Applied Surface Science 353 (2015) 793803

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

The inuence of gold nanoparticles on the conductivity response

of SnO2 -based thin lm gas sensors
G. Korotcenkov a, , V. Brinzari b , L.B. Gulina c , B.K. Cho a,
a
School of Material Science and Engineering, Gwangju Institute of Science and Technology, Gwangju, Republic of Korea
b
Department of Theoretical Physics, State University of Moldova, Chisinau, Republic of Moldova
c
Institute of Chemistry, St. Petersburg State University, St. Petersburg, Russia

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

Article history: The results presented in this study demonstrate that the successive ionic layer deposition (SILD) method
Received 9 April 2015 for gold nanoparticle formation can be used for surface functionalization of SnO2 lms to improve their
Received in revised form 26 June 2015 gas sensing properties. As a result of successive treatments in HAuCl4 nH2 O and NaBH4 solutions, gold
Accepted 29 June 2015
nanoparticles can be formed on the surface of SnO2 crystallites. The size of the gold particles varies
Available online 10 July 2015
over the range of 150 nm depending on the number of SILD cycles. Gas sensing characteristics of the
Au-modied SnO2 lms are discussed as well. Unlike most studies focused on the development of CO
Keywords:
sensors, the present research focuses on the specics of the response of the SnO2 :Au-based sensors to
SnO2
Films
other gases, such as hydrogen and ozone. It is established that gold nanoparticles deposited on the SnO2
Gold clusters surface are active toward both reducing and oxidizing gases, and the effect of the SnO2 surface decoration
Surface modication by the gold nanoparticles on the gas sensing characteristics depends on the number of deposition cycles
SILD (i.e., the size of the gold particles). The sensitization to ozone and hydrogen suggests that the application
Gas sensors of the surface modication by gold in the eld of gas sensor design should not be limited by optimization
Characterization of the CO sensors parameters. Models showing the promotional role of Au additives are discussed, and
Optimization a mechanism of sensitization in the SnO2 :Au-based gas sensor is proposed.
2015 Elsevier B.V. All rights reserved.

1. Introduction using AuNPs for surface functionalization of metal oxides in solid

For many years, it was believed that only Pd and Pt, showing
pronounced catalytic properties, were the most suitable materials
for surface functionalization of metal oxides and optimization of
gas sensor parameters [13]. However, studies carried out during
recent decades have shown that gold, which was previously con-
sidered an inert material, at the transition to nanosized particles
supported by metal oxides has started to show enhanced catalytic
activity [47]. For example, it was found that a reaction of CO oxida-
tion, with the participation of an Au-based catalyst, could proceed
at an increased rate at signicantly lower temperatures than when
using conventional catalysts [8]. Therefore, during the last decade
among the research aimed at using gold nanoparticles (AuNPs)
in heterogeneous catalysis [9], there have been reports related to
Corresponding authors at: School of Material Science and Engineering, Gwangju
Institute of Science and Technology, 123 Cheomdan-gwagiro, Buk-gu, 500-712,
Gwangju, Republic of Korea.
E-mail addresses: ghkoro@yahoo.com (G. Korotcenkov), chobk@gist.ac.kr
(B.K. Cho).
state sensors, including in conductometric gas sensors [1015]. It
was assumed that surface modication with gold nanoparticles
would allow for the design of selective CO gas sensors that could be
operated at low temperature. However, the same studies showed
that achieving these indicated objectives is not a trivial task, and
that achieving enhanced low-temperature sensitivity of the metal
oxide sensors to CO requires the execution of several specic con-
ditions to AuNPs synthesis and deposition, related to both the size
and gold state in the cluster as well as the properties of the used
metal oxide support. These conditions have been reviewed in Ref.
[16].
Research has shown that, depending on the purpose, various
methods can be used for gold nanoparticle deposition on the surface
of metal oxides to form a gas-sensitive matrix. For example, AuNPs
can be prepared using various physical deposition methods, such
as evaporation, sputtering, laser ablation, and discharge plasma
synthesis [17]. Methods of deposition from the gas phase, such as
chemical vapor deposition (CVD), can also be used for the formation
of gold nanoparticles [18]. However, physical methods, as well as
the CVD method, are rather expensive. In addition, they have signif-
icant limitations for the formation of clusters and nanoparticles on

http://dx.doi.org/10.1016/j.apsusc.2015.06.192
0169-4332/ 2015 Elsevier B.V. All rights reserved.
794 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
the surfaces developed. Wet chemical methods do not have such
constraints and have therefore recently begun to attract signi-
cant attention. Wet chemical methods include the TurkevichFrens
method [19], the BrustSchiffrin method [20], impregnation [6,21],
solgel [22], coprecipitation [6] and some other that can be found in
the literature [12]. However, one should note that till now there are
problems associated with the formation and stabilization of AuNPs
of optimal size on the required surface.
Present study shows that the technology of successive ionic
layer deposition (SILD) of gold nanoparticles can also be used for
the surface functionalization of metal oxide-based gas sensors. The
specicity of this technique is based on multiple, successive treat-
ments of required samples in solutions, which provide adsorption
on the substrate surface of anions and cations and their subsequent
interactions, and are accompanied by the formation of poorly sol-
uble compounds. This technique has been described in detail in
[2325]. The advantages of this method, which is one version of
the layer by layer (LbL) deposition technique and in many articles
has the name successive ionic layer adsorption and reaction (SILAR)
[2629], include precise control of the thickness of the growing
layer and the size of the surface clusters formed. The primary objec-
tive of this work was to evaluate the possibilities of this method
for the formation of gold nanoparticles of a required size and to
determine the optimal synthesis conditions for their use in the
manufacturing of SnO2 conductometric gas sensors. Earlier studies
in this area have not been conducted. Only a couple of papers are
devoted to the formation of gold nanoparticles on Al2 O3 and TiO2
substrates for plasmon excitation studies using this method [28].
Currently, the SILAR method is being used usually for the synthesis
of metal chalcogenide semiconductor quantum dots [27,29].
Unlike most studies aimed at developing SnO2 :Au-based CO
sensors, the present research focused on studying the specics
of the SnO2 :Au-based sensor response to other gases, such as
hydrogen and ozone. It is well known that hydrogen and ozone
are the basis for promising, environmentally clean technologies
[30,31]. Therefore, it is important to determine whether there are
any restrictions for using SnO2 lms with surface modied with
gold nanoparticles for improving parameters of sensors designed
for the detection of the aforementioned gases. This study also
aimed to understand the role of the gold nanoparticles in gas
sensing effect and to determine the factors that are responsible
for controlling the parameters of SnO2 :Au gas sensors. SILD
technology has previously been used for the surface modica-
tion of SnO2 lms with gold nanoparticles [32,33]. However, in
those studies, SILD technology was used for deposition of the
SnO2 Au nanocomposites. Simultaneously with the deposition of
the gold nanoparticles a ne dispersed SnO2 phase was formed
on the surface of the SnO2 crystallites. It was established that
surface modication by SnO2 Au nanocomposites could be used
for improving the operating characteristics of conductometric
SnO2 -based gas sensors. In particular, an increase in sensor
response and a decrease in response and recovery times have
been observed. However, it should be noted that this situation,
when the gold nanoparticles and the ne dispersed metal oxide
phase are deposited simultaneously on the surface of the SnO2
crystallites, creates difculties in interpreting the obtained results
and understanding a real role for AuNPs in gas-sensitive effects.
Therefore, we decided to conduct new research using only gold
nanoparticles for the surface modication of SnO2 lms.
2. Experimental details
For surface modication by gold nanoparticles, we have been
using SnO2 lms obtained by a spray pyrolysis deposition from
SnCl4 water solutions at temperatures (Tpyr ) of 450 C. Some
features of this process used for the deposition of gas sensing
lms have been described in Refs. [34,35]. The main advantages
of this method for metal oxide lm deposition include simplicity of
design, ease of operation, the possibility of depositions of complex
composition, low cost, and the ability to use cheap non-toxic pre-
cursors with low vapor pressure. The thickness of the SnO2 lms,
equal to 4050 nm, was chosen because of the need to achieve
optimal parameters of gas sensors. According to [36], these thick-
nesses provide maximum sensor response to ozone at a minimum
response time. At such thicknesses, diffusion processes do not limit
the kinetics of the sensor response. The SnO2 lms were deposited
on alumina ceramic substrates.
2.1. Surface modication
Deposition of the gold nanoparticles by SILD technology was
conducted using the following route: in the rst SILD cycle, a SnO2
lm on the substrate was treated in a metal salt solution, and then
the samples were washed with distilled water to remove the non-
reacted reagents, treated with a water solution of NaBH4 , and again
washed with distilled water. Such a treatment represents one depo-
sition cycle. As a precursor for surface modication by the gold
nanoparticles, a water solution of HAuCl4 was used. Gold nanopar-
ticles were formed according to reaction:
8HAuCl4 + 3NaBH4 + 6H2 O = 8Au + 3NaBO2 + 32HCl (1)
One of the main advantages of the indicated process is the
irreversibility of the reaction and high reaction rate at room tem-
perature. This means that the reduction of HAuCl4 with NaBH4 can
take place at room temperature. The size of the gold nanoparti-
cles was controlled by changing the number of deposition cycles.
During the present experiments, this varied from 1 to 8 SILD cycles.
HAuCl4 nH2 O with a gold mass content of 49.47% obtained from
Aurat Ltd. (Russia) and NaBH4 obtained from Vekton (Russia) were
used as the reactants for the gold nanoparticle synthesis. Working
water solutions with required concentrations of HAuCl4 and NaBH4
were prepared directly before synthesis. For preparation of solu-
tions as well as for washing procedures, Milli-Q high pure water
with a resistivity higher than 18 M was used.
The choice of precursor concentration in solutions prepared for
AuNPs synthesis was based on preliminary experiments, which
showed that, in our case, 0.001 M HAuCl4 solution and 0.02 M
NaBH4 solution are optimal concentrations of reactants. Signi-
cantly higher concentrations of the reducing agent are required
for complete reduction of adsorbed gold ions. Further increase in
concentration is undesirable because at higher concentrations of
reagent the solutions pH is too high. It has been found that the
indicated concentrations provide an acceptable process duration,
which is required for the formation of gold nanoparticles with the
desired size. The treatment time in each solution, including wash-
ing, varied in the range of 0.52 min. A more detailed description
of this process can be found in Ref. [37].
2.2. Film characterization
For structural characterization of the lms, X-ray diffraction,
scanning electron microscopy (SEM) and laser ellipsometry were
used. These methods provide control of the thickness, microstruc-
ture and morphology of the deposited lms. For these purposes,
Philips XL30 ESEM and FEI Nova Nanolab SEM/FIB scanning elec-
tron microscopes were used. All SEM images were obtained in
secondary electron detection mode using an acceleration voltage
of 1030 kV. X-ray photoelectron spectroscopy (XPS) was used for
surface characterization. X-ray photoelectron spectra have been
collected from an ultrahigh vacuum system equipped with the
hemispherical electrostatic analyzer Omicron EA125 with the Al
K line (h = 1486.7 eV) for excitation. The O, Sn, In, Au, Cl, and
 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
C lines were recorded in detail with a band pass energy of 20 eV.
A Zeiss Merlin scanning electron microscope equipped with an
Oxford instruments Inca X-act EDX detector for X-ray microanalysis
was also used for characterization of the surface composition.
2.3. Sensor fabrication and testing
Gas sensor prototypes were fabricated on alumina ceramic sub-
strates using thin-lm technology. The tested samples had Au
contacts. They were deposited by thermal gold evaporation on
the SnO2 :Au lms already formed on alumina substrate using the
technology described above. The distance between the measuring
contacts was 23 mm. Such a long distance between the con-
tacts allows to reduce their inuence on the analyzed gas sensing
characteristics. The width of the samples was 2 mm.
The gas-sensing properties of as-deposited and modied SnO2
lms were investigated using a specially designed automated setup
that can conduct measurements in either stationary conditions
or in the conditions of controlling transition processes. For these
measurements, the samples were placed in a special ow-type
reactor with a controlled gas atmosphere and ambient humidity.
For the samples heating an external heater was used. The mea-
sured chamber volume was 0.5 cm3 . The small volume of the
chamber allowed to control transient processes with a time con-
stant of more than 23 s. Measurements of sensor response were
conducted in the temperature range of 25450 C. However, the
primary measurements were conducted at operating temperatures
corresponding to the maxima of the sensor response, which were
observed to be in the temperature range of 300500 C. It is known
that the most successful operation of conductometric sensors is
observed in this precise temperature range. In this range, the inu-
ence of water vapor and surface poisoning on sensor parameters is
substantially reduced. To exclude instability [38], we exposed the
tested samples to stabilizing annealing at a temperature of 450 C,
and all experiments were carried out at a constant humidity, which
was maintained at 3545% relative humidity (RH).
While studying gas-sensitive properties, the sensor response
(Rozone /Rair for ozone detection and Rair /Rgas for the detection
of reducing gases) and the kinetics of the sensor response were
controlled. Sensor testing was performed using the measurement
cycle air (air + gas) air. Carbon monoxide, hydrogen and ozone
were used as the test gases. For the ozone source, a special ozone
generator based on an ultraviolet radiation lamp was used. The
ozone concentration in the tested gas was 1 ppm. The concentra-
tion of H2 and CO during these experiments was equal to 1000 ppm.
The response and recovery times were determined during the
measurement cycles air (air + gas) and (air + gas) air, respec-
tively. Time constants of transient processes were determined on a
0.9 level from the steady state value of the lm conductivity. Mea-
surements of transient characteristics at each temperature point
Fig. 1. SEM image of SnO2 lms deposited by spray pyrolysis and Au-modied by the SILD method: (a) 1, (b) 4, and (c) 8 deposition cycles (Tan = 400 C).
795
Table 1
The average size of the gold clusters formed by the SILD technology on the surface
of SnO2 lms with the size of crystallites varied in the range of 25 15 nm.
Number of SILD cycles 0.5 1 2 4 8
Size of AuNPs, nm <3 36 47 510 1030
were conducted after temperature stabilization and establishment
of the steady-state value of the lm conductivity. To control the
reproducibility of the results, we repeated every measurement
cycle three to four times for a series of three samples manufactured
with the same process. Deviations in the values obtained during
the measurements are reected in the gures.
3. Results and discussion
3.1. SEM of the SnO2 :Au lms
Detailed analysis of gold nanoparticle formation on the surface
of SnO2 lms by the SILD method and further material charac-
terization have been published previously [37]. This allows us to
avoid repeating the previously published results and simply to state
that SILD technology is capable to form gold nanoparticles with
controlled size. As established in Ref. [37], the size of the AuNPs
depends on the conditions of the synthesis and increases with the
number of deposition cycles used. Representative SEM images of
SnO2 lms modied with Au by varying the numbers of SILD cycles
are shown in Fig. 1. As can be seen in Table 1, the particle size,
depending on the number of SILD cycles, can vary from 15 nm to
1015 nm or higher.
Analysis of the SEM images presented in Fig. 1 shows that the
particle growth occurs mainly near the tops of the crystallites as
well as within the cavities formed by several crystallites of the base
material. SEM images also show that, after 4 deposition cycles, each
crystallite contains 12 gold particles. According to [31], these
formations of 3D nanoparticles occur due to the aggregation of 1D
and 2D clusters from the whole surface of crystallographic planes
faceting the crystallite. This regularity generally coincides with reg-
ularities established for nanoparticles formed on smooth surfaces,
where the growth and accumulation of the gold clusters rst takes
place at the step edges [39]. It is known that, in these places, the
substrate atoms have the largest number of uncoordinated bonds.
In particular, according to Wahlstrom et al. [40], the step edges of
oxide surfaces can be considered a collection of oxygen vacancies.
However, the synthesized particles unfortunately have a large
variation in size [31], and along with small clusters, particles with
a substantially larger size are present on the surface (Fig. 1c). This
is a major disadvantage of the SILD method and of most meth-
ods of AuNPs synthesis [18], including wet chemical methods,
because nanoparticles with different sizes have different functional
796 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
Fig. 2. Full-range XPS spectra of the SnO2 lms modied by Au nanoparticles
deposited by the SILD method (8 deposition cycles).
properties [47]. However, the number of gold particles with an
abnormally large size is signicantly lower than the number of
grains (see Fig. 1c). Therefore, they should not have a signicant
effect on the functional properties of modied lms. Moreover,
their appearance and growth was particularly intense when a large
number of deposition cycles were used. Further research related
to the study of gas-sensitive properties of SnO2 lms (presented in
Section 3.3) shows that SnO2 surface modication by gold using a
large number of deposition cycles was not optimal for achieving
high gas sensitivity.
3.2. XPS of the SnO2 :Au lms
Typical full-range XPS spectra of the SnO2 :Au lms are shown in
Fig. 2. The data indicate that the surface of the samples contains only
gold, tin, oxygen and ordinary surface species, such as carbon ele-
ments. Quantitative analysis of the surface chemistry of SnO2 lms
was based on the area (intensity) of the main core level XPS O1s, Sn
3d, and C 1s, weighted by the corresponding atomic sensitivity fac-
tor (ASF) and showed that SnO2 is slightly non-stoichiometric with
an [O]/[Sn] ratio of 1.71.8. This value is typical for nanostructured
metal oxides [41], which have oxygen vacancy defects in the sur-
face region of the SnO2 grains. XPS measurements also revealed that
carbon is the main surface contaminant of the SnO2 grains. From
our estimations, the [C]/[Sn] ratio is equaled to 1. This means that
the surface concentration of carbon is sufcient. However, this sit-
uation is typical for metal oxides stored under ambient conditions
[41].
Energy-dispersive X-ray (EDX) spectroscopy data (see Fig. 3)
also prove that the gold nanoparticles without impurities, such
as chlorides and sodium, are really present on the surface. This
means that the gold nanoparticles either do not contain contami-
nants that are present in the solutions used or their concentration
is lower than the threshold sensitivity of the EDX and XPS methods.
Fig. 3. EDX spectra of SnO2 lms deposited on a Si substrate and modied by AuNPs
using 3 SILD cycles.
Fig. 4. XPS Au 4f core level spectra of SnO2 lms with their surface modied by Au
nanoparticles deposited by SILD methods: (1) 0.5, (2) 2, and (3) 4 deposition cycles.
The 0.5 cycle means that the time of the treatment in HAuCl4 and NaBH4 solutions
was reduced 2-fold compared to the usual route.
The absence or small concentration of chlorine is a good indication
of the effectiveness of the washing procedure used in SILD. This
feature is a signicant advantage of the SILD method because the
removal of excess reactants and reaction products already occurs
during the gold nanoparticles deposition, in contrast to many other
methods of chemical deposition used for AuNP synthesis.
Typical XPS Au 4f (4f5/2 and 4f7/2 ) core level spectra are shown
in Fig. 4. XPS spectra show that repetition of deposition cycles is
accompanied by an increase in gold content at the metal oxide
surface. Moreover, the change in the intensity of the Au 4f peaks
corresponds to variations in the number of SILD cycles. For exam-
ple, the XPS data revealed that the surface concentration of gold
atoms [Au]/[Sn] increased from 0.01 after 0.5 deposition cycles
to 0.03 after 2 deposition cycles and to 0.06 after 4 SILD cycles.
This means that SILD technology truly provides the opportunity to
control the gold content on the surface of metal oxide lms. It is
important to note that XPS Au 4f peaks corresponding to binding
energies of 84 and 88 eV are already clearly visible after surface
modication when using a 0.5 deposition cycle. This means that an
appreciable amount of gold already appears on the surface of the
lms after such a treatment. However, no AuNPs were found on
the SEM images of these samples. This fact indicates that the size
of the gold particles formed on the surface of the SnO2 grains after
a 0.5 SILD cycle is less than the threshold resolution of the micro-
scope used, which was in the range of 13 nm. It looks realistic. For
example, the gold nanoparticles at initial stages of growth on a at
TiO2 surface during thermal evaporation have sizes in the range of
15 nm [42].
Analysis of the energy position of Au 4f peaks (binding energy
(BE) = 84.2 and 87.8 eV) suggests that gold on the SnO2 surface is
in the metallic state. For ionic Au3+ , the BEs are equal to 85.3 and
88.9 eV [43]. In principle, this outcome is not surprising because
the gold reduction to metal during thermal treatment is a typical
process for all systems containing gold deposited using wet chem-
ical methods. Typically, full gold reduction occurs at temperatures
above 300 C [44,45]. In the present experiments, the samples were
annealed at Tan = 450 C, and other chemical states of gold were
therefore not expected.
The XPS core level spectra, corresponding to the metal of the
dominant oxide (i.e., Sn 3d, see Fig. 5a), showed that the appear-
ance of the component corresponding to lower oxide states, such
as Sn2+ and Sno , did not take place. Sn 3d spectra are identical for
all samples regardless of the number of gold deposition cycles. Fur-
thermore, there is no change in the energy position of the peaks.
This means that there are no changes in the band bending. The
presence of gold also does not affect the shape of the O1s peak (see
Fig. 5b).
 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803 797

Fig. 7. Conductivity of the SnO2 lms modied by Au vs. the number of SILD depo-
sition cycles in different atmospheres at the operation temperature Toper = 280 C:
(1) air and (2) air + ozone (1 ppm).

Fig. 5. XPS (a) Sn 3d and (b) O 1s core level spectra of SnO2 lms with their surface
modied by Au clusters deposited by the SILD method: (1) initial SnO2 lms and (2)
SnO2 :Au samples after 4 deposition cycles.

All of this indicates that a signicant chemical interaction with

the oxide material does not take place during the gold deposition,
and the appearance of gold on the SnO2 surface is not accompanied
by a change in the initial ratio of adsorbed species present on the
SnO2 surface. It is also important to note that the intensities of the
primary XPS peaks of tin and oxygen, in contrast to Au 4f intensity,
are changed very slightly, which is evidence of the fact that gold Fig. 8. (a) Conductivity responses to H2 and CO (1000 ppm) of the SnO2 lms
occupies a small part of the surface. modied by Au vs. the number of SILD deposition cycles. (b) Typical temperature
dependencies of SnO2 -based sensor responses to H2 : (1) unmodied samples and
(2) SnO2 :Au sensors modied by AuNCs (1 deposition cycle).
3.3. Gas sensing characteristics

The results of the SnO2 -based gas sensor testing after sur- in the air and in atmospheres containing hydrogen (Fig. 6) and
face modication by AuNPs are shown in Figs. 69. In particular, ozone (Fig. 7). Figs. 8a and 9a present results related to the inu-
Figs. 6 and 7 show the inuence of the number of SILD cycles during ence of the number of SILD cycles during gold deposition on sensor
gold deposition on sheet resistance of the SnO2 :Au lms measured responses to reducing gases and ozone, respectively. The effect of

Fig. 6. Conductivity of the SnO2 lms modied by Au vs. the number of SILD depo- Fig. 9. (a) Inuence of the number of Au deposition cycles on the SnO2 :Au sensor
sition cycles in different atmospheres at the operation temperature Toper = 450 C: response to ozone. (b) Typical temperature dependencies of SnO2 -based sensors in
(1) air and (2) air + hydrogen (1000 ppm). response to ozone.
798 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
the operating temperature on the sensor responses is shown in
Figs. 8b and 9b. The results presented in Figs. 69 correspond to
operating temperatures at which there is a maximum of sensor
response. It is observed that the maximum response to reduc-
ing gases takes place at Toper of 450 C, whereas the maximum
response to ozone is observed at Toper of 280 C. Such a major dif-
ference in the behavior of the sensor responses to reducing and oxi-
dizing gases is typical for metal oxide sensors and can be explained
by a difference in the reactivity of the tested gases [10,15,36,46].
To eliminate the side effects of treatments used during SILD of
AuNPs on the sensor parameters, we performed additional experi-
ments with the studied samples; tested sensors were subjected to
the same treatments as they were during gold deposition, except
that the treatment in an aqueous solution of HAuCl4 was replaced
by washing with water. In Figs. 69, 0 deposition cycles cor-
responds to this treatment. This exact state was considered as a
reference point for the analysis of the inuence of gold deposition
on the properties of the SnO2 lms. 0.5 deposition cycles corre-
sponds to the treatment when the processing time in the HAuCl4
and NaBH4 water solutions was reduced two times in comparison
with the time of treatments used in all of the other experiments.
Initial in Figs. 69 corresponds to the parameters of the SnO2
gas sensors before any surface treatment. Detailed analysis of SnO2
gas sensor parameters with an unmodied surface can be found in
previously published articles [3436,4649].
Analysis of the results presented in Figs. 68 establishes that
the treatment with 0 deposition cycles, unlike other treatments
accompanied by deposition of gold, increases the lm resistance
(Figs. 6 and 7) and reduces the sensor response to reducing gases
(Fig. 8) relative to the initial unmodied samples. Unfortunately, we
do not know the real cause of the increase in the resistance after
the 0 deposition cycle treatment because this treatment included
washing with distilled water, treatment with a water solution of
NaBH4 , washing again with distilled water and annealing at 450 C.
Perhaps changes in the surface state of SnO2 lms occurred during
partial surface reduction after treatment with a water solution of
the treatment NaBH4 and subsequent thermal reoxidation during
annealing. However, such changes in SnO2 sample properties after
the 0 deposition cycle treatment, suggests that the increase in
sensor response and the decrease in the lm resistance observed for
tested SnO2 :Au samples after surface modication by gold clusters
associated with the appearance of AuNPs on the SnO2 surface.
There is an assumption that the active (i.e., the smallest) Au
nanoparticles are negatively charged through electron donation
from the conduction band of metal oxides. This assumption is
based on the experimentally established fact that gold atoms pre-
fer to bind to the site of oxygen vacancies (VO ) [50]. It is also
based on the results of theoretical studies [51] showing that gold
atoms can take electrons from VO . This assumption is important
because the presence of a negative charge on the gold nanopar-
ticles promotes either the activation or dissociation of molecular
oxygen and thus stimulates the oxidation of CO, 2 , alcohol, and
so forth. The same conclusion was made by Tsunoyama et al.
[52] regarding the Au:(poly(N-vinyl-2-pyrrolidone)-based catalyst.
Moreover, they found that the catalytic activity was enhanced with
increasing electron density on the Au core. In addition, the same
studies [51] conducted on TiO2 samples have shown that charge
transfer is only possible for small clusters, such as Au1 , Au3 , Au5
and Au7 and for certain Au strips on the surface. This behavior pro-
vides a basis for the conclusion that the interaction of the large gold
particles with the substrate is not as strong as that of the small
clusters.
As is known, electron transfer on gold nanoparticles should be
accompanied by the formation of depletion zones under the parti-
cles and an increase in metal oxide resistance. However, this effect
is not observed. Moreover, the resistance of the lm modied by
gold is slightly decreased (see Figs. 6 and 7). Such behavior can have
the following explanations: (1) because of their large size, most of
the gold particles on the SnO2 surface are neutral due to the lack
of electron exchange with support; (2) the negative charge trans-
ferred from the metal oxide to gold is less than the negative charge
captured by the species on the free SnO2 surface at the area equiva-
lent to the area of the gold particles; and (3) the appearance of gold
nanoparticles on the surface of the SnO2 crystallites is accompanied
by a decrease in the chemisorbed oxygen concentration.
Figs. 69 also demonstrate that the gold nanoparticles deposited
on the SnO2 surface are active to both reducing and oxidizing
gases (Figs. 8a and 9a). However, the increase in sensor response to
reducing gases is not signicant (see Fig. 8a). In principle, a strong
increase in sensitivity to reducing gases was not expected because
thin lms, especially those formed by thin-lm technology due to
the peculiarities of the morphology, are not optimal for detecting
such gases [49]. Films formed using thin-lm technology are usu-
ally characterized by lower porosity, a lack of necks, a larger area
of intergrain contacts, and an increased size of the crystallites rel-
ative to gas sensing material prepared using thick-lm technology
[53]. In addition, due to the factors indicated above, the maximum
sensitivity of sensors based on such lms as a rule is shifted to
higher temperatures in comparison to sensors fabricated by thick-
lm technology. An essential point in the obtained results was that
the increase in sensitivity was observed relative to both CO and
H2 (see Fig. 8a). At the same time, a signicant increase in the
response of SnO2 :Au-based sensors to ozone was unexpected. As
shown in Fig. 9a, the growth of sensor response to ozone may be as
large as two orders of magnitude. The sensitization to ozone leads
to the conclusion that the eld of using surface modications by
gold should not be limited to optimization of CO sensor parame-
ters [14]. These results along with data given by Krivetskiy et al. [15]
indicate that modication by gold can also be effective in the devel-
opment of SnO2 -based sensors of ozone, acetone vapors, hydrogen,
and so forth. Regarding NO2 sensors, more research is needed
because studies presented in Refs. [15,53,54] gave inconsistent
results.
Furthermore, the results presented in Figs. 8 and 9 have shown
that the effect of SnO2 surface decoration by AuNPs on gas sensing
characteristics depends on the number of deposition cycles (i.e.,
the size of the gold particles; see Figs. 8a and 9a). Thus, as in the
case of surface modication by noble metals such as Pd and Pt
[13], there is an optimal level of surface doping, and this level
of doping corresponds to a very low degree of surface coverage. As
seen in Figs. 8 and 9, the maximum sensor response is observed for
the samples corresponding to the 0.5 deposition cycle, for which
the presence of gold nanoparticles on SEM images has not been
observed. However, XPS studies indicated the presence of gold on
the surface of these samples (see Fig. 4). This signies that gold is
responsible for the observed effect and that atomically dispersed
gold or gold nanoparticles with a size not exceeding the resolution
of microscopes are the most active in gas sensing effects. The reso-
lution of the microscope used in the present studies was 23 nm.
This is consistent with data obtained for heterogeneous catalysis
[7,8], where the most catalytically active clusters had a size of
2.53.0 nm. However, one should note that a further increase of
deposition cycles, in which the gold nanoparticles appear on the
SEM images and their size reaches 610 nm or more [37], is not
accompanied by a sharp drop in sensor response, which should
occur if the effect of the gold particles size on the catalytic activity
is taken into account [7,8]. This result suggests that small parti-
cles can form on the surface of SnO2 rather than exclusively after
the rst deposition cycles and that the gas-sensitive effect involves
not only small but also large particles. This conclusion is consistent
with ndings made by Carabineiro and Thompson [55], who found
that gold-based catalysts are the most active in the 25 nm gold
 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
particle range, but that smaller and larger gold particles also have
activity and may play signicant roles.
It is important to note that surface modication by the gold
nanoparticles inuences the SnO2 lm conductivity measured in
the air without the addition of any target gas (Figs. 6 and 7). More-
over, for reducing gases, the lm resistance and sensor response
have identical dependences on the number of deposition cycles
(see Figs. 6 and 8). This suggests that most likely the same processes
are responsible for the increase in the conductivity of the SnO2 :Au
lms measured in the air without the addition of target gas and
for the growth of sensor response to reducing gases. As indicated
above, the gold particles formed on the surface of already deposited
SnO2 lms, and therefore AuNCs could not affect the bulk proper-
ties of the lms or their structure. This means that the gold particles
could only affect the processes having a surface nature. Analysis
of such processes suggests that the back spillover of chemisorbed
oxygen, which is intensied in the presence of reducing gases, is
the most likely process, which may explain the observed behavior
of both conductivity and sensor response in the presence of gold
nanoparticles (see Section 3.4).
The absence of a shift in the response maximum in the lower
temperature range for the SnO2 sensors with a modied surface is
another important result of the present study. The maximum sen-
sor response for the modied and unmodied SnO2 :Au samples
was observed at the same temperatures (Figs. 8b and 9b). From our
point of view, the absence of a shift of the sensor response max-
imum in the range of lower temperatures is quite natural for the
studied samples, because after the heat treatments used during gas
sensor fabrication, (i) the coalescence of most catalytically active
small gold particles with the formation of larger but less active par-
ticles takes place [47], and (ii) gold transforms to a metallic state
(see Section 3.2) in which gold does not show increased catalytic
activity in low temperature range [44,56]. The increased size of the
SnO2 crystallites and the large distance between gold particles can
also contribute to the observed behavior of S = f(Toper ) dependence.
As seen in the SEM images (Fig. 1), the 2050 nm SnO2 crystallites
only have 12 gold nanoparticles on their surface. However, when
the distance between the gold particles is too big, a signicant gas
sensing effect requires high temperature to provide high mobility
of the surface species participating in the detection reactions (see
Section 3.4). Otherwise, the area of spillover zones around the gold
particles is not sufcient for effective inuence of the gold particles
on the gas sensing properties of the SnO2 lms. Regarding crys-
tallite size, it is necessary to note that, according to Ref. [16], the
achievement of high AuNPs reactivity at low temperature requires
that metal oxide crystallites not exceed 56 nm. This statement is
justied because oxides with such small crystallite size perform
chemistry that is different than the chemistry of the same mate-
rials with larger crystallites. For example, the smaller metal oxide
nanoparticles with a spherulite shape may supply more active sites
and contribute to the strong interaction between gold and the
nanocrystalline metal oxide. Unfortunately, forming porous metal
oxides with such small crystallite size using thin-lm technology
is quite a difcult task [48,49]. As shown in Ref. [35], crystallites in
lms deposited on a heated substrate using thin-lm technologies
have a size that is proportional to the lm thickness.
It should be noted that the absence of a signicant shift in the
sensor response maximum of the SnO2 :Au-based sensors in the
low-temperature range that is characteristic of the current exper-
iments is also typical of almost all such studies [10,11,54,5760].
Almost all these studies were aimed at the development of sensors
suitable for the sensor market, and therefore heat treatment at
Tan 400 C was used in the fabrication technology. Such treatment
is necessary for the sensor parameter stabilization. It is important
that the absence of a temperature shift of the sensor response
maximum was observed regardless of the method used for the
799
Fig. 10. Inuence of the number of deposition cycles on the recovery time of
SnO2 :Au sensors after interacting with ozone.
surface modication by gold. Low temperature sensitivity to CO
was observed only for sensors that were not subjected to stabiliza-
tion annealing [61] or stabilized at temperatures below 200 C [12].
Low temperature sensitivity to CO was also observed by Ramgir
et al. [62], who reported that the SnO2 :Au lms used in gas sensors
were deposited by spray pyrolysis at Tspray = 450 C. However, in
this case, we doubt that the temperature was correct because spray
pyrolysis is accompanied by strong cooling of the substrate [63]. For
a prolonged spray pyrolysis, the temperature of the substrate can
be decreased by several hundred degrees. This situation appears
to have occurred in the experiments of Ramgir et al. [62], evi-
denced by the unusual morphology of the SnO2 :Au layers studied
[62].
Fig. 10 presents results related to the effect of surface modica-
tion on the recovery time of the sensor resistance after interacting
with ozone. It is observed that surface modication by gold is
accompanied by a decrease in the recovery time ( rec ) to the initial
state of the SnO2 :Au sensors after interacting with ozone. It should
be noted that this is an important effect because a long recovery
time is one of the major disadvantages of SnO2 -based ozone sen-
sors [63]. As shown in Fig. 10, the maximum effect of  rec reduction
was observed for the samples prepared using the maximum num-
ber of gold deposition cycles. Regarding the nature of this effect, one
can then suggest the following mechanism: Because the recovery
time in the case of ozone detection is determined by the lifetime of
chemisorbed atomic oxygen remaining on the metal oxide surface
after interacting with ozone [63], we presume that gold stimulates
reactions that reduce this time. Reverse oxygen spillover and disso-
ciative adsorption of water, carbon dioxide or hydrogen presenting
in the atmosphere and interacting with chemisorbed oxygen pre-
sented on the SnO2 surface are examples of such reactions. The
decreased recovery time with an increasing number of deposi-
tion cycles agrees with this hypothesis because the increase in
the size of the clusters and their number should decrease the dis-
tance between the clusters and should thus increase the role of the
spillover effect in the gas sensing phenomenon. It is clear that more
specic statements will require more research.
While analyzing the kinetics of the detection of reducing gases,
no positive effects from the surface modication by gold were
observed. In the range of operating temperatures between 300 C
and 400 C, surface modication by gold nanoparticles did not prac-
tically affect the kinetics of sensor response. We presume that
such a situation exists because the kinetics of the SnO2 :Au gas
sensor response is controlled by adsorption/desorption processes
taking place at the surface of SnO2 without participation of the gold
nanoparticles, which is quite probable assuming that the kinetics
of the sensor response are controlled by adsorption/desorption of
oxygen and water on the SnO2 surface. Earlier in Refs. [64,65], this
800 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
conclusion was conrmed for SnO2 -based sensors with unmodied
surfaces.
3.4. Sensitization mechanism in the SnO2 :Au-based gas sensor
Taking into account the close relationship of the gas sensi-
tive effect observed in conductometric sensors with heterogeneous
catalysis [66], one can state that the increased sensor response
is conditioned by the appearance of the catalytically active gold
nanoparticles on the SnO2 surface, which participate in a vari-
ety of reactions on the surface involved in sensor response, for
example such as the oxidation of CO and H2 . In Section 3.2, it was
shown that SnO2 surface at room temperature is contaminated with
carbon. However, we did not consider the inuence of this contam-
ination on gas sensing properties of SnO2 :Au. During the surface
modication experiments of SnO2 with gold, we did not observe
any correlation between concentration of carbon on the surface
measured at room temperature, and gas sensing properties. The
concentration of carbon remained almost unchanged. However, a
clear correlation between the concentration of gold on the surface
and gas sensing effects was detected. In addition, it was established
that at increased temperature and in an ozone-rich atmosphere,
this concentration strongly decreases [67]. It has been suggested
that the decrease in the concentration of carbon is due to the
oxidation reaction that occurs with participation of chemisorbed
oxygen and are accompanied by desorption of CO or CO2 . For
example Cataldo [68] showed that graphite nanoparticles react
with O3 already at room temperature with evolution of CO2 . Such
behavior of surface carbon explains why carbon has a low inu-
ence on gas sensing effects measured at temperatures higher than
180200 C. At these temperatures, highly reactive chemisorbed
oxygen appears at the surface of metal oxides. Because of this,
our attention was focused on gold nanoparticles. In addition, the
inclusion of carbon in our model may further complicate the con-
sideration of gas sensing properties of SnO2 :Au, that even without
carbon is rather complicated.
It is known that the increased sensor response should only be
observed in the case when electron transfer between surface cata-
lysts and metal oxide accompanies this catalytic reaction [66,69]. In
Ref. [6], based on the obtained data, H2 oxidation with the partici-
pation of Au/MeOx -based catalysts was presumed to occur without
electron transfer, whereas the oxidation of CO with electron trans-
fer is possible according to Ref. [39]. It appears from these studies
that during CO and H2 detection, a signicant difference in sen-
sor parameters should be observed. However, in the present study,
any essential difference in the behavior of the gas sensing charac-
teristics of the SnO2 Au sensors during CO and H2 detection were
not observed (see Fig. 6). On the basis of this fact, one can assume
that for the studied SnO2 Au system, the mechanisms of the sensor
response increase, observed during the detection of reducing gases
CO and H2 , are the same, at least at elevated temperatures.
It should be noted that at present there is no consensus
regarding the mechanism of gold nanoparticles participation in
gas sensing effects. Therefore, both electronic and chemical
[1,2,66,69] mechanisms of sensitization can be found in explana-
tions proposed by various authors who studied gas-sensing effects
in AuMeOx -based sensors. For example, Rogers et al. [70], analyz-
ing optical properties of AuYSZ lms, came to the conclusion that
between AuNPs and YSZ at T = 500 C, charge transfer takes place,
and the gas surrounding (CO, H2 , and O2 ) inuences this process.
However, it is not clear what the reason for this charge transfer, and
does this process take place at the Au surface or in the bulk of YSZ
(redox)? In Refs. [57,71,72], it was also noted that, due to a charge
transfer between the gold nanoparticles and SnO2 , the depletion
area is formed around gold nanoparticles on the surface of SnO2
nanobelts. In addition, it was concluded that this effect plays the
primary role in the sensitization of SnO2 :Au-based gas sensors. At
the same time, Hubner et al. [11], studying SnO2 :Au-based gas sen-
sors fabricated using the gel impregnation method, believed that
there is no electronic interaction between the gold nanoparticles
and host oxide and that the sensitization effect of Au during CO and
H2 detection can be attributed to the spillover effect. According
to this model, the Au particles enrich the surface of the active metal
oxide with oxygen species, which subsequently react with reduc-
ing gases such as CO and H2 . This statement is based on the fact that
the addition of gold during SnO2 synthesis was accompanied by an
increase in the lm resistance. However, it is known that molec-
ular oxygen does not chemisorb dissociatively onto a gold surface
within the temperature range of 25500 C [73,74]. This eliminates
the increase in the concentration of chemisorbed oxygen on the
surface of metal oxide due to oxygen spillover effects. In addition,
the experiment showed that the gold additive signicantly modi-
es the conditions of SnO2 synthesis and thus has a signicant effect
on crystallite properties, such as the size, shape, and lm morphol-
ogy [10,15,62]. From our point of view, these precise changes may
be the reason for the increased resistance observed in [13]. In the
present study, the effect of gold on the structural properties of the
SnO2 lm is excluded because the gold deposition was conducted
on an already formed lm. This means that gold could not inu-
ence the structure of the lm, and, therefore, changes observed in
the gas sensing properties had a purely surface nature. Moreover,
the data obtained (see Figs. 6 and 7) indicate that the resistance
of the SnO2 lm after modication by gold decreases. This sug-
gests that in the temperature range used there is a reduction in
the chemisorbed oxygen concentration on the surface of SnO2 :Au
crystallites but not its growth. This means that, in such a situation,
oxygen back spillover is more likely than the direct spillover effect
considered in [11]. However, at the same time, one can agree with
Hubner et al. [11] that, during the detection of reducing gases, there
is no change in the chemical state of Au. As shown in Section 3.2,
gold particles are already metallic in the initial state and there-
fore this state cannot change in a reducing atmosphere. This means
that the chemical mechanism seems preferable for the detection
of reducing gases. Certainly, one can agree with statements made
in numerous papers [11,61,75] that the processes responsible for
improvement in the sensor response of SnO2 :Au-based devices to
reducing gases take place at the periphery around the gold particles
(i.e., at the perimeter interface between the gold particle and the
metal oxide support, whereas oxygen species participating in oxi-
dation reactions responsible for gas sensing effects are provided by
the support (see Fig. 11a). It should be noted that the statements
made above correlate with results discussed in the previous sec-
tion, where it was determined that the sensor response is largely
controlled by processes occurring at the free surface of the SnO2
crystallites.
With regard to ozone detection, from our point of view, the
electronic mechanism is thus the most preferred for explaining
the observed effects. This mechanism is associated with oxidation
of gold in the ozone atmosphere and a corresponding increase in the
work function (see Fig. 11b). This should encourage the transition
of electrons from the metal oxide on the cluster and thus promote
an increase in the resistance of the metal oxide lm. As shown by
Miller et al. [76], small gold particles can be oxidized quite eas-
ily, whereas big clusters do not have such capability. Experiments
have shown that a metallic gold lm on TiO2 is stable toward heat-
ing in an oxygen atmosphere. However, Venkov et al. [77] have
established that, in a NO + O2 gas mixture, metallic gold on the
TiO2 surface is oxidized even at 573 K. The formation of a stable
gold oxide, Au2 O3 , after treatment in oxygen d.c. plasma was also
reported by Pireaux et al. [78] and Tsai et al. [79]. This oxide state of
Au corresponds to a formal state 3+. This means that Au oxidation
or at least signicant oxygen chemisorption on the gold surface in
 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
Fig. 11. Schematic diagram illustrating mechanisms of AuNP inuence on the gas sensing characteristics of SnO2 :Au lms in the case of (a) reducing gases (CO, H2 ) and (b)
oxidizing gases (O3 ): (a) adsorption of reducing gases, back spillover of chemisorbed oxygen and reaction of these species at the periphery of gold nanoparticles as the main
processes controlling reducing gas detection. (b) In the case of ozone, the mechanism of detection includes two processes: (1) oxidation/reduction of gold nanoparticles,
which is accompanied by electron transfer between SnO2 and gold nanoparticles, and (2) dissociative adsorption of ozone with following spillover of chemisorbed oxygen.
the atmosphere of a strong oxidizing gas such as ozone (O3 + O2 )
is possible. In particular, it is known that gold is reactive enough
to catalyze surface reactions, such as ozone dissociation [80]. The
results obtained by Saliba et al. [81], Puckett et al. [82], Biener et al.
[83], and King [84] also indicate an interaction of gold nanoparti-
cles with ozone. For example, King [84] found that gold surfaces
were oxidized by a combination of UV light and ozone generated
from a mercury lamp, and after such treatment, the gold surfaces
were enriched in oxygen. According to King [84], the oxide layer
was found to be 1.7 nm thick. Saliba et al. [81] also established
that, after interaction with ozone, the Au(1 1 1) surface was cov-
ered by chemisorbed oxygen, and an electron transfer took place
from the Au substrate to the oxygen adlayer, induced by the change
of the work function up to 0.80 eV. The change in the work func-
tion of the Au surface after UV/ozone treatment was also observed
by Suzue et al. [85]. They found that the work function changed at
0.55 eV. Here, it should be noted that this state is stable because the
chemisorbed oxygen species could be removed from the gold sur-
face only by heating the surface to temperatures of 600 K (375 C).
For comparison, as mentioned above, dissociative O2 adsorption on
the Au surface was observed only at temperatures exceeding 500 C
[73,74].
However, taking into account the inuence of gold particles on
the magnitude of sensor response to ozone, it must be recognized
that due to the small area of the gold nanoparticles on the surface
of the SnO2 crystallites, the electronic mechanism of sensitiza-
tion can hardly explain such a strong increase in sensor response.
It appears in this case that a combined mechanism works when
the oxidation/reduction of the gold nanoparticles is accompanied
by a spillover of chemisorbed oxygen, which is formed at the sur-
face of the gold clusters as a result of the dissociative adsorption of
ozone [80,81]. The spillover effect in this case stimulates electronic
exchange between SnO2 and the gold particles and also provides
growth of the concentration of chemisorbed oxygen on the SnO2
surface. In other words, the spillover effect, which occurs during the
interaction with ozone, promotes the growth of a negative charge
captured by a surface species and thus contributes to the increase in
band bending and the increased resistance of polycrystalline SnO2
lms.
4. Conclusions
The results presented in this study demonstrate that successive
ionic layer deposition (SILD) technology for gold nanoparticle for-
mation can be used for surface functionalization of SnO2 lms to
improve their gas sensing properties. It was found that the size of
the gold particles varies in the range of 150 nm depending on the
number of SILD cycles. It is established that the gold nanoparticles
deposited on the SnO2 surface are active to both reducing (CO
and H2 ) and oxidizing (O3 ) gases and that the effect of the SnO2
801
surface decoration by AuNPs on the gas sensing characteristics also
depends on the number of deposition cycles (i.e., the size of the
gold particles). The maximum effect is observed with the smallest
size gold nanoparticles. Sensitization to O3 and H2 suggests that
applications of the gold surface modication in the eld of gas
sensor design should not be limited to the optimization of the CO
sensor parameters.
Models showing the promotional role of Au additives were also
discussed, and a mechanism of sensitization in the SnO2 :Au-based
gas sensor was proposed. Based on the results obtained, it was
assumed that (1) during interaction with reducing gases, gold does
not change its chemical state (i.e., AuNCs remain in a metallic
state); (2) processes that are responsible for improving the sen-
sor response occur at the periphery around the Au nanoparticles;
and (3) oxygen back spillover is more likely than is a direct spillover
effect. With regard to the detection of ozone, it was concluded that
an electronic mechanism, which is associated with the oxidation
of gold nanoparticles in ozone atmosphere, and the increase of the
work function seem to be preferred. The increase of the work func-
tion should stimulate the transition of electrons from the metal
oxide to the gold particles and thus increase the resistance of the
metal oxide lm.
However, the same analysis also conrms that our knowledge of
the processes taking place in the AuSnO2 system is rather limited
and that to extend this fundamental understanding, additional
research is required. The SILD technology analyzed in this paper
also requires further development and optimization. In particular,
from our point of view, it is necessary to nd criteria that allow an
increase in the number of gold nanoparticles of the required size
formed on the surface of metal oxide crystallites (i.e., increasing
the density of their distribution and decreasing the inter-particles
distance). It is also important to elucidate the role of the size of the
SnO2 crystallites in gas-sensitive effects involving gold nanoparti-
cles.
Acknowledgments
This work was supported by National Research Foundation
(NRF) grants funded by the Korean government (Nos. 2011-
0028736 and 2013-K000315), by the Basic Science Research
Program through the NRF funded by the Ministry of Science, ICT
and Future Planning of Korea (2012-R1A1A2041564), by the Rus-
sian Foundation for Basic Research (Grant No. 15-03-08045A), and
by the Moldova Government under grant 15.817.02.29F and ASM-
STCU project #5937. The authors are also thankful to Dr. X.Y. Chen
and Prof. J. Schwank from the University of Michigan, USA for help
in SnO2 :Au lm characterization and Prof. V.P. Tolstoy from St.
Petersburg State University, Russia, for participation in the design
of the SILD technology used for SnO2 surface modication by gold
nanoparticles.
802 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
References
[1] D. Kohl, The role of noble metals in the chemistry of solid-state gas sensors,
Sens. Actuators B 1 (16) (1990) 158165.
[2] N. Yamazoe, New approaches for improving semiconductor gas sensors, Sens.
Actuators B 5 (1991) 719.
[3] G. Korotcenkov, V. Brinzari, Y. Boris, M. Ivanov, J. Schwank, J. Morante, Surface
Pd doping inuence on gas sensing characteristics of SnO2 thin lms
deposited by spray pyrolysis, Thin Solid Films 436 (1) (2003) 119126.
[4] D.Y. Cha, G. Parravano, Surface reactivity of supported gold. I. Oxygen transfer
between carbon monoxide and carbon dioxide, J. Catal. 18 (1970) 200211.
[5] M. Haruta, T. Kobayashi, H. Sano, N. Yamada, Novel gold catalysts for the
oxidation of carbon monoxide at a temperature far below 0 C, Chem. Lett.
(1987) 405406.
[6] M. Haruta, N. Yamada, T. Kobayashi, S. Iijima, Gold catalysts prepared by
coprecipitation for low-temperature oxidation of hydrogen and of carbon
monoxide, J. Catal. 115 (1989) 301309.
[7] M. Haruta, Size- and support-dependency in the catalysis of gold, Catal. Today
36 (1997) 153166.
[8] A.K. Santra, D.W. Goodman, Catalytic oxidation of CO by platinum group
metals: from ultrahigh vacuum to elevated pressures, Electrochem. Acta 47
(2002) 35953609.
[9] Gold: chemistry, materials and catalysis, Chem. Soc. Rev. 37 (2008)
17452140.
[10] A. Cabot, J. Arbiol, J.R. Morante, U. Weimar, N. Barsan, W. Gopel, Analysis of
the noble metal catalytic additives introduced by impregnation of as obtained
SnO2 solgel nanocrystals for gas sensors, Sens. Actuators B 70 (2000)
87100.
[11] M. Hubner, D. Koziej, J.-D. Grunwaldt, U. Weimar, N. Barsan, An Au clusters
related spill-over sensitization mechanism in SnO2 -based gas sensors
identied by operando HERFD-XAS, work function changes, DC resistance and
catalytic conversion studies, Phys. Chem. Chem. Phys. 14 (2012)
1324913254.
[12] S. Wang, Y. Zhao, J. Huang, Y. Wang, H. Ren, S. Wu, S. Zhang, W. Huang,
Low-temperature CO gas sensors based on Au/SnO2 thick lm, Appl. Surf. Sci.
253 (2007) 30573061.
[13] L. Wang, H. Dou, Z. Lou, T. Zhang, Encapsuled nanoreactors (Au@SnO2 ): a new
sensing material for chemical sensors, Nanoscale 5 (2013) 26862691.
[14] B. Bahrami, A. Khodadadi, M. Kazemeini, Y. Mortazavi, Enhanced CO
sensitivity and selectivity of gold nanoparticles-doped SnO2 sensor in
presence of propane and methane, Sens. Actuators B 133 (2008) 352356.
[15] V. Krivetskiy, A. Ponzoni, E. Comini, S. Badalyan, M. Rumyantseva, A. Gaskov,
Selectivity modication of SnO2 -based materials for gas sensor arrays,
Electroanalysis 22 (23) (2010) 28092816.
[16] G. Korotcenkov, V. Brinzari, B.K. Cho, What restricts gold clusters reactivity in
catalysis and gas sensing effects: a focused review, Mater. Lett. 147 (2015)
101104.
[17] K. Saha, S.S. Agasti, C. Kim, X. Li, V.M. Rotello, Gold nanoparticles in chemical
and biological sensing, Chem. Rev. 112 (2012) 27392779.
[18] M. Okumura, K. Tanaka, A. Ueda, M. Haruta, The reactivities of
dimethylgold(III)-diketone on the surface of TiO2 : a novel preparation
method for Au catalysts, Solid State Ionics 95 (1997) 143149.
[19] J. Turkevich, P.C. Stevenson, J. Hiller, A study of the nucleation and growth
processes in the synthesis of colloidal gold, Discuss. Faraday Soc. 11 (1951)
5575.
[20] M. Brust, M. Walker, D. Bethell, D.J. Schiffrin, R. Whyman, Synthesis of thiol
derivatized gold nanoparticles in a 2-phase liquidliquid system, J. Chem. Soc.
Chem. Commun. 1994 (1994) 801802.
[21] J. Schwank, S. Galvagno, G. Parravano, Isotopic oxygen exchange on supported
ruthenium and gold catalysts, J. Catal. 63 (1980) 415424.
[22] I. Fasaki, M. Suchea, G. Mousdis, G. Kiriakidis, M. Kompitsas, The effect of Au
and Pt nanoclusters on the structural and hydrogen sensing properties of
SnO2 thin lms, Thin Solid Films 518 (2009) 11091113.
[23] V.P. Tolstoi, Synthesis of thin-layer structures by the ionic layer deposition
method, Russ. Chem. Rev. 62 (3) (1993) 237242.
[24] V.P. Tolstoy, Successive ionic layer deposition. The use in nanotechnology,
Rus. Chem Rev. 75 (2) (2006) 161175.
[25] G. Korotcenkov, V. Tolstoy, J. Schwank, Successive ionic layer deposition
(SILD) as a new sensor technology: synthesis and modication of metal
oxides, Meas. Sci. Technol. 17 (2006) 18611869.
[26] S.S. Kale, R.S. Mane, H. Chung, M.-Y. Yoon, C.D. Lokhande, S.-H. Han, Use of
successive ionic layer adsorption and reaction (SILAR) method for amorphous
titanium dioxide thin lms growth, Appl. Surf. Sci. 253 (2006) 421424.
[27] R. Salazar, A. Delamoreanu, B. Saidi, C. Lvy-Clment, V. Ivanova, CdTe
deposition by successive ionic layer adsorption and reaction (SILAR)
technique onto ZnO nanowires, Phys. Stat. Solidi (A) 211 (9) (2014)
21152120.
[28] K.G. Stamplecoskie, J.S. Manser, Facile SILAR approach to air-stable naked
silver and gold nanoparticles supported by alumina, Appl. Mater. Interfaces 6
(20) (2014) 1748917495.
[29] H. Lee, H. Leventis, S. Moon, P. Chen, S. Ito, S. Haque, T. Torres, F. Nesch, T.
Geiger, S. Zakeeruddin, M. Grtzel, M.K. Nazeeruddin, PbS and CdS quantum
dot-sensitized solid-state solar cells: old concepts, new results, Adv. Funct.
Mater. 19 (2009) 27352742.
[30] P. Hoffmann, Tomorrows Energy: Hydrogen Fuel Cells and the Prospects for a
Cleaner Planet, MIT Press, Cambridge, 2012.
[31] J.S. Murphy, J.R. Orr (Eds.), Ozone Chemistry and Technology: A Review of the
Literature 19611974, Franklin Institute Press, Philadelphia, 1975.
[32] G. Korotcenkov, B.K. Cho, L. Gulina, V. Tolstoy, Ozone sensors based on SnO2
lms modied by SnO2 Au nanocomposites synthesized by the SILD method,
Sens. Actuators B 138 (2009) 512517.
[33] G. Korotcenkov, B.K. Cho, L. Gulina, V. Tolstoy, SnO2 thin lms modied by the
SnO2 Au nanocomposites: response to reducing gases, Sens. Actuators B 141
(2009) 610616.
[34] G. Korotcenkov, V. Brinzari, J. Schwank, A. Cerneavschi, Possibilities of aerosol
technology for deposition of SnO2 -based lms with improved gas sensing
characteristics, Mater. Sci. Eng. C 19 (12) (2001) 7377.
[35] G. Korotcenkov, B.K. Cho, V. Brinzari, Spray pyrolysis of metal oxides SnO2 and
In2 O3 as an example of thin lm technology: advantages and limitations for
application in conductometric gas sensors, Adv. Mater. Res. 748 (2013) 2227.
[36] G. Korotcenkov, I. Blinov, M. Ivanov, J.R. Stetter, Ozone sensors on the base of
SnO2 thin lms deposited by spray pyrolysis, Sens. Actuators B 120 (2007)
679686.
[37] G. Korotcenkov, L.B. Gulina, B.K. Cho, V. Brinzari, V.P. Tolstoy, Synthesis by
successive ionic layer deposition (SILD) methodology and characterization of
gold nanoclusters on the surface of the tin and indium oxide lms, Pure Appl.
Chem. 86 (5) (2014) 801817.
[38] G. Korotcenkov, B.K. Cho, Instability of metal oxide-based conductometric gas
sensors and approaches to stability improvement, Sens. Actuators B 156
(2011) 527538.
[39] T. Minato, T. Susaki, S. Shiraki, H.S. Kato, M. Kawai, K. Aika, Investigation of the
electronic interaction between TiO2 (1 1 0) surfaces and Au clusters by PES and
STM, Surf. Sci. 566568 (2004) 10121017.
[40] E. Wahlstrom, N. Lopez, R. Schaub, P. Thostrup, A. Rnnau, C. Africh, E.
Lgsgaard, J.K. Nrskov, F. Besenbacher, Bonding of gold nanoclusters to
oxygen vacancies on rutile TiO2 (1 1 0), Phys. Rev. Lett. 90 (2003) 026101.
[41] M. Sitarz, M. Kwoka, E. Comini, D. Zappa, J. Szuber, Surface chemistry of SnO2
nanowires on Ag-catalyst-covered Si substrate studied using XPS and TDS
methods, Nanoscale Res. Lett. 9 (2014) 43.
[42] A.K. Santra, A. Kolmakov, F. Yang, D.W. Goodman, Growth of Au on TiO2 (1 1 0)
on a cluster-by-cluster basis, J. Appl. Phys. 42 (2003) 47954798.
[43] G. Korotcenkov, L.B. Gulina, B.K. Cho, S.H. Han, V.P. Tolstoy, SnO2 Au
nanocomposite synthesized by successive ionic layer deposition method:
characterization and application in gas sensors, Mater. Chem. Phys. 128
(2011) 433441.
[44] S. Wang, J. Huang, Y. Zhao, S. Wang, X. Wang, T. Zhang, S. Wu, S. Zhang, W.
Huang, Preparation, characterization and catalytic behavior of SnO2
supported Au catalysts for low-temperature CO oxidation, J. Mol. Catal. A:
Chem. 259 (2006) 245252.
[45] H.Y.Y. Ko, M. Mizuhata, A. Kajinami, S. Deki, Preparation of Au nanoparticle
dispersed Nb2 O5 composite lm by liquid phase deposition, J. Electroanal.
Chem. 559 (2003) 9198.
[46] G. Korotcenkov, V. Brinzari, V. Golovanov, Y. Blinov, Kinetics of gas response
to reducing gases of SnO2 lms deposited by spray pyrolysis, Sens. Actuators
B 98 (1) (2004) 4145.
[47] G. Korotcenkov, I. Blinov, V. Brinzari, J.R. Stetter, Effect of air humidity on gas
response of SnO2 thin lm ozone sensors, Sens. Actuators B 122 (2007)
519526.
[48] G. Korotcenkov, V. Brinzari, M. DiBattista, J. Schwank, A. Vasiliev, Peculiarities
of SnO2 thin lm deposition by spray pyrolysis for gas sensor application,
Sens. Actuators B 77 (12) (2001) 244252.
[49] G. Korotcenkov, B.K. Cho, Thin lm SnO2 -based gas sensors: lm thickness
inuence, Sens. Actuators B 142 (2009) 321330.
[50] A. Vijay, G. Mills, H. Metiu, Adsorption of gold on stoichiometric and reduced
rutile TiO2 (1 1 0) surfaces, J. Chem. Phys. 118 (2003) 65366551.
[51] S. Chrdtien, H. Metiu, Density functional study of the charge on Aun clusters
(n = l7) supported on a partially reduced rutile TiO2 (1 1 0): are all clusters
negatively charged? J. Chem. Phys. 126 (2007) 104701.
[52] H. Tsunoyama, N. Ichikuni, H. Sakurai, T. Tsukuda, Effect of electronic
structures of Au clusters stabilized by poly(N-vinyl-2-pyrrolidone) on aerobic
oxidation catalysis, J. Am. Chem. Soc. 131 (2009) 70867093.
[53] N.M. Shaalan, T. Yamazaki, T. Kikuta, Synthesis of metal and metal oxide
nanostructures and their application for gas sensing, Mater. Chem. Phys. 127
(2011) 143150.
[54] E.Y. Sevastyanov, N.K. Maksimova, V.A. Novikov, F.V. Rudov, N.V.
Sergeychenko, E.V. Chernikov, Effect of Pt, Pd, Au additives on the surface and
in the bulk of tin dioxide thin lms on the electrical and gas-sensitive
properties, Semiconductors 46 (6) (2012) 801809.
[55] S.A.C. Carabineiro, D.T. Thompson, Catalytic applications for gold
nanotechnology, in: U. Heiz, U. Landman (Eds.), Nanocatalysis (Nanoscience
and Technology Series), Springer, Berlin, Heidelberg, 2007, pp. 377489.
[56] F.E. Wagner, S. Galvano, C. Milone, A.M. Visco, Mossbauer characterization of
gold/iron oxide catalysts, J. Chem. Soc. Faraday Trans. 93 (1997) 34033409.
[57] P. Montmeat1, J.-C. Marchand, R. Lalauze, J.-P. Viricelle, G. Tournier, C. Pijolat,
Physico-chemical contribution of gold metallic particles to the action of
oxygen on tin dioxide sensors, Sens. Actuators B 95 (2003) 8389.
[58] S.M. Badalyan, M.N. Rumyantseva, S.A. Nikolaev, A.V. Marikutsa, V.V. Smirnov,
A.S. Alikhanian, A.M. Gaskov, Effect of Au and NiO catalysts on the NO2 sensing
properties of nanocrystalline SnO2 , Inorg. Mater. 46 (3) (2010) 232236.
[59] X. Wang, S. Qiu, C. He, G. Lu, W. Liu, J. Liu, Synthesis of Au decorated SnO2
mesoporous spheres with enhanced gas sensing performance, RSC Adv. 3
(2013) 1900219008.
 G. Korotcenkov et al. / Applied Surface Science 353 (2015) 793803
[60] S. Ahlers, G. Mller, Th. Doll, Factors inuencing the gas sensitivity of metal
oxide materials, in: C.A. Grimes, E.C. Dickey, M.V. Pishko (Eds.), Encyclopedia
of Sensors, vol. 3, American Scientic Publisher, Valencia, CA, 2006, pp.
413447.
[61] P. Manjula, S. Arunkumar, V. Sunkara, Manorama, Au/SnO2 an excellent
material for room temperature carbon monoxide sensing, Sens. Actuators B
152 (2011) 168175.
[62] N.S. Ramgir, Y.K. Hwang, S.H. Jhung, H.-K. Kim, J.-S. Hwang, I.S. Mulla, J.-S.
Chang, CO sensor derived from mesostructured Au-doped SnO2 thin lm,
Appl. Surf. Sci. 252 (2006) 42984305.
[63] G. Korotcenkov, B.K. Cho, Ozone measuring: what can limit the application of
SnO2 -based gas sensors? Sens. Actuators B 161 (2012) 2844.
[64] V. Brynzari, G. Korotchenkov, S. Dmitriev, Simulation of thin lm gas sensor
kinetics, Sens. Actuators B 61 (1999) 143153.
[65] V. Brynzari, G. Korotchenkov, S. Dmitriev, Theoretical study of semiconductor
thin lm gas sensitivity: attempt to consistent approach, J. Electron. Technol.
33 (2000) 225235.
[66] M. Madou, S.R. Morrison, Chemical Sensing With Solid State Devices,
Academic Press, Boston, 1990.
[67] J.R. Vig, UV/ozone cleaning of surface, J. Vac. Sci. Technol. A 3 (3) (1985)
10271034.
[68] F. Cataldo, Ozone reaction with carbon nanostructures. 2: The reaction of
ozone with milled graphite and different carbon black grades, J. Nanosci.
Nanotechnol. 7 (45) (2007) 14461454.
[69] G. Korotcenkov, Gas response control through structural and chemical
modication of metal oxides: state of the art and approaches, Sens. Actuators
B 107 (2005) 209232.
[70] P.H. Rogers, G. Sirinakis, M.A. Carpenter, Direct observations of
electrochemical reactions within AuYSZ thin lms via absorption shifts in
the Au nanoparticle surface plasmon resonance, J. Phys. Chem. C 112 (17)
(2008) 67496757.
[71] A. Kolmakov, D.O. Klenov, Y. Lilach, S. Stemmer, M. Moskovits, Enhanced gas
sensing by individual SnO2 nanowires and nanobelts functionalized with Pd
catalyst particles, Nano Lett. 5 (2005) 667673.
[72] L.H. Qian, K. Wang, Y. Li, H.T. Fang, Q.H. Lu, X.L. Ma, CO sensor based on
Au-decorated SnO2 nanobelt, Mater. Chem. Phys. 100 (2006) 8284.
803
[73] M.A. Chesters, G.A. Somorjai, The chemisorption of oxygen, water and
selected hydrocarbons on the (1 1 1) and stepped gold surfaces, Surf. Sci. 52
(1975) 2128.
[74] A.G. Sault, R.J. Madix, Adsorption of oxygen and hydrogen on Au(1 1 0)-(1 2),
Surf. Sci. 169 (1986) 347356.
[75] L.H. Qian, K. Wang, H.T. Fang, Y. Li, X.L. Ma, Au nanoparticles enhance CO
oxidation onto SnO2 nanobelt, Mater. Chem. Phys. 103 (2007) 132136.
[76] J.T. Miller, J. Kropf, Y. Zha, J.R. Regalbuto, L. Delannoy, C. Louis, E. Bus, J.A. van
Bokhoven, The effect of gold particle size on AuAu bond length and
reactivity toward oxygen in supported catalysts, J. Catal. 240 (2006)
222234.
[77] Tz. Venkov, K. Fajerwerg, L. Delannoy, Hr. Klimev, K. Hadjiivanov, C. Louis,
Effect of the activation temperature on the state of gold supported on titania:
an FT-IR spectroscopic study, Appl. Catal. A 301 (2006) 106114.
[78] J. Pireaux, M. Liehr, P.A. Thiry, J.P. Delrue, R. Caudano, Electron spectroscopic
characterization of oxygen adsorption on gold surfaces: II. Production of gold
oxide in oxygen DC reactive sputtering, Surf. Sci. 141 (1984)
221232.
[79] H. Tsai, E. Hu, K. Pemg, M. Chen, J. Wu, Y. Chang, Instability of gold oxide
Au2 O3 , Surf. Sci. 537 (2003) L447L450.
[80] J. Kim, E. Samano, B.E. Koel, Oxygen adsorption and oxidation reactions on
Au(2 1 1) surfaces: exposures using O2 at high pressures and ozone (O3 ) in
UHV, Surf. Sci. 600 (2006) 46224632.
[81] N. Saliba, D. Parker, B. Koela, Adsorption of oxygen on Au(1 1 1) by exposure to
ozone, Surf. Sci. 410 (1998) 270282.
[82] S.D. Puckett, J.A. Heuser, J.D. Keith, W.U. Spendel, G.E. Pacey, Interaction of
ozone with gold nanoparticles, Talanta 66 (2005) 12421246.
[83] J. Biener, A. Wittstock, L.A. Zepeda-Ruiz, M.M. Biener, V. Zielasek, D.R. Kramer,
N. Viswanath, J. Weissmller, M. Bumer, A.V. Hamza,
Surface-chemistry-driven actuation in nanoporous gold, Nat. Mater. 8 (2009)
4751.
[84] D.E. King, Oxidation of gold by ultraviolet light and ozone at 25 C, J. Vac. Sci.
Technol. A 1 (3) (1995) 12471253.
[85] Y. Suzue, T. Manaka, M. Iwamoto, Currentvoltage characteristics of
pentacene lms: effect of UV/ozone treatment on Au electrodes, Jpn. J. Appl.
Phys. 44 (1B) (2005) 561565.