Thin Solid Films 515 (2007) 8699 8704

www.elsevier.com/locate/tsf

On the structural changes during thermal oxidation

of evaporated Zn thin films
G.G. Rusu a , M. Rusu a,, N. Apetroaei b
a
Solid State and Theoretical Physics Department, Al.I. Cuza University, Carol I Blvd., No. 11. Iasi 700506, Romania
b
Plasma Physics Department, Al.I. Cuza University, Iasi 700506, Romania

Available online 1 April 2007

Abstract

Metallic Zn thin films (d = 200 nm500 nm) were deposited in vacuum onto unheated glass substrate by quasi-closed volume technique at a
source temperature of 723 K. Sets of samples simultaneously deposited on horizontally and vertically arranged substrates were prepared. The as-
deposited Zn films were heated under ambient atmosphere at various temperatures ranged between 300 K and 650 K. By XRD and AFM
techniques, the microstructural characteristics and their changes during Zn films heating were investigated. The influence of the deposition
conditions on the structural changes during the oxidation process is also discussed.
2007 Elsevier B.V. All rights reserved.

Keywords: Vacuum evaporation; Zinc oxide; Thin films; Structural characteristics

1. Introduction
Zinc oxide (ZnO) thin films belong to the class of transparent
conductive oxide films and are subject of numerous investiga-
tions due to their great technological importance in highly
integrated optoelectronic devices and transparent electronics.
Many growth techniques such as chemical vapor deposition [1],
electro-deposition [2], the sol-gel technique [3], metal-organic
chemical vapor deposition [4,5], spray pyrolysis [6], r.f.
magnetron sputtering [7], pulsed laser deposition [8,9], etc.
were used to prepare ZnO thin films. Another technique used
for the preparation of the oxide films is the thermal oxidation of
vacuum-deposited metallic (Cd, Sn, In) films [10,11]. Com-
pared with other deposition techniques, this is a relative simple
and without any catalyst method. Due to the relative easy
control of the deposition parameters, the physical vapor
deposition (PVD) permits to prepare both small and large area
metallic coating films. Also, the temperature for their further
thermal oxidation is enough moderate to be easily applied in
thin-film device technology.
Corresponding author. Tel.: +40 232 201165; fax: +40 232 201150.
E-mail addresses: rusugxg@uaic.ro (G.G. Rusu), mirusu@uaic.ro
(M. Rusu), neculairo@yahoo.com (N. Apetroaei).
0040-6090/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2007.03.105
However, this method is still little used to obtain ZnO films.
In our previous paper, some electrical and optical properties of
the ZnO films prepared by this method were investigated [12].
Our experimental measurements of the electrical resistivity of
Zn films during their thermal oxidation revealed a fast increase
of the electrical resistivity starting on temperature of 550 K.
Simultaneously, a modification of Zn film color from silver-
grey, at room temperature, to black-brown at temperature of
about 500 K and, finally to a white-like transparent aspect at
higher temperature was observed. This behavior makes evident
the structural changes that take place during film oxidation.
In present paper, a detailed study on these structural modi-
fications during the thermal oxidation of Zn films deposited by
PVD technique is presented.
2. Experimental
The metallic zinc was evaporated in standard vacuum
equipment by quasi-closed volume technique onto unheated
glass substrates. The used experimental setup consists in a
vertical quartz cylinder ( 8 cm high) placed between Zn
evaporation source and the substrate holder. To study the
influence of the substrate position relative to the evaporation
source during film deposition on the structural characteristics
of the films, a set of samples simultaneously deposited on
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Table 1
Growth and structural data of the typical studied samples
Sample d (nm) (degree) r (nm/s) D (nm)
300 K 550 K 650 K
Z1 240 0 4 25.2 14.7 19.9
Z2 420 60 7 24.6 14.9 20.5
dfilm thickness; incidence angle; rgrowth rate; Daverage crystallite
size at various heating temperature.

similar conditions with constant heating rate of 5 K/min. To

Fig. 1. XRD patterns for normally evaporated Zn film (sample Z1) at various
heating temperature: (a) as-deposited; (b) after first heating up to 550 K; (c) after
second heating up to 650 K.
horizontally and vertically arranged substrates was prepared. A
special substrate holder mounted on the lateral wall of the
deposition chamber was used to obtain obliquely deposited Zn
films. For such samples, the angle between the normal to the
substrate and the direction of the incident vapors was about 60.
The evaporation source temperature, Tev, maintained constant
during the film deposition, was of 723 K. More details of the
used experimental setup are presented in [13].
The film thickness, d, measured with an interference micro-
scope, varied between 200 nm and 500 nm.
After deposition, Zn films were heated under ambient
atmosphere in the temperature range from 300 K to 650 K.
Because the structural and physical properties of the thermal
oxidized films are influenced both of the time and temperature
of heat treatment [10,14], all studied samples were heated in
investigate the temperature dependence of the structural
modifications, the samples were heated step by step up to
various temperatures. After each step, the samples were cooled
down to room temperature and XRD and AFM measurements
were performed. Then, the respective samples were heated
again to the higher temperature and so on. For a correct analysis
of the experimental results, both the XRD and AFM dates were
recorded successively on the one and the same typical sample,
before and after their heating up to various temperatures.
The structure of the as-deposited and annealed samples was
investigated using standard X-ray diffraction (XRD) technique
with CuK radiation ( = 1.5418 ) in the 2 range of 2080.
Atomic force microscope in the tapping mode was used to study
the surface topography of the films. A commercial standard
silicon cantilever N8C 21 having a force constant of 17.5 Nm 1,
210 kHz resonance frequency and tip with 10 nm radius was used.
3. Results and discussion
3.1. XRD studies
Typical XRD patterns for two representative Zn films grown
simultaneously onto normal and oblique substrates are shown
in Figs. 1 and 2, respectively. Some deposition parameters
for these films are indicated in the Table 1. As it results from
Figs. 1a and 2a, the respective as-deposited Zn samples are
polycrystalline and have a hexagonal structure [15]. It may be
observed that the substrate position during evaporation of Zn
films influences the preferential orientation of the crystallo-
graphic planes. Whereas the obliquely deposited Zn film
presents a crystalline structure similar to bulk Zn, with
crystallites light (101) oriented, the normally deposited sample
has a pronounced textured structure. The sharp diffraction peak
at 2 = 36.3 from Fig. 1a corresponds to the (002) plane of the
hexagonal Zn structure and indicates that, in respective film, the

Table 2
Relative intensity Ihkl of XRD peaks for two representative as-deposited Zn
films
Sample Ihkl (%)
(002) (100) (101) (102) (103)
Z1 100 9.5 50.2 13.3 18.1
Z2 26.2 13.9 100 16.4 5.7
Zn hexagonal phase [15] 53 40 100 28 25
Fig. 2. XRD patterns for obliquely evaporated Zn film (sample Z2) at various
heating temperature: (a) as-deposited; (b) after first heating up to 550 K; (c) after The data for Zn films have been normalized relative to the maximum intensity
second heating up to 650 K. peak for each pattern.
 G.G. Rusu et al. / Thin Solid Films 515 (2007) 86998704 8701

crystallites grow preferentially with the (002) plane parallel to
the substrate. The calculated data from Table 2 confirm this
conclusion. In the respective table, the relative intensity, Ihkl, of
different diffraction peaks of as-deposited Zn samples,
normalized to the maximum line for each pattern are presented.
In the same table, the standard intensities for Zn powder are
indicated. One may observe that the value of I002 (100%),
corresponding to the peak (002) in the diffraction pattern of the
normally deposited Zn film is much greater than the standard
value (53%). This indicates that the film crystallites grow with
their c-axis normally to the substrate. This feature can be cor-
related with the fact that the [002] direction is a close-packed
one, leading to a preferred growth in this direction [16,17]. The
substrate position during the film preparation and the lower
value of the growth rate (of 4 nm/s for normally deposited
sample compared with those of 7 nm/s for obliquely deposited
sample) may also favor the observed structural behaviors.
The XRD patterns for the same two typical samples, re-
corded after first heating step, are presented in Figs. 1b and 2b.
The well defined diffraction peaks at 2 = 31.7, 34.4, 36.2
and 47.6 from both figures, are characteristic for polycrystal-
line structure of bulk ZnO [18] and indicate the formation of

Fig. 3. AFM images for normally deposited Zn film (sample Z1) heated up to various temperature: (a) as-deposited; (b) after first heating up to 550 K; (c) after second
heating up to 650 K.
8702 G.G. Rusu et al. / Thin Solid Films 515 (2007) 86998704

respective compound. It may be also observed that the re-
spective diffraction patterns exhibit some additional peaks: at
2 = 39.0 (in pattern 1b) and at 2 = 39.0 and 43.2 (in pattern
2b). These peaks correspond to the reflection on (100) and (101)
planes of the hexagonal Zn structure, respectively. This
indicates that at heating temperature of 550 K, the respective
samples are characterized by a mixture of metallic zinc and ZnO
phases. Such behavior is more pronounced for the obliquely
deposited Zn samples.
The increase of heating temperature up to 650 K determines
the complete oxidation of the Zn films as it results from Figs. 1c
and 2c.
In Table 1, the values of crystallite size, D, calculated
relative to the four main maxima for each XRD pattern with
DebyeScherrer formula [16,19], are also indicated. As it may
be seen, the crystallite size has almost the same values for both
typical Z1 and Z2 samples. The relative lower values of
crystallite size indicate that the studied films are characterized

Fig. 4. AFM images for obliquely deposited Zn film (sample Z2) heated up to various temperature: (a) - as-deposited; (b) - after first heating up to 550 K; (c) after
second heating up to 650 K.
 G.G. Rusu et al. / Thin Solid Films 515 (2007) 86998704 8703

Table 3 3.2. AFM studies

Roughness parameters for typical samples after heating up to various temperatures
Sample Rrms (nm) Ra (nm) Figs. 3 and 4 present a selection of 3 m 3 m sized atomic
300 K 550 K 650 K 300 K 550 K 650 K force micrographs of studied Zn films at various heating tem-
Z1 35.6 46.1 152.1 28.5 36.2 126.7 peratures. Some quantitative data about the surface roughness
Z2 52.9 39.3 73.6 42.2 32.5 59.6 and the grain height distributions for respective samples are
presented in Table 3 and Fig. 5. The analysis of these data
indicates that the deposition conditions and the heat treatment
by a nanocrystalline structure. Moreover, for the both samples, influence the surface morphologies both of the as-deposited and
the effect of the film heating on the variation of crystallite size is finally oxidized Zn films.
analogous: a decrease of these size after the first heating step, Thus, from Figs. 3a and 4a it results that in the case of the
followed by a small increase after the second heating step. obliquely as-deposited Zn films, the hillock-like grains growth
These facts indicate that the preparation conditions and the on film surface more oriented in one and the same direction in
oxidation process do not much influence the nanocrystalline comparison with those from surface of the normally as-de-
structure of the films. posited Zn films. This feature can be associated with the oblique

Fig. 5. Grain height distributions for typical studied Zn samples heated up to various temperatures: Leftnormally deposited sample (Z1); Rightobliquely deposited
sample (Z2) (a) as-deposited; (b) after first heating up to 550 K; (c) after second heating up to 650 K.
8704 G.G. Rusu et al. / Thin Solid Films 515 (2007) 86998704
position of the film substrate during deposition process which
may favor the respective orientation. Indeed, in the case of
obliquely deposited films, certain crystalline planes may be
favored in growth over the other, and therefore, the crystallites
may grow with other planes parallel to the substrate [13,20].
Consequently, other texture orientation of the grains on the film
surface may occur. The XRD patterns from Figs. 1a and 2a
confirm this assumption.
The different growth mechanisms of the film grains depending
on the deposition conditions also determine the different values
both of the roughness parameters (Table 3) and the grain high
distributions (Fig. 5) for as-deposited samples. The sample
obliquely deposited presents a greater roughness and a larger
grain height distribution as normally deposited sample.
In Figs. 3b and 4b, the surface morphologies after the first
heating step of the films up to 550 K are shown. One may
observe that the temperature increasing favors the grain
interlinking and the increase of their size. In the case of the
obliquely deposited sample (sample Z2) the new formed clusters
on the film surface are more large and uniform in height (Fig. 5b)
in respect to those from sample Z1. Simultaneously, a decrease
of the roughness parameters for Z2 sample, whereas those for Z1
increase can be observed (Table 3).
The interconnection and size increase of the clusters as
consequence of the film heating can be correlated with the
inclusion of the absorbed oxygen atoms in the Zn lattice during
oxidation process that take place at higher temperatures [14].
In the Figs. 3c and 4c, the morphologies of the same samples,
Z1 and Z2, after second heating step, up to 650 K, are presented.
One may remark that the increase of the heating temperature
determines a noticeable increase both of the cluster size and
surface roughness, this feature being clearer in the case of
normally deposited sample. As it results from Table 3, the
roughness parameters of such sample increase of about four
times related to the initial values. Also, a larger grain height
distribution of the clusters in this last case can be seen from
Fig. 5c. It must also observe that in the case of the obliquely
deposited sample, the interconnected grains keep their orienta-
tion on the film surface as at beginning. This fact indicates that
the position of the Zn film substrates and the crystalline
structure of the as-deposited films represents an important factor
that influences the surface morphology of finally oxidized ZnO
films.
Similar results regarding the influence of the preparation
conditions of the electron beam evaporated Zn layers onto
silicon substrate, on the finally obtained ZnO nanoparticles are
reported by K. Giannakopulos et al. in [21].
4. Conclusions
Polycrystalline Zn thin films were deposited in vacuum at
room temperature by quasi-closed volume technique onto nor-
mally and obliquely arranged glass substrates. By means of
XRD and AFM techniques, the structural changes during
heating of as-deposited Zn films were investigated in the
temperature range 300 K650 K. Analysis of XRD data have
been indicated that the normally as-deposited Zn films show a
(002) preferred orientation with c-axis normal to the substrate,
whereas those obliquely deposited present a (101) orientation.
The increase of the heating temperature up to 650 K
determines the film oxidation, the formed ZnO films having a
nanocrystalline structure with average crystallite size of about
20 nm. The AFM investigations revealed a more orientated
arrangement of the surface grains in obliquely deposited Zn
films in comparison with those from normally deposited films.
This behavior is maintained in finally oxidized ZnO films. The
increase of the heating temperature up to 650 K determines
the strong increase of the surface clusters size and the surface
roughness.
The obtained results indicate that the position of the Zn film
substrates during their preparation represents an important
factor which influences the structural characteristics of the as-
deposited Zn films and surface morphology of the finally
oxidized ZnO films.
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