Materials Chemistry and Physics 113 (2009) 756–763

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Materials Chemistry and Physics

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(Cu, Fe, Co, or Ni)-doped tin dioxide films deposited by spray pyrolysis:
Doping influence on thermal stability of the film structure
G. Korotcenkov a,b,∗ , Sang Do Han a,∗
a
Future Fundamental Technology Research Department, Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu, Daejeon 305-343, Republic of Korea
b
Technical University of Moldova, Bld. Stefan cel Mare 168, Chisinau 2004, Republic of Moldova

a r t i c l e i n f o a b s t r a c t

Article history: The results of doping influence on thermal stability of the SnO2 film morphology are presented in this
Received 9 May 2008 article. The SnO2 films doped by Fe, Cu, Ni, Co (16 at.%) were deposited by spray pyrolysis from 0.2 M
Received in revised form 6 August 2008 SnCl4 –water solution at Tpyr 350–450 ◦ C. The annealing at 850–1030 ◦ C was carried out in the atmosphere
Accepted 11 August 2008
of the air. The change of such parameters as film morphology, the grain size, texture and the intensity
of X-ray diffraction (XRD) peaks have been controlled. For structural analysis of tested films we have
Keywords:
been using X-ray diffraction, Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM)
Oxides
techniques. It was established that the doping does not improve thermal stability of both film morphology
Thin films
Annealing
and the grain size. It was made a conclusion that the increased contents of the fine dispersion phase of
Microstructure tin oxide in the doped metal oxide films, and the coalescence of this phase during thermal treatment are
the main factors, responsible for observed changes in the morphology of the doped SnO2 films.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction including SnO2 , In2 O3 , and TiO2 [3,10–14]. It is necessary to note

High thermal stability of structure is indispensable requirement
to any material designed for practical application, including metal
oxides [1]. It is known that the sintering rate of ceramic materials
is usually controlled by the grain boundary transport kinetics. It
was also established that the appearance of additional intergrain
boundaries between the adjacent grains of metal oxides inhibits
the cation inter-diffusion and the crystallite growth. It means that
the incorporation of the second phase through modification of the
grain boundaries’ properties could provide controlled influence on
the mechanism and kinetics of the sintering and the final proper-
ties of the ceramic materials [2]. So, there is an assumption that
the doping, accompanied by the appearance of the second phase,
can promote the improvement of thermal stability of the metal
oxide structure. Numerous experiments carried out with metal
oxide powders, synthesized by using standard methods, such as
sol–gel method, have confirmed this assumption [3–9]. Metal oxide
powders doped by Cr, Nb, Ce, Er, Ni and Al had considerably bet-
ter stability of the grain size during thermal treatments than the
undoped powders. Such effect was observed for many metal oxides,
∗ Corresponding authors at: Future Fundamental Technology Research Depart-
ment, Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu, Daejeon
305-343, Republic of Korea. Tel.: +82 42 860 3509; fax: +82 42 860 3307.
E-mail addresses: ghkoro@yahoo.com (G. Korotcenkov), sdhan@kier.re.kr
(S.D. Han).
that the prevention of the grain growth during any thermal treat-
ments is also important for achievement the high sensitivity of gas
sensors [15].
For the thin films doped by various additives we do not have
such a reliable experimental basis for conducting a similar anal-
ysis. As it is known, the structure and the composition of doped
metal oxides, formed under the conditions of the powder synthe-
sis and the film deposition, differ from each other. It means that
peculiarity of the change of both the morphology and the crys-
tallite size in doped metal oxide films during thermal treatment
could be essentially different from the regularities established for
the metal oxide ceramics. So, the enlarging research in the field of
doped metal oxide thin film’s study is required.
The results presented in this article are a continuation of
research, started in Refs. [16,17]. In indicated papers we have con-
sidered the influence of doping by Cu, Fe, Co and Ni (0–16 at.%)
on the cathodoluminescence and the structure of the SnO2 films,
deposited by spray pyrolysis method. We have established that the
SnO2 doping was accompanied by the sharp quenching of cathodo-
luminescence in comparison with undoped samples [17]. We have
also found out that the increase in the contents of the fine dispersed
phase in as-deposited films is one of the most important conse-
quences of the SnO2 doping by mentioned above impurities [16].
In present article we are trying to answer the questions regard-
ing our ability to control the morphology of doped SnO2 films
during thermal treatments, and regarding the importance of the
appearance of mentioned above fine dispersed phase for thermal

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.08.031
 G. Korotcenkov, S.D. Han / Materials Chemistry and Physics 113 (2009) 756–763 757

Fig. 1. SEM images of undoped SnO2 films and films doped by Co, Ni, Fe or Cu before and after annealing at T = 850 ◦ C. Films were deposited at Tpyr = 450 ◦ C and had thickness
∼120 nm.
758 G. Korotcenkov, S.D. Han / Materials Chemistry and Physics 113 (2009) 756–763

stability of those films’ structural parameters. The wide use of the films. Even more, at used concentrations (0–16 at.%) those additives
SnO2 doping by Cu, Fe, Co and Ni for optimization of the gas sensors do not control that changes. Noticeable distinction in the morphol-
parameters is an additional motivation of present research [1,13,18]. ogy of as-deposited films and similarity of their structure after
As it is known, working temperatures of gas sensors could be in the annealing allows concluding that the doping influence on the film
range of 100–600 ◦ C; and the determination of consequences of morphology at the stage of deposition is much stronger than dur-
doping for the structure stability of gas sensing materials gained a ing the process of the following annealing. It means that the grain
special significance for the improvement of working characteristics shape after annealing is being determined first of all by the tem-
of those devices. perature of thermal treatment and the grain size, but not by the
doping element.
2. Experimental details The comparison of SEM images presented in Figs. 1 and 2 shows
that the shape of the grains, formed as a result of annealing at
During present research we have been using the SnO2 films similar to the ones
described in Refs. [16,17]. Films, which thickness varied from 50–70 nm to 400 nm, Tan ∼ 850 ◦ C does not depend on Tpyr of annealed SnO2 films. After
were deposited by spray pyrolysis from 0.2 M SnCl4 –water solution on oxidized annealing at 850 ◦ C the SnO2 films deposited at Tpyr = 350 ◦ C and
Si substrate at Tpyr = 350 ◦ C and 450 ◦ C [19,20]. Such wide range of the thicknesses 450 ◦ C had very similar SEM images. Further thermal treatment at
was conditioned by the fact that SnO2 films find an application in devices, where
Tan = 950 ◦ C did not influence the film morphology and the grain
requirements to the thickness are being varied in very wide range.
The annealing was carried out in a flow type reactor in the atmosphere of air. The
size, confirming our assumption that the main changes in SnO2
annealing temperature was varied from 850 ◦ C to 1030 ◦ C. The choice of indicated film morphology were connected with coalescence of the fine dis-
temperatures was necessary for obtaining effect, applicable for analysis. As it was persion phase and the small grains, which has already taken place at
found in Refs. [21,22], noticeable changes in the morphology and the grain size of
the SnO2 films deposited by spray pyrolysis take place only after thermal treatments
at Tan higher 600–700 ◦ C. The duration of annealing was usually equaled to 1 h.
Fe, Cu, Co, and Ni have been used as doping additives, embedded into sprayed
solution in the form of chlorides. The concentration of doping elements in sprayed
solution was equaled 16 at.%. At lower concentration of additives (1–8 at.%) the
doping influence was not so clear shown as at the concentration equaled 16 at.%.
Therefore it was decided that consideration of the behavior of the film structure
with maximum concentration of doping additives would be enough for establishing
a general peculiarities of the influence of the dopants’ nature on the transformation
of the films morphology during thermal treatment.
X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Atomic Force
Microscopy (AFM) have been used for structural characterization of analyzed films.
XRD measurements were conducted by a Rigaku Rotaflex X-ray diffractometer with a
rotating anode source, working with the K␣ of the Cu. For structural characterization
we have been using the /2 mode of measurements. The size of the crystallites,
forming the film, was evaluated by Scherrer’s formula.
For SEM measurements we have been using scanning electronic microscopes
Philips XL30, and Stereoscan JS360 Cambridge Instruments with structural resolu-
tion ∼0.3–0.4 nm. AFM images were obtained by using MultiMode Scanning Probe
Microscope with Nanoscope IIIa Controller of Digital Instruments. These measure-
ments have been carried out in contact scanning mode using AS-0.5 scanner (scan
rate 2 Hz; resolution 0.4 nm).

3. Experimental results and discussions

3.1. Annealing influence on morphology of doped SnO2 films

In Fig. 1 it is shown the influence of thermal treatment on the

morphology of the SnO2 films doped by various additives. As it is
seen from SEM images, the annealing sufficiently influences the
morphology of deposited films. At that all films, regardless of dop-
ing additives are exposed to transformation. If before annealing at
SEM images for the majority of the SnO2 films we have been observ-
ing the diamond like formations; after thermal treatment they were
transformed into formations without clear cutting. The variety of
aggregate specimens’ configurations in as-deposited SnO2 films
we connect with multiple twinning of the SnO2 crystallites. As it
is known, SnO2 is inclined to twinning during the growth of the
films [23,24]; and, as it was shown in Ref. [16], the doping had an
influence on this process.
We do not know the reasons of such strong change of the film
morphology and the shape of the grains (crystallites). However one
can suppose that existing changes in the crystallite shape is a con-
sequence of the grain size’s change connected with a coalescence
of grains. We believe that after coalescence of the grains, forming
agglomerates, the new grains acquire a shape, peculiar to their big-
ger size. As it is seen in the Fig. 1, after annealing the SnO2 films’
morphology obtains common type for all studied films, regardless
of initial morphology and doping additive. Thus, observed changes Fig. 2. SEM image of undoped SnO2 film (Tpyr = 350 ◦ C; d ∼ 250 nm) before and after
testify that doping does not inhibit structural changes in the SnO2 annealing at Tan = 850 ◦ C and Tan = 1030 ◦ C.
 G. Korotcenkov, S.D. Han / Materials Chemistry and Physics 113 (2009) 756–763 759

lower temperature. The following considerable change of the SnO2

films’ morphology took place only at Tan > 1000 ◦ C, when the notice-
able increase of the crystallites size was observed. The typical image
of the SnO2 films after annealing at T > 1000 ◦ C is shown in Fig. 2.
The same processes take place for doped films. We have to note,
that observed regularities are very much similar to those, we have
been observing while making thermal stability study of undoped
In2 O3 films’ structure [21].

3.2. Transformation of XRD patterns of doped films during

thermal annealing

Typical XRD patterns of studied films are presented in Fig. 3. As

an example there are shown XRD patterns of undoped SnO2 and
doped SnO2 :Cu films, for which the strongest influence of the dop-
ing on the film morphology is observed (see Fig. 1). As it follows
from the analysis of XRD patterns, the X-ray diffraction peak’s posi-
tion corresponds to cassiterite structure, characteristic for SnO2 . At
that the doping in used range of dopants concentrations (0–16 at.%)
does not exert an essential influence on the XRD patterns’ shape.
XRD patterns of doped SnO2 are only slightly different from the
ones of undoped SnO2 . As it is seen from the results obtained for
films deposited at different temperatures and presented in Fig. 3,
the shape of XRD patterns depends more on the temperature of
deposition then on the doping. It means that in spite of existing
changes in the morphology of doped SnO2 films (see Fig. 1), the
films retain crystallographic structure, peculiar to undoped films.
The same result was also described in other papers [12,13]. For
example, in Ref. [12] XRD measurements of Fe- or Ni-doped SnO2 ,
synthesized by the polymeric precursor method, have shown the
presence of only the SnO2 tetragonal phase, even at 30 mol.% of both
additives.
Present research has shown that the thermal treatment in the
range of 800–1000 ◦ C has also weak influence on the shape of
XRD patterns of doped SnO2 . XRD patterns after annealing had the
shape, similar to the one of XRD patterns of undoped SnO2 films
[22,25]. We just observe some change in the correlation of inten-
sities of individual XRD peaks. In particular, for the doped SnO2
films deposited at Tpyr = 450 ◦ C, we have observed the increase of
the ratio of the main XRD peaks intensities I(1 1 0)/I(2 0 0) in 1.5–1.7
folds. However as it was established, these changes were almost
similar to the ones observed for undoped SnO2 films. It means that
observed changes in the shape of XRD patterns are not connected
with the doping process.
The absence of any additional peaks, related to the second phase
at XRD patterns of doped SnO2 , in spite of the fact that, according
to EDAX measurements, this phase exists [16], allows confirming
the conclusion made in Ref. [16], where it was established that the
concentration of doping element in grown SnO2 films was close
to concentration of this element in sprayed solution. In Ref. [16] it Fig. 3. XRD patterns of undoped and Cu (16 at.%) doped SnO2 films: (a) films
was concluded that in doped SnO2 films very low concentration of deposited at Tpyr = 450 ◦ C, d ∼ 70 nm; (b) films deposited at Tpyr = 350 ◦ C, d ∼ 250 nm.

dopants is found in the state of bulk solid solution; while the most
part of the dopants is segregated on the surface of the SnO2 crys-
tallites in the form of small grains with size smaller than 2–4 nm.
It is known that X-ray diffraction on the crystallographic planes of
the grains with such small size does not give any noticeable peaks.
The absence of significant shifts in the position of X-ray
diffraction peaks in comparison with undoped SnO2 is additional
confirmation of the made-above conclusion. Even after annealing
at 1000 ◦ C the shift in XRD peak position in doped films in compar-
ison with undoped ones was in the limits of experimental error. It
means that the doping is not accompanied by the change of lattice
parameter of SnO2 . Such situation at used levels of doping is pos-
sible only in case when the solubility of doping elements is small,
i.e. only small part of doping additives incorporates in the lattice
of SnO2 . It is necessary to note that the small limiting solubility of
various metal oxides is typical for SnO2 [12,14].
3.3. Doping influence on grain size stability
Regarding the influence of the nature of doping additives on the
stability of the SnO2 grain size, obtained XRD data allows to make
the following conclusions.
Additives actually affect the thermal stability of the SnO2 grain
size. However it is necessary to note, that optimizing influence, i.e.
the decrease of the grain size change during thermal treatment,
in contrast to the results obtained for the SnO2 powders, is not
being observed for all studied additives. For example, the addition
760 G. Korotcenkov, S.D. Han / Materials Chemistry and Physics 113 (2009) 756–763

Table 1
Doping influence on the intensity of X-ray diffraction at (1 1 0) plane of SnO2 grains

Tpyr (◦ C) d (nm) Doping element XRD intensity (1 1 0)

As-deposited Tan = 850 ◦ C

350 250 ± 20 – 80 244

Cu 52 487

450 120 ± 10 – 356 586

Cu 158 804
Fe 189 510
Co 308 736
Ni 365 538

450 400 ± 20 – 1660 2500

Cu 1620 3000
Fe 1670 2520
Co 1400 2800

a rule, the bigger the drop of XRD peaks’ intensity in as-deposited

Fig. 4. Influence of annealing on average grain size in undoped and Cu-doped
SnO2 films estimated by XRD method. Studied films were deposited at Tpyr = 350 ◦ C
(d ∼ 250 nm).
of nickel practically does not influence the stability of the tin diox-
ide grain size during thermal treatment at 850 ◦ C. The changes of
average grain sizes estimated on the base of XRD data in SnO2 and
SnO2 :Ni films with the same thickness were similar. While in the
presence of Fe, Co and especially cooper additives, thermal stability
of structural parameters of doped SnO2 films is being considerably
deteriorated.
At that indicated influence was in full accordance with regu-
larities established for undoped SnO2 films. The higher is pyrolysis
temperature and the less is film thickness, the smaller is the change
of the crystallites size during the annealing [21]. For example,
if in doped SnO2 :Cu films with thickness ∼120 nm deposited at
Tpyr = 450 ◦ C, after thermal treatment at Tan = 850 ◦ C the average
grain size changed on average for 3–5 nm; while for the films
deposited at Tpyr ∼ 350 ◦ C with the same thickness the grain size
change exceeds 15 nm. For thicker films (d ∼ 250 nm; Tpyr = 350 ◦ C)
those changes are even bigger and exceed 20 nm (see Fig. 4). For
information, in as-deposited undoped SnO2 films with thickness
∼120 nm deposited at Tpyr = 450 ◦ C the average grain size is equaled
∼27 nm, and in as-deposited SnO2 :Cu films the average grain size
is equaled ∼18 nm. Films with thickness 250 nm (Tpyr = 350 ◦ C) had
initial average crystallite size equaled 13–14 nm (see Fig. 4).
doped films is, the greater is the growth of the XRD peaks’ intensity,
and the bigger is the growth of the grain size after annealing (see
Fig. 4 and Table 1). It means that the changes, taking place during
the annealing, are mainly a reflection of the changes, existing during
the film deposition.
In Ref. [16] we have concluded that the doping of SnO2 during
spray pyrolysis deposition is accompanied by the increase of con-
tents of the fine dispersed amorphous-like SnO2 phase. Under fine
dispersed phase we meant the SnO2 grains with size smaller than
2–3 nm. As it is known, X-ray diffraction at crystallites of this size
(t < 2–3 nm) does not show well-defined peaks at the XRD patterns.
We believe that discussed in this paper effect of strong increase
of X-ray diffraction peaks’ intensity for doped SnO2 films after their
annealing is a consequence of the presence of this fine dispersed
SnO2 phase. Due to coalescence with already existing bigger crys-
tallites during thermal treatment it promotes both the increase of
the grain size and the improvement of the film crystallinity.
However the second oxide phase (Fe2 O3 , NiO, Cu2 O or CoO), in
spite of the fact that it is segregated on the surface of the grains
of basic oxide [12,14] is not able to block this process. Apparently
the fine dispersed phase of the basic oxide (SnO2 ), filling inter-
crystallite space, even at the presence of the second oxide phase
is able to form the channels for intensive mass transfer between
crystallites (from the smaller crystallite to the bigger one), neces-
sary for their growth (see Fig. 5). Either theoretical calculations, and
experimental results have shown that already at the crystallites size
smaller than 5 nm, the temperature of melting could decrease in
more than 2–3 times [21,26,27]. As a result, already at sufficiently

3.4. Mechanism of the grain size instability in doped SnO2 films

Analyzing obtained results we have concluded that the doping

exerts the most evident influence on the intensity of XRD patterns.
It was established that after thermal treatment the intensity of char-
acteristic X-ray diffraction peaks has been sharply increasing (see
Table 1). At that the maximum increase of XRD peaks’ intensity
appears mainly for the films, doped by Cu and Fe, for thin films, and
for the films, deposited at low pyrolysis temperatures. As it is seen
from data presented in Table 1, during the annealing at T = 850 ◦ C
the intensity of X-ray diffraction peaks of doped SnO2 films, espe-
cially of SnO2 :Cu, may increase up to 8 times. For undoped films for
the same conditions the X-ray diffraction peaks’ intensity does not
increase in more than 3 times. As it is known, the increase of XRD
peak’s intensity usually is being considered as an evidence of the
improvement of the tested films’ crystallinity.
At that the changes of the intensity after the annealing were in
Fig. 5. Diagram illustrating the influence of the fine dispersed phase on the forming
direct correlation with both the doping influence on XRD patterns of channels for mass transfer between the grains of SnO2 in the presence of the
of as-deposited films, and with observed change of the grain size. As second oxide phase between them.
 G. Korotcenkov, S.D. Han / Materials Chemistry and Physics 113 (2009) 756–763
low temperatures the necks with essentially big area (diameter)
could be formed between crystallites. The presence of the necks
between grains can be considered as factor, promoting the coa-
lescence of closely located grains. This fact could be an important
reason of degradation of the sensors parameters after high tem-
perature annealing. In this context, a considerable improvement of
the sensors parameters after mechanical milling of sintered metal
oxide powders could be considered as a result of those necks’ break-
ing [28].
The mechanism of the appearance of the fine dispersed phase we
have discussed earlier in Ref. [16]. According to suggested model,
the growth of contents of the fine dispersed phase in doped films is
conditioned by the appearance of additional nucleation centers for
the SnO2 growth, formed by the second oxide phase. As we indi-
cated earlier the second oxide phase, appearing during the process
of SnO2 growth as a rule is being segregated on the surface of basic
oxide grains [4,12,29], which stimulates the appearance on the sur-
face of big crystallites of the layer of the fine dispersed phase, filling
inter-crystallite space. It is necessary to note that we are not the
only ones, using such approach in analyzing structural properties
of the SnO2 films. In Ref. [30] it was also mentioned the form-
ing of the fine dispersed amorphous-like phase during the growth
of the SnO2 films. The authors of mentioned work, as well as in
our case, have been observing both the increase of contents of the
fine dispersed phase at the lowering of deposition temperature and
the sharp reduction of this phase’s concentration at the following
annealing at Tan > 500 ◦ C.
On the base of the assumption that the main changes in the
grain size of doped SnO2 films during the annealing at Tan ∼ 850 ◦ C
are connected with the presence of the fine dispersed phase, and
basing on the data of the annealing influence on the intensity of
X-ray diffraction peaks, we receive the confirmation of the con-
clusion made in Ref. [16] that the maximum contents of the fine
dispersion phase in the SnO2 films during spray pyrolysis deposi-
tion are being formed after doping by Cu. With regard to another
doped SnO2 films, we can concluded that the contents of the fine
dispersed phase have been decreasing in the line SnO2 :Cu, SnO2 :Fe,
SnO2 :Co, SnO2 :Ni, SnO2 . Given line reflects the degree in the change
of the XRD peaks intensity as a result of thermal treatment.
The same conclusion one can make analyzing AFM images of
doped SnO2 films (see Fig. 6). As we have shown in Ref. [16], the
sharpness (image detail) of the grain contours, observed at AFM
images for doped SnO2 films is being worsening due to the pres-
Fig. 6. AFM images of SnO2 :Cu films (a) before and (b) after thermal treatments at 850 ◦ C. SnO2 films were deposited at Tpyr = 350 ◦ C and had thickness equaled d ∼ 250 nm.
761
ence of the fine dispersed phase. After annealing at Tan = 850 ◦ C
all AFM images even for SnO2 films doped by cooper (see Fig. 6b)
had clearly defined contours of grains, confirming the absence in
the SnO2 matrix of the grains with sizes, smaller than the limit of
resolution of used measuring instruments.
It is important to note that the morphology of the SnO2 films
after thermal treatments replicates the macrostructure of the films
formed by agglomerates (see Fig. 6). Such behavior one can con-
sider as the evidence of the fact that the transformation of the
film morphology first of all takes place through the coalescence
of crystallites forming the agglomerates.
Comparing the influence of annealing on the XRD patterns of
both thick and thin SnO2 films, deposited at the same tempera-
ture, one can see that the change of the X-ray diffraction peaks’
intensity after thermal treatments is higher for the thin films (see
Table 1). For the SnO2 films with thickness of 400 nm (Tpyr = 450 ◦ C),
the change of the X-ray diffraction peaks’ intensity after annealing
at T = 850 ◦ C was equaled 1.5–2 times, while for the films with thick-
ness of 100 nm this change could exceed 3–5 times. Basing on our
assumptions this effect can be easily explained, since in the thin
films the contents of the fine dispersion phase is bigger. This is
understandable, because with the thickness’ growth the grain size
is being increased as well [20,25]. Besides that, as we have shown
earlier in Ref. [15], the SnO2 films at the interface with substrate
always had transient layer with thickness of ∼3–10 nm, consist-
ing from randomly oriented fine dispersed crystallites. Therefore,
the contribution of this transition layer crystallization and struc-
ture ordering in XRD patterns of the thin films should be obviously
higher, than in the thick films.
The comparison of data presented in Table 1 also indicates that
the films deposited at low temperatures (Tpyr ∼ 350 ◦ C) subjected
to much more structural changes than the films, grown at higher
temperatures (Tpyr > 400–450 ◦ C). This result is quite appropriate,
because the coalescence of the fine dispersed grains formed dur-
ing the process of the growth with big crystallites could take place
already at the stage of the film growth. It means that devices, man-
ufactured of the base of films, grown at high temperatures would
be more stable during exploitation in comparison with the ones,
fabricated on the base of low temperature films.
From our point of view the increase of contents of the fine dis-
persed phase in doped SnO2 films has great importance for doped
films’ application in real devices, since the appearance of the fine
dispersed phase can change such metal oxides’ parameters as real
762 G. Korotcenkov, S.D. Han / Materials Chemistry and Physics 113 (2009) 756–763
area of intergrain contacts, the active surface area, the surface activ-
ity, gas penetrability of gas sensing matrix, and so on. For example,
the presence of the fine dispersed phase, inclined to coalescence
already at low temperatures could be a reason, responsible for
observed temporal drift of the sensors parameters [1,15,31–33]. As
it is known, the instability of the gas sensing material structure is
the main reason of instability of the gas sensors parameters [15,32].
Therefore, indicated peculiarity of doped films should be taken into
account while analyzing the doping influence on electro-physical
properties of deposited films. In particularly, for avoidance of pos-
sible temporal instability it is desirable to age as-deposited doped
films through their additional thermal treatment.
It is necessary to note that this statement receives good exper-
imental confirmation. Numerous researches have shown that the
decrease of the grain size is inevitably accompanied by the degrada-
tion of thermal stability of the film structure even for metal oxides,
having maximum thermodynamic stability among well-known
materials [21,34,35]. It was shown that the fine dispersed phase
with the grain size smaller than 1–3 nm was inclined to coalescence
with bigger crystallites already at low temperatures, which did not
exceeded 300–400 ◦ C, promoting their growth [21,26,36,37].
Structural disorder and the growth of concentration of the point
defects in doped SnO2 films is another important factor, stimulating
structure’s instability of doped films during the process of anneal-
ing. As we have established earlier in Ref. [17], basing on the analysis
of cathodoluminescence and optical transmission, the doping of
the SnO2 films is accompanied by structure disordering, appearing
through the growth of the concentration of centers of non-radiating
recombination and the appearance of the tails of electronic states
inside the band gap. At that maximal effect from the doping was
observed exactly for the films, doped by Cu, for which the maxi-
mum instability of the film’s structural parameters was found. The
authors of Refs. [13,38] have also indicated an essential growth of
structural defects in doped SnO2 films. For example in Ref. [13] the
increase in the stacking fault density of the SnO2 films has been
observed already after doping by Fe with concentration 2%. In Ref.
[38] the authors believed that Co creates oxygen vacancies in the
SnO2 lattice. According to Ref. [14], the growth of structural defects
concentration stimulates surface diffusion, responsible for mass
transfer during the annealing process.
High degree of densification, which could be attained for doped
metal oxides under conventional sintering at high temperatures,
is a direct consequence of those processes [11,14,38–40]. As it is
known, the undoped tin dioxide is characterized by a relatively low
densification even at high temperatures of sintering [14]. It is neces-
sary to note that recorded effect of densification evidently is not an
optimizing effect for gas sensing material and cannot promote the
improvement of operating characteristics of SnO2 -based gas sen-
sors. As it is known, high porosity and big active surface area are
the metal oxides’ parameters, important for gas sensor applications
[1,35,41].
4. Conclusion
It was established, that SnO2 doping by Cu, Co, Ni, and Fe
during spray pyrolysis deposition does not improve thermal sta-
bility of the SnO2 film’s structure in studied range of annealing
temperatures 600–1000 ◦ C. Moreover, such additives as cooper
stimulate noticeable grain’s growth during the process of high tem-
perature annealing in comparison with the grain size change in
undoped SnO2 films. It was concluded that observed effect was
connected with increased contents of the fine dispersed phased in
doped SnO2 films. The bigger contents of the fine dispersed phase
are in as-deposited films, the greater is the change of the grain
size after thermal treatment. At that the contents of this phase
are being increased in the line SnO2 , SnO2 :Ni, SnO2 :Fe, SnO2 :Co,
and SnO2 :Cu. It was assumed that the fine dispersed phase, fill-
ing inter-crystalline space, besides coalescence with the big grain
creates conditions for mass transition from one grain to another
one, necessary for coalescence of bigger crystallites, forming film.
After annealing the morphology of doped and undoped SnO2 films
becomes similar. The grains lose clearly defined faceting.
Such unexpected influence of additives on the SnO2 films struc-
ture, i.e. the decrease of the grain size in as-deposited SnO2 films in
comparison with undoped films and the increase of the grain size
after annealing, forces researchers to be careful while elaborating
the technologies of gas sensing layers’ forming on the base of doped
and multi-component materials. For example, the presence of the
fine dispersed phase could be a reason of instability of the metal
oxide films’ structure and generate temporal drift of the parameters
of gas sensors, manufactured on their base.
Therefore, while choosing additives for either the gas sensor
optimization or for the film structure stabilization one should take
into account that after changing of the conditions of synthesis,
exploitation, or parameters of post-deposition thermal treatments,
the consequences of the doping could be substantially different
from the ones, observed during our initial experiments with as-
deposited films.
Acknowledgements
This work was supported by the Supreme Council of Science
and Advanced Technology of the Republic of Moldova, as well as by
the Korean Brain Pool Program. The authors are thankful to Prof.
J. Schawnk from University of Michigan, USA, and Dr. V. Brinzari
from Technical University of Moldova for their help in structural
characterization of studied samples.
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