Mater. Res. Express 6 (2019) 056408 D Bulut and M H Yükselici

Figure 3. Surface SEM micrographs of as-deposited Zn thin film (a) and heat-treated for 1 h at 450 °C (b) for 1 h at 500 °C (c) for 2 h at
500 °C (d) same as in (d) high magnification (e) for 3 h at 600 °C (f) after deposition.

element composition tables are also shown. Similar SEM micrographs have been reported earlier [16, 22].
Mihailova et al deposited Zn glass slides by thermal evaporation in vacuum and oxidized at 530 °C for 15 min in
air and grown needle shape nanostructures. Shaik et al prepared ZnO thin films by conducting different routes of
thermal evaporation and oxidation. However a route including deposition of Zn thin film and then annealing in
air lead to thin films with needle like nanometer size structures. In the present work, SEM micrographs display
flakes like hexagonal button shaped grains for as-deposited thin film which turns to needle like nanometer size
structures with heat treatment displaying pile of straw stock (b) The needle like structures grow with increasing
heat treatment time and/or temperature (c, d and f). A higher magnified image for the thin film annealed at
500 °C for 2 h is presented in figure 3(e) to show the form of needle like structures.

2.4. Raman scattering

Raman measurements were carried out on Renishaw 250 mm focal length in Via Spectrometer system using
Rayleigh line rejection filter allowing Raman spectrum to 100 cm−1 from a laser line. Raman spectra excited by a
cw laser line at 532 nm are presented in figure 5(a) for as deposited Zn thin film, in figure 5(b) for the Zn thin film
heat treated at 500 °C for 2 h and in figure 5(c) for the Zn thin film heat treated at 600 °C, for 3 h. We presume

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Mater. Res. Express 6 (2019) 056408 D Bulut and M H Yükselici

Figure 4. EDS spectra and element composition tables of as-deposited (a) and heat-treated for 3 h at 600 °C (b) ZnO thin films.

that the as-deposited thin films are partially oxidized prior to heat treatment and rich in zinc as suggested by the
xrd results discussed in section 4. The evolution of Raman spectrum for as deposited thin film rich in zinc to
Raman spectrum of ZnO thin film as a result of heat treatment is in support of this proposal. The intense Raman
mode at ∼439 cm−1 belongs to E2 symmetry group assigned to oxygen vibration at high frequency in ZnO
(E 2high ) and the other member of E2 symmetry is assigned to zinc vibration at low frequency (not shown) (E 2low )
[23–25]. The peak at 331.94 cm−1 is assigned to the difference mode between high and low frequency modes
E 2high - E 2low. The lines at 205.94, 331.94 and 439 cm−1 observed in figure 5(b) are red-shifted by 7 to 9 cm−1 in
figure 5(a) due to possible oxygen vacancies in zinc rich ZnO thin film [24]. Besides the observation of peak at
around 582 cm−1 for all of the heat treated thin films which is absent in as-deposited thin film might indicate
oxygen deficiency or zinc interstitials [26]. The low intensity peaks at 382.06 and 582.91 cm−1 are reported
previously and assigned to A1(TO) and A1(LO) Raman modes [17]. The broad lines at between 1000 and
1200 cm−1 in figure 5 b were also reported by Nikitenko et al [27] who studied ZnO powders and by Wang et al
[28] who identified the line at around 1100 cm−1 as the acoustical combination of A1 and E2 symmetries. The
line at 1156.95 cm−1 is the third optical overtone of A1 symmetry [28]. We note that these lines overlap as
observed in figure 5(a) for the as deposited zinc thin films and are resolved for the zinc films heat treated for 3 h at
600 °C as seen in figure 5(c). The xrd pattern is sensitive to the crystal structure and therefore able to distinguish
hcp Zn and wurtzite ZnO structures. On the other hand the Raman vibrational modes are sensitive to the
composition and therefore a change in the stoichiometry cause a shift in Raman peak positon. Both
measurements are consistent in this regard.

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Mater. Res. Express 6 (2019) 056408 D Bulut and M H Yükselici

Figure 5. Raman spectra of as-deposited Zn thin film (a) heat-treated for 2 h at 500 °C (b) and for 3 h at 600 °C (c) after deposition.

3. Shift in xrd and raman spectra

Two main contributions to the shift in Raman vibrational modes include strain and phonon confinement due to
finite size of grains. The observed peak position for the i th mode [29, 30] is given by
Pi = Pibulk + Dw conf
i + Dw istrain where Pibulk is the bulk peak position, Dw conf
i the shift due to phonon
confinement and Dw i strain
shift due to strain. The zone center phonon dispersion is at a maximum therefore we
do not expect a blue shift due to phonon confinement [31, 32]. However the Raman spectra display blue shift for
the vibrational lines. The Grüneisen parameter (γ) relates the change in peak position of Raman lines (ω) to the
change in crystallite’s unit cell volume (V ), g = - ¶¶InVInw
. We find, after integrating from an initial vibrational
Dw DV
frequency at an initial volume to a final one w
= -g V . We determine ΔV/V in terms of lattice constants for
DV Da Dc
hexagonal crystal structure, V = 2 a + c
. The diffraction peaks in xrd spectra shift and broaden due to
finite size of grains, strain and instrumental errors. The total broadening is the sum of these three contributions
[21, 33, 34]. The full width at half maximum (FWHM) decreases with increasing grain radius and the peak
position is shifted due to strain. By using the results of xrd analysis we determine a1=0.325511 nm and
c1=0.516183 nm for the as-deposited ZnO thin film and a2=0.325835 nm and c2=0.521720 nm for the
ZnO thin film heat-treated at 600 °C for 3 h. We employ literature value for γ=−1.6 and find
(Δω/ω)xrd=0.02. The ratio of the blue shift in the E 2high line from 432.11 cm−1 for as-deposited film to
438.9 cm−1 for heat-treated film in Raman spectra is (Δω/ω)Raman=0.015 which is less than
(Δω/ω)xrd=0.02. We estimate the average size of grains to assess relative weight of phonon confinement on the
overall shift and understand whether the difference of 0.005 cm−1 between two values is due to phonon
confinement. We employ Debye–Scherrer relation to estimate grain size: D (2qhkl ) = 0.89l /2R ave cos qhkl
where Rave is the average radius of grains and Cu Kα(λ)=1.54016 Å is the wavelength of the x rays. The values
Δ(2θ002)=0.37×π/180 rad and θ002=34.72/2 deg yield Rave=∼11 nm for as-deposited ZnO thin film and
the values Δ(2θ002)=0.32×π/180 rad and θ002=34.34/2 deg yield Rave=∼13 nm for ZnO thin film heat-
treated at 600 °C for 3 h. We note that the exciton Bohr radius for bulk ZnO crystal of ∼1.8 nm is an order of
magnitude less than the grain size estimated here. That is why we do not expect quantum size effect play any
significant effect on the shift observed in xrd and Raman spectra.

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Mater. Res. Express 6 (2019) 056408 D Bulut and M H Yükselici

4. Discussion

The xrd data presented in figure 2 indicate the transformation from a zinc rich hcp structure to a zinc oxide
wurtzite structure by partial oxidation in air due to: (i) the emergence of a peak at 31.66° attributed to the (002)
plane of ZnO with heat treatment at 500 °C for 2 h and the increase in its magnitude with heat treatment at
600 °C for 3 h , (ii) the rise of ZnO peaks with heat treatment at between 45° and 70° as observed in figure 2 at
angles 47.44°, 56.49°, 62.8° and 67.88° due to the (102), (110), (103) and (112) planes of wurtzite ZnO
respectively (b) and (c) and (iii) the persistence of the most intense peak at 36.27° before heat-treatment (see
figure 2(a)) and at 36.14° after heat-treatment (see figure 2(b)) attributed to the (101) plane of wurtzite ZnO and/
or the (002) plane of hcp Zn. Furthermore, it is evident from the EDS spectrum/table presented in figure 4 that
the wt % decreases (increases) from 2.28 (1.15) to 1.46 (3.49) for zinc (oxygen) with heat-treatment at 600 °C for
3 h. SEM micrographs display flakes like hexagonal button shaped grains dispersed uniformly for as-deposited
thin film as shown in figure 3(a) which turns to needle like nanometer size structures with heat treatment as
shown in figures 3(c)–(f). That the diffraction peaks in figure 2(a) display patterns which are due to both ZnO
and Zn crystal structure and that the atomic percentage of oxygen of 11.15 increase to 55.21 while that of zinc of
62.16 decreases to 31.32 during post deposition heat treatment according to EDS data presented in element
composition tables in figure 4 suggest that zinc deposited films under vacuum are partially oxidized during
deposition prior to the heat treatment. That is why we emphasize oxygen deficiency with 0<x„1: ZnOx. We
propose that the equilibrium conditions in our deposition chamber favour both the growth on (002) and (101)
planes of hexagonal crystal structure. Such a competitive growth between (002) and (101) planes has been
reported previously in literature [15]. The crystal plane with the lowest density of surface energy is the one
constructed by Wulff’s method [35]. However it should be noted that a change in deposition condition might
lead to different crystal pattern as reported by Fujimura et al [14] who found the lowest energy density of
0.099 eV A−1 for the ZnO thin film growth on the (0001) plane of hexagonal crystal system under the gas
composition of Argon of 75% and Oxygen of 25%. We calculated the relative shift due to strain with the help of
xrd texture and Raman spectra and found that both results agree: (Δω/ω)Raman≈(Δω/ω)xrd.

5. Conclusion

We have studied ZnO thin films grown on glass slides by thermal evaporation in vacuum. The SEM images show
that as-deposited films are rich in zinc and oxidized upon heat treatment in air at temperature range from 450 to
600 °C for time intervals between 1 and 3 h. Both the xrd and Raman results agree with SEM. The xrd pattern for
as-deposited thin film displays a zinc hcp structure which transforms to ZnO wurtzite structure with heat-
treatment. The nanometer size needle like structures are grown with heat treatment after deposition. We
employed Grüneisen model to relate the shift in Raman modes to the strain and found that the strain extracted
from results of xrd analysis presented in section 2.2 are consistent. The red shift of the intense mode at around
439 cm−1 in Raman spectra for as-deposited thin film relative to the heat treated films and the introduction of a
line at around 582 cm−1 indicate that ZnO thin films have defects such as oxygen vacancies. We related the shift
in vibrational modes to the lattice contraction/stretch which were determined with the help of xrd texture and
Bragg Law and then estimated the relative shift in Raman lines. A direct calculation of relative shift in vibrational
frequencies from the observed shift in Raman spectra agree well with the shift calculated using xrd data.

Acknowledgments

This work was conducted at Yıldız Technical University (YTU) and supported by YTU Scientific Research
Projects Coordination under project no 2014-01-01-DOP01.We thank Prof Dr Şaban Aktaş at Physics
Department, Faculty of Science, Trakya University for SEM micrographs.

ORCID iDs

D Bulut https://orcid.org/0000-0003-3373-2681
M H Yükselici https://orcid.org/0000-0001-5052-5575

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