Sensors and Actuators B 175 (2012) 163–172

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Sensors and Actuators B: Chemical

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Nanopowders of chromium doped TiO2 for gas sensors

B. Lyson-Sypien a,∗ , A. Czapla a , M. Lubecka a , P. Gwizdz a , K. Schneider a , K. Zakrzewska a , K. Michalow b ,
T. Graule b , A. Reszka c , M. Rekas d , A. Lacz d , M. Radecka d
a
Faculty of Electrical Engineering, Automatics, Computer Science and Electronics, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Cracow, Poland
b
EMPA, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for High Performance Ceramics, Uberlandstrasse 129, 8600 Duebendorf, Switzerland
c
Institute of Physics, Polish Academy of Science, al. Lotników 32/46, 02-668 Warsaw, Poland
d
Faculty of Materials Science and Ceramics, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Cracow, Poland

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

Article history: Nanocrystalline powders of TiO2 and TiO2 :Cr (0.1–10 at.% Cr) obtained by flame spray synthesis (FSS),
Available online 24 February 2012 are used as starting materials for preparation of gas sensors. Characterization of nanopowders is carried
out by thermogravimetry (TG), Brunauer–Emmett–Teller (BET), adsorption isotherms, X-ray diffraction
Keywords: (XRD), and scanning electron microscopy (SEM). Gas sensing materials are calcined at 400 ◦ C in a form of
TiO2 nanopowders tablets, the morphology of which is similar to that of starting materials. The mass loss of nanopowders
Cr dopant
upon heating, as determined from its temperature profile in TG, is correlated with the specific surface
Gas sensors
area (SSA) obtained from BET measurements. High SSA exceeding 100 m2 /g is inherently related to the
Hydrogen detection
Flame spray synthesis
enhanced decomposition of organic residua below 400 ◦ C. XRD diffraction patterns indicate small crystal-
lite sizes (6–27 nm) and the presence of both polymorphic forms: anatase and rutile, independently of the
form of nanomaterials. SEM images demonstrate agglomeration of crystallites into spherical grains. Gas
sensing characteristics of TiO2 :Cr nanosensors upon interaction with H2 are recorded in a self-assembled
experimental system. Detection of hydrogen is carried out over the concentration range of 50–3000 ppm
at the temperatures extending from 200 to 400 ◦ C. It is demonstrated that nanomaterials based on TiO2 :Cr
are attractive for ultimate sensor applications due to a substantial decrease in the operating tempera-
ture down to 210–250 ◦ C. At a certain level of doping (of about 5 at.%) a reversal of the sensor response
from that of n-type to that of p-type semiconductor is seen. This effect can be accounted for by the
acceptor-type substitutional defects CrTi built into TiO2 lattice.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction faces or interfaces. Therefore, smaller particle size, by its favorable

impact on the specific surface area, i.e., an increased surface-to-
In 1991, Yamazoe [1] demonstrated an important improvement volume ratio, is expected to enhance the density of centers active
in performance of metal oxide semiconducting gas sensors with for chemisorption [2,10]. When the average size of a building block
a nanometric crystallite size. Since then substantial efforts have of a nanomaterial becomes comparable with the width of the deple-
been made to produce and test nanostructured materials for gas tion region, the sensitivity and kinetics of response to gases are
sensing [2] with the ultimate aim to increase their sensitivity and improved. Furthermore, nanosensors can work at lower temper-
selectivity, decrease the response time and temperature of opera- atures as compared with their microcrystalline counterparts. This
tion while still preserving long term stability and reproducibility. is particularly important for reduction of both power consumption
Different forms of nanomaterials were proposed, among which the and cost of operation of any sensor system.
most attractive seem to be nanotubes [3–5], nanobelts [6,7] and Titanium dioxide is a well known and extensively examined
nanowires [8,9]. gas sensing material. Resistive gas sensors based on TiO2 emerged
Nanostructures offer not only a decreased particle size, but also thanks to promising features such as: reversible and large changes
an increased specific surface area, which results in many new phys- in the electrical resistance along with the exceptional chemical
ical and chemical phenomena that are impossible to encounter stability of titania [11–13].
at the micrometer scale. The mechanism of gas sensing involves Early studies brought up the subject of TiO2 bulk sensor working
adsorption and desorption processes at the grain boundaries, sur- over high temperature range [14,15] and governed by thermody-
namics of point defects. Since that time an extensive effort has
been made to improve TiO2 based gas sensor’s parameters, i.e., to
∗ Corresponding author. Tel.: +48 12 617 29 01; fax: +48 12 633 23 98.
decrease the operating temperature [3,16], response and recovery
E-mail address: Barbara.Lyson@fis.agh.edu.pl (B. Lyson-Sypien).
times [16,17], costs of operation and to lower the detection limit

0925-4005/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2012.02.051
164 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172

[17,18]. Additional requirements include: improved thermal sta-

bility [19], increased selectivity and sensitivity towards different
agents, e.g., H2 [20,21], alcohol [16,22], CO [23,24], NH3 [25,26],
organic vapors [27], NO2 [28] and humidity [29,30].
There are different approaches to the problem of modification of
TiO2 necessary for fabrication of efficient gas sensors. Among many
others, the most exploited for the moment seems to be synthesis of
nanostructured TiO2 in a form of nanopowders [31,32], nanotubes
[4,33,5], nanowires [34,35] and nanofibers [36,37].
More traditional methods consist in loading TiO2 with metal
additives such as: Pt [19,27,38], La [22], Cu [19,23], Nb [19,28,29],
Pd [19,33,36], Ag [17,39]. Modification of the surface of TiO2
nanostructures [17,40] becomes a new promising technology. It is
generally accepted that basic parameters characterizing gas sensor
performance such as sensitivity, selectivity and response time of
TiO2 -based sensors can be optimized by choosing an appropriate
type and level of doping [41–44].
Many attempts have been undertaken in the past to exploit the  of Cr dopant as a function of
Fig. 1. Specific surface area SSA and concentration
the sum of precursors’ mole number per minute nprec for TiO2 :Cr nanopowders
influence of a trivalent Cr dopant acting as an acceptor type impu-
obtained by FSS.
rity on the electrical and gas sensing properties of TiO2 [45–48].
It has been demonstrated that doping improves the response time
and sensitivity [45,46]. Moreover, it enables to decrease the ini- The motivation for this study is to decrease the temperature of
tial resistivity (baseline) of the sensor thus widens the signal hydrogen detection as well as to investigate the size effect with
detection range [45,47,48]. Furthermore, it has been observed respect to gas sensing properties. The effect of chromium concen-
that Cr additive can change the type of conductivity from n to p tration and crystallite size on the sensor dynamic responses to
[47–51], which is particularly interesting for detection of oxidizing hydrogen is discussed.
gases.
Incorporation of Cr is accompanied by formation of additional
defects like oxygen vacancies VO and titanium interstitials Tii and 2. Experimental
leads to a shift of n → p transition towards lower oxygen partial
pressure [50,51]. Owing to that, not only the detection range of the Nanopowders of TiO2 :Cr with up to 10 at.% Cr were obtained
sensor can be extended but also the baseline resistance is lowered, by flame spray synthesis (FSS) as described in detail in [59,60].
as well. Therefore, the operation temperature can be reduced. Titanium tetra-isopropoxide TTIP and a solution of chromium
Chromium forms several oxides among which the best-known acetyloacetonate CHAA in m-xylene were used as precursors of
and the most important are chromium (VI) oxide CrO3 , chromium Ti and Cr, respectively. The total feed flow rate FRTotal of precur-
(III) oxide Cr2 O3 and hydrated chromium dioxide CrO2 ·nH2 O. At sors was kept constant during the synthesis process. In order to
temperatures below 400–500 ◦ C various oxygen-rich phases exist, increase chromium concentration in TiO2 nanoparticles, the feed
and the compositions of oxide phases in the Cr2 O3 –CrO3 region are flow rate FRdopant of Cr precursor was increased and FRTTIP of the
reported to be CrO2.65 (beta-oxide), CrO2.44 (gamma oxide), Cr6 O15 , main precursor of titanium TTIP was diminished. This resulted in a
Cr5 O15 , CrO2 [52–54]. Cr2 O3 is the only solid chromium oxide which simultaneous increase in the Cr concentration in TiO2 and, as shown
is stable at high temperatures above 500 ◦ C. in Fig. 1, an enhanced specific surface area, SSA.
Despite of lot of effort spent on the studies of the mechanism Specific surface area, SSA, of nanopowders was determined from
of incorporation of Cr into TiO2 , this problem remains unresolved. nitrogen adsorption BET (Brunauer–Emmett–Teller) isotherms
It is usually assumed that Cr3+ substitutes for Ti up to 5 at.% [48]. obtained with a Beckman-Coulter SA3100. Powders were annealed
According to the phase diagrams of Cr2 O3 –TiO2 [55] up to 10 at.% under nitrogen atmosphere at 180 ◦ C for 2 h in order to desorb
of Cr can be accommodated in TiO2 without any visible precipi- water from their surface.
tation of new phases. In nanopowders, this solubility limit can be As self-contained nanopowders cannot be used directly in gas
extended to higher values. sensing experiments, further processing of the starting materials
However, some authors [56,57] claim that Cr(VI) can be present into tablets by calcinations was necessary.
in TiO2 along with Cr(III). In order to establish an appropriate temperature of the
Our previous papers concentrated on titanium dioxide thin films subsequent calcinations, thermogravimetry (TG) measurements
and microcrystalline ceramics for gas sensing applications [43,58]. were carried out on SDT 2960 TA INSTRUMENTS apparatus. The
Nanopowders doped with chromium were applied as photocat- nanopowder samples of mass around 20 mg were placed in the
alytic materials [59,60]. standard platinum crucibles and heated at a rate of 10 ◦ C min−1 .
The analysis of structure and morphology as well as the mecha- The measurements were carried out under dynamic conditions
nism of Cr incorporation into TiO2 nanopowders obtained by flame (the flow of 100 cm3 min−1 ) in synthetic air atmospheres (<15 ppm
spray synthesis (FSS) has been performed in [59,60]. FSS method H2 O). The volatile products of decomposition were analyzed by a
has been applied as an attractive technology because it provides quadrupole mass spectrometer (THERMOSTAR QMD 300 BALZERS)
crystalline powders in a single step due to a high temperature in connected on-line to SDT 2960 system by a quartz capillary heated
the flame [61]. up to 200 ◦ C.
The ultimate aim of the present work is to fabricate sensi- Then, the nanosensors were prepared in a form of circular tablets
tive hydrogen nanosensors from these TiO2 :Cr nanopowders and of 7 mm diameter and 1 mm thickness. Nanopowders have under-
to determine the suitable conditions for sensor preparation. The gone calcinations at a pressure of 25 MPa and temperature of 400 ◦ C
processing of sensors from nanopowders should be controlled following the results of DTA–TG. Planar silver electrodes were
especially because it involves calcinations at elevated temperature applied 5 mm apart. In order to understand the influence of the
that can have detrimental effect on the nanostructure. processing of tablets on the properties of the material used for gas
 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172 165

Fig. 2. Schematic diagram of a gas sensing experimental set-up.

sensors, i.e., the morphology, crystallinity and phase composition

standard characterization methods were employed.
Dimensions of crystallites were analyzed on the basis of XRD
patterns recorded with the help of X’Pert MPD Philips diffractome-
ter both for nanopowders and sensing tablets.
The crystallite size was calculated from XRD patterns using
Scherrer method [62] as:
0.9
DXRD = (1)
 cos 
where  is X-rays wavelength,  denotes a full width at half max-
imum (FWHM),  is the diffraction angle.
Scanning electron microscopy (SEM) of nanopowders and
tablets was performed with a Hitachi SU-70 apparatus.
Dynamic changes in the electrical resistance R/R0 upon hydro-
gen exposure were detected over low-to-medium concentration
range of 50–3000 ppm at 200–400 ◦ C in a custom-made system
described in detail elsewhere [63]. Here, the schematic diagram of
the experimental set-up is presented in Fig. 2. Prior to all measure-
ments, the standardization procedure was applied for each sensor. Fig. 3. Mass loss determined from thermogravimetric TG measurements as a
The sensing tablets were heated up to 400 ◦ C for 18 h in a synthetic function of temperature (a) for FSS-made and commercial (Evonic Degussa and
air atmosphere. The temperature increase was kept constant at Sigma–Aldrich) nanopowders of TiO2 with different specific surface area SSA and (b)
for FSS-made TiO2 :Cr nanopowders with different concentrations of Cr; specification
2◦ /min. Gas sensors placed in a measuring chamber were not pow-
is given in Table 1.
ered continuously but a multiplexer was used to switch between
the measured signals connected to the Hewlett Packard HP34401
multimeter. The multimeter measured sequentially 5 signals: volt-
age drop at the Pt–RhPt thermocouple, and two sensor resistances SSA. Namely, higher precursor’s mole number per time unit is
at two different current polarizations R+ and R− . The sensor sig- related to lower SSA, because higher concentration of precursor
nal was calculated as: (R+ + R− )/2. The time between switching was in the flame leads to the higher supersaturation and as a result to
programmed and its value could be chosen within the range from the creation of bigger particles.
10 s to 1 min. Results of the thermogravimetric measurements concerning
Air, at the flow rate of 120 sccm, was used as a reference gas. the mass loss upon heating are shown in Fig. 3. Undoped TiO2
Sensor response, S was calculated as nanopowders obtained by flame spray synthesis (FSS) are com-
R0 − R pared with commercial nanopowders: P25 from Evonic Degussa
S= (2) and TiO2 rutile from Sigma–Aldrich in Fig. 3a. As it can be seen, the
R0
mass loss that starts at about 30–40 ◦ C and continues up to 400 ◦ C
where R represented the electrical resistance upon interaction with is more pronounced for nanopowders of an enhanced specific sur-
gas and R0 denoted the electrical resistance in the reference gas face area (SSA) and thus smaller particle size. This applies to both
(air). undoped and Cr doped TiO2 nanopowders.
As the nanopowders are synthesized from organic precursors,
3. Results the mass loss observed below 400 ◦ C is due to the combustion of
organic residua. Mass spectra indicate emission of CO2 and H2 O,
Flame spray synthesis (FSS) provided us with the nanocrys- only, upon heating. For undoped TiO2 and for nanopowders with
talline powders of undoped TiO2 and Cr-doped TiO2 with a large low Cr content, up to 0.5 at.% the loss of mass is of the order of 5%
specific surface area SSA over the range of 37–160 m2 /g and a small and has been completed at 400 ◦ C. At higher Cr concentration much
crystallite size of 6–27 nm (see Table 1). smaller loss of mass continues above 400 ◦ C and for TiO2 :5 at.% Cr it
The increase in SSA with higher chromium concentration is amounts to about 0.64% over the temperature range of 400 ◦ C and
determined by the synthesis parameters. As can be seen in Fig. 1 800 ◦ C. The reasons of this instable behavior are difficult to verify
there is a correlation between the precursor’s mole number and experimentally. We took into account the possible conversion
166 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172

Table 1
Results of the quantitative analysis of XRD diffraction patterns of Cr-doped TiO2 nanopowders.

at.% Cr Type of sample Specific surface area SSA (m2 /g) Crystallite size from XRD (nm) Lattice parameters (nm)

Anatase (A) Rutile (R) a c

0 As prepared 37.5 26.8 13.6 0.3784 (A) 0.9512 (A)

0.4606 (R) 0.2956 (R)
0.1 As prepared 48.4 21.2 9.6 0.3785 (A) 0.9511 (A)
0.4598 (R) 0.2955 (R)
0.2 As prepared 47.6 22.7 11.2 0.3785 (A) 0.9507 (A)
0.4597 (R) 0.2953 (R)
0.2 Annealed 450 ◦ C – 22.3 18.7 0.3787 (A) 0.9508 (A)
0.4594 (R) 0.2959 (R)
0.2 Annealed 800 ◦ C – 32.3 30.2 0.3787 (A) 0.9508 (A)
0.4595 (R) 0.2960 (R)
0.5 As prepared 72.2 15.7 13.0 0.3784 (A) 0.9511 (A)
0.4597 (R) 0.2951(R)
1 As prepared 87.1 13.8 9.3 0.3786 (A) 0.9507 (A)
0.4595 (R) 0.2954 (R)
5 As prepared 126.6 9.1 7.5 0.3781 (A) 0.9499 (A)
0.4596 (R) 0.2950 (R)
10 As prepared 160.7 6.0 6.5 0.3779 (A) 0.9514 (A)
0.4595 (R) 0.2953 (R)
◦
10 Annealed 800 C – 22.0 19.4 0.3784 (A) 0.9510 (A)
0.4593 (R) 0.2958 (R)

Table 2
Calculated mass loss due to oxygen removal according to (3) and (4) reactions given
in the text; calculation were performed for TiO2 :5 at.%Cr.

Reaction Mass of O2 (g) (for 1 mol Ti0.95 Cr0.05 ) Mass variation (%)

Reaction (3) 0.3999 0.4995

Reaction (4) 1.2015 1.4857

of Cr(IV) or Cr(VI) to Cr(III) with oxygen loss above 400–450 ◦ C

according to the following reactions:

2CrO2 → Cr2 O3 + 1/2O2 (3)

2CrO3 → Cr2 O3 + 3/2O2 (4)

Theoretically predicted values of mass loss due to oxygen removal

are given in Table 2 for TiO2 :5 at.% Cr.
Reaction (3) seems to be quite probable at higher temperatures
as the calculated mass loss agrees with the one experimentally
observed. On the other hand, the presence of Cr(IV) in TiO2 can-
not be excluded on the basis of XPS measurements as shown in our
previous paper [59].
Fig. 4 shows comparison between X-ray diffraction patterns
of nanopowders and calcined tablets. Two polymorphic forms of
TiO2 , i.e., rutile and anatase are clearly seen. The fraction of anatase
largely dominates over rutile, but the rutile amount increases pro-
gressively with the addition of Cr, as shown before [59,60]. Up to
10 at.% Cr none of the secondary phases, neither chromium oxide
nor chromium titanates have been identified. This is compatible
with the reported solubility limit of Cr3+ in TiO2 and the fact that the
ionic radii of Cr3+ and Ti4+ are very similar [64]. The lattice constants
of TiO2 remain almost unaffected upon variation in Cr concentra-
tion, as shown in Table 1, indicating substitutional incorporation of
chromium at titanium lattice sites.
As can be seen in Fig. 4, apparently there is no big difference
between XRD patterns of nanopowders and tablets. The crystallite
size does not change during material processing at 400 ◦ C. How-
ever, small differences in the intensities of X-ray diffraction peaks
between powders and tablets remain and can be attributed to the
decomposition of organic residua during calcination up to 400 ◦ C
as identified by TG measurements (Fig. 3). Fig. 4. Comparison of XRD patterns for TiO2 -based nanopowders and gas sensors
In order to study evolution of the crystallographic structure of tablets calcined from nanopowders at the pressure of 25 MPa at the temperature
nanopowders upon post-synthesis heat treatment, in Fig. 5 we have of 400 ◦ C. P25 Evonic Degussa powder with the SSA = 50 m2 /g, well-known for its
excellent photocatalytic properties, is given as a reference; A – anatase; R – rutile.
demonstrated XRD patterns for two nanopowder samples of TiO2
doped with 0.2 at.% Cr (Fig. 5a) and 10 at.% Cr (Fig. 5b) annealed at
 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172 167

Fig. 5. XRD patterns of Cr-doped TiO2 nanopowders annealed at 450 ◦ C and 800 ◦ C: (a) 0.2 at.% Cr and (b) 10 at.% Cr; A – anatase; R – rutile.

Fig. 6. Comparison of morphology for TiO2 -based nanopowders (SEM images) and for gas sensors tablets prepared from nanopowders at the pressure of 25 MPa at the
annealing temperature of 400 ◦ C. The influence of the increasing amount of Cr can be seen.
168 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172

Fig. 7. Dynamic changes in the electrical resistance for TiO2 and TiO2 :5 at.% Cr
nanosensors upon exposure to 500, 1100 and 3000 ppm H2 at a constant tempera-
ture of 350 ◦ C.

Fig. 9. Gas sensor response S as a function of temperature at a constant hydrogen

concentration of (a) 200 ppm and (b) 1100 ppm.

450 ◦ C and 800 ◦ C. As can be noticed, in the case of samples heated

at 450 ◦ C anatase polymorphic form predominates. However, the
contribution from rutile appears and increases upon annealing at
800 ◦ C. Rutile amount is more significant for TiO2 :10 at.% Cr than
for TiO2 :0.2 at.% Cr at 800 ◦ C which is related to the increased den-
sity of vacancies accompanying Cr doping. Higher density of oxygen
vacancies is believed to enhance the anatase to rutile transforma-
tion [65].
SEM images of the nanopowders and tablets of TiO2 and TiO2 :Cr
are shown in Fig. 6. Nanopowders particle morphology is typical for
flame spray synthesis. Large, spherical grains of the size up to 40 nm
are formed for pure TiO2 and at low Cr concentration (0.2 at.%).
These large agglomerates are composed of much smaller crys-
tallites in agreement with X-ray diffraction analysis. The size of
crystallites decreases systematically with the increasing Cr com-
position (see Table 1). This is a consequence of a dilution effect
described in detail in [66] and explained in Fig. 1. It is possible that
Cr prevents an excessive agglomeration.
Fig. 7 presents changes of the electrical resistance R of undoped
TiO2 and TiO2 doped with 5 at.% Cr sensor materials upon interac-
tion with the reducing gas H2 as a function of time at a constant
temperature of 350 ◦ C. Large and reproducible responses of the
sensors follow the step changes 0–500 ppm–0, 0–1100 ppm–0,
0–3000 ppm–0 in H2 concentration. As we can see, there is a sys-
Fig. 8. Absolute value of the gas sensor response |S| as a function of hydrogen
tematic decrease in the electrical resistance R for undoped TiO2
concentration at a constant temperature of (a) 250 ◦ C and (b) 350 ◦ C. upon exposure to H2 , whereas for the TiO2 :5 at.% Cr the same
parameter R increases upon interaction with H2 . Such changes in
 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172 169

Fig. 10. Repeatability of the dynamic responses in the electrical resistance R upon exposure to H2 for (a) undoped TiO2 (SSA = 37.5 m2 /g) at 350 ◦ C; (b) undoped TiO2
(SSA = 106.8 m2 /g) at 350 ◦ C; (c) TiO2 :0.2 at.% Cr (SSA = 47.6 m2 /g) at 300 ◦ C.

R upon adsorption of hydrogen indicate that undoped TiO2 and best candidates for commercially used sensors in terms of possible
TiO2 doped with up to 1 at.% Cr behave as n-type semiconduc- costs are TiO2 :5 at.% Cr and TiO2 :10 at.% Cr.
tors, whereas starting from 5 at.% Cr the samples exhibit p-type In order to investigate stability of the gas sensing performance
conductivity. of synthesized TiO2 nanomaterials the hydrogen sensing measure-
Moreover, as one can see in Fig. 7, incorporation of 5 at.% Cr into ments were repeated intentionally. Fig. 10a and b demonstrates
TiO2 causes a decrease by two orders of magnitude in the base- dynamic changes in the electrical resistance for undoped TiO2
line electrical resistance R0 of the material in air, as compared with with different specific surface areas: SSA = 37.5 m2 /g (Fig. 10a) and
undoped TiO2 . SSA = 106.8 m2 /g (Fig. 10b) upon interaction with H2 at 350 ◦ C
In order to compare the sensors sensitivity the absolute value recorded in two consecutive experiments performed after one year
|S| is presented in Fig. 8 because of the observed sign reversal of (Fig. 10a) and one month (Fig. 10b). As it can be seen for both sam-
the sensor response S defined by Eq. (2) when approaching 5 at.% ples the curves remain in good agreement as far as dynamics of the
Cr. At 250 ◦ C the best sensor response is obtained at 5 at.% of Cr, sensor response is concerned. However, the decrease in the initial
whereas at higher temperatures of 350 ◦ C undoped TiO2 is slightly electrical resistance value (base line) after one year (Fig. 10a) and
better than TiO2 :5 at.% of Cr. This is due to the fact that at 250 ◦ C one month (Fig. 10b) cannot be neglected.
the baseline resistance of undoped TiO2 is too high and the signal is The same type of measurement was also implemented for
not measurable. The responses are nonlinear and tend to saturate TiO2 :0.2 at.% Cr (SSA = 47.6 m2 /g). Fig. 10c presents dynamic
at high hydrogen concentrations. changes in the electrical resistance of the sample upon exposure
Fig. 9 demonstrates the response S of the TiO2 :Cr nanosen- to H2 at 300 ◦ C observed in two experiments performed after two
sors as a function the operating temperature for a given change weeks. In this case both dynamics of the sensor response and the
in the hydrogen concentration (from 0 to 200 ppm and from 0 to base line remain in good conformity being a proof of satisfying short
1100 ppm). As can be noticed, with the decreasing temperature term stability of the sample.
the sensor responses have a tendency to increase what is espe-
cially important from the point of view of power consumption. For
undoped TiO2 the lowest temperature at which the baseline resis- 4. Discussion
tance could be measured was 300 ◦ C. This relatively high operating
temperature for the undoped TiO2 can be lowered to 210–250 ◦ C Theoretical models of the gas sensing mechanism and the influ-
by adding Cr. Moreover, Cr incorporation enables the extension of ence of the grain size on the metal-oxide sensor performance take
the temperature range under which the sensors work. The opti- into account the relation between grain size D and Debye length D
mum operating temperature depends on the sensor composition. which corresponds to the width of depletion or accumulation near
Taking into account the relatively low operating temperature the surface layer formed by ions chemisorbed at the surface [67,68].
170 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172

Fig. 11. The relation between crystallite size DXRD and double Debye length 2D as
a function of the concentration of ionic defects Nd calculated at 298 K and 600 K.

For the purposes of this work, the Debye length D was cal-
culated assuming that Cr dopant is completely ionized, Cr ions
substitute for Ti ions in TiO2 lattice and there is no segregation
of dopants. The following formula was used:

εε0 kT
D = (5)
e2 Nd

where ε denotes the dielectric constant, ε0 is the permittivity of

vacuum, k is the Boltzmann constant, e is an elementary charge, T
denotes temperature while Nd represents the concentration of ionic
Fig. 12. Diagram of the electronic structure of nanomaterials in contact with the
defects related to the concentration of chromium dopant intro- gas phase for (a) undoped TiO2 and (b) TiO2 doped with Cr; D is Debye length; Eg
duced into TiO2 lattice. The concentration of ionic defects Nd was – band gap energy, EV – valence band edge; EC – conduction band edge; EF – Fermi
calculated following the formula: energy, E – electron energy; x – distance in real space.

 · NA p
Nd = · (6) The influence of trivalent chromium dopant becomes predominant
M 100
as the concentration of additive increases (starting from TiO2 :5 at.%
where  is the density of anatase, NA denotes Avogadro constant, M
Cr). Cr ions incorporate into TiO2 structure substitutionally accord-
is molecular mass of TiO2 , whereas p stands for atomic percentage
ing to reaction:
of ionic defects.
Fig. 11 illustrates the ratio of the crystallite size DXRD and dou- 1
Cr2 O3 + O2 → 2CrTi + 4OO + 2h• (8)
ble Debye length 2D as a function of the concentration of ionic 2
defects Nd for temperatures 298 K and 600 K (left vertical and bot- which modifies the concentration of electrons and electron holes
tom horizontal scales). The crystallite size DXRD as a function of and leads to transfer from n-type to p-type conductivity.
Cr concentration (right vertical and top horizontal scales) is also Fig. 12 presents the band diagram proposed for two discussed
presented. The crystallite size DXRD for pure TiO2 sample is com- limits of the Debye length. Fermi level EF is placed below the bottom
parable to 2D which means that the relatively large crystallite is of the conduction band EC (x), which comes as a consequence of the
almost fully affected by the interaction with gas. As we enhance the positive ionic defects resulting from the oxygen nonstoichiometry
amount of chromium dopant the two effects, namely the increase in TiO2 . For the crystallite diameter exceeding the twice the Debye
of concentration of ionic defects which leads to the decrease in the length 2D , the interior of crystallites exhibits an n-type behav-
Debye length as well as the decrease of crystallite size due to dilu- ior, but the near-surface layers may show a p-type conductivity
tion effect overlap and as a result the ratio DXRD /2D increases. This due to the band bending that stems from oxygen chemisorptions
means that in the case of TiO2 doped with Cr the near surface layer (Fig. 12a).
affected by the interaction with gas is comparatively thin when Taking into consideration that mobilities of electrons and elec-
confronted with the crystallite size. tron holes in TiO2 assume comparable values, the following criteria
Chromium dopant affects the electronic structure of TiO2 and on n- and p-type conductivity across the grain (0 < x < rg , where rg
forms localized acceptor levels in the forbidden band gap. Although, is the grain radius) can be given:
as far as we consider both pure TiO2 as well as TiO2 lightly doped
with Cr (up to 1 at.% Cr) the gas sensing mechanism is governed n-type : EC (x) − EF < EF − EV (x)
••
by doubly ionized oxygen vacancies VO which are formed sponta- p-type : EC (x) − EF > EF − EV (x)
neously according to the reaction:
Fermi level EF of TiO2 with smaller Debye length at higher
1 chromium content, is demonstrated in Fig. 12b. Fermi level EF is
OO ↔ O2(g) + V••
O + 2e

(7)
2 located just above the maximum of the valence band edge EV (x)
 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172 171

due to the acceptor-type substitutional defects CrTi formed accord- [12] C. Lu, Z. Chen, High-temperature resistive hydrogen sensor based on thin
ing to Eq. (8). In this case, the material exhibits p-type conductivity nanoporous rutile TiO2 film on anodic aluminum oxide, Sens. Actuators B Chem.
140 (2009) 109–115.
across the whole grain. [13] A. Teleki, S.E. Pratsinis, K. Kalyanasundaram, P.I. Gouma, Sensing of organic
vapors by flame-made TiO2 nanoparticles, Sens. Actuators B Chem. 119 (2006)
5. Conclusions 683–690.
[14] L.A. Harris, A titanium dioxide hydrogen sensor, J. Electrochem. Soc. 127 (1980)
2657–2662.
The results obtained in the course of these studies allow to for- [15] W. Göpel, G. Rocker, R. Feierabend, Intrinsic defects of TiO2 (1 1 0): interaction
mulate the following conclusions: with chemisorbed O2 , H2 , CO and CO2 , Phys. Rev. B 28 (1983) 3427–3438.
[16] L. Sun, L. Huo, H. Zhao, S. Gao, J. Zhao, Preparation and gas-sensing property
of a nanosized titania thin film towards alcohol gases, Sens. Actuators B Chem.
• Crystalline nanopowders of mostly anatase TiO2 , grown by flame 114 (2006) 387–391.
spray synthesis, constituting starting materials for gas sensors, [17] X. Cheng, Y. Xu, S. Gao, H. Zhao, L. Huo, Ag nanoparticles modified TiO2 spherical
heterostructures with enhanced gas-sensing performance, Sens. Actuators B
are characterized by large specific surface area and small crystal- Chem. 155 (2011) 716–721.
lite size depending on Cr doping. [18] Y. Wang, G. Du, H. Liu, D. Liu, S. Qin, N. Wang, C. Hu, X. Tao, J. Jiao, J. Wang, Z.L.
• The mass loss of nanopowders upon heating up to 400 ◦ C is higher Wang, Nanostructured sheets of Ti–O nanobelts for gas sensing and antibacte-
rial applications, Adv. Funct. Mater. 18 (2008) 1131–1137.
for more developed specific surface area SSA.
[19] A.M. Ruiz, A. Cornet, K. Shimanoe, J.R. Morante, N. Yamazoe, Effects of various
• Calcination temperature of 400 ◦ C is suitable for gas sensor pro- metal additives on the gas sensing performances of TiO2 nanocrystals obtained
cessing from nanopowders. from hydrothermal treatments, Sens. Actuators B Chem. 108 (2005) 34–40.
• Morphology of gas sensing materials calcined at 400 ◦ C in a form [20] Y. Shimizu, N. Kuwano, T. Hyodo, M. Egashira, High H2 sensing performance of
anodically oxidized TiO2 film contacted with Pd, Sens. Actuators B Chem. 83
of tablets is similar to that of starting nanomaterials. (2002) 195–201.
• Nanosensors obtained from TiO2 :Cr nanopowders show promis- [21] A.Z. Sadek, J.G. Partridge, D.G. McCulloch, Y.X. Li, X.F. Yu, W. Wlodarski, K.
ing dynamic characteristics in response to hydrogen. The sensor Kalantar-Zadeh, Nanoporous TiO2 thin film based conductometric H2 sensor,
Thin Solid Films 518 (2009) 1294–1298.
responses are large and reproducible. [22] A.M. Ruiz, A. Cornet, J.R. Morante, Performances of La–TiO2 nanoparticles as gas
• The electrical resistance R decreases upon hydrogen exposure up sensing material, Sens. Actuators B Chem. 111–112 (111) (2005) 7–12.
to 1 at.% Cr while the reversed effect is observed at 5 at.%. [23] A.M. Ruiz, A. Cornet, K. Shimanoe, J.R. Morante, N. Yamazoe, Transition met-
als (Co, Cu) as additives on hydrothermally treated TiO2 for gas sensing, Sens.
• The sensor performance clearly improves with a decrease in the
Actuators B Chem. 109 (2005) 7–12.
operating temperature. Incorporation of 1 at.% and 5 at.% of Cr [24] E. Comini, V. Guidi, C. Frigeri, I. Ricco, G. Sberveglieri, CO sensing properties
into TiO2 allows to attain the measurable baseline resistance over of titanium and iron oxide nanosized thin films, Sens. Actuators B Chem. 77
(2001) 16–21.
the temperature range of 210–250 ◦ C thus proving high sensor [25] D. Biskupski, B. Herbig, G. Schottner, R. Moos, Nanosized titania derived from
sensitivity to hydrogen. a novel sol–gel process for ammonia gas sensor applications, Sens. Actuators B
• Electronic structure of TiO2 is modified by doping with Chem. 153 (2011) 329–334.
[26] R. Moos, R. Müller, C. Plog, A. Knezevic, H. Leye, E. Irion, T. Braun, K.-J. Marquardt,
chromium. The point defect structure of TiO2 :Cr is proposed.
K. Binder, Selective ammonia exhaust gas sensor for automotive applications,
• The n–p transition depends on the dopant concentration and Sens. Actuators B Chem. 83 (2002) 181–189.
crystallite size of nanopowders. [27] E. Comini, G. Faglia, G. Sberveglieri, Alcohol and organic vapors sensor based on
nano-sized TiO2 thin films, in: Proceedings of the Conference on Optoelectronic
and Microelectronic Materials and Devices, Perth, WA, December 14–18, 1998.
Acknowledgements [28] Y. Yamada, Y. Seno, Y. Masuoka, T. Nakamura, K. Yamashita, NO2 sensing char-
acteristics of Nb doped TiO2 thin films and their electronic properties, Sens.
This work is supported by the Polish Ministry of Science and Actuators B Chem. 66 (2000) 164–166.
[29] P.M. Faia, C.S. Furtado, A.J. Ferreira, Humidity sensing properties of a thick-film
Higher Education (2009–2012) grant no. N N507 466537. titania prepared by a slow spinning process, Sens. Actuators B Chem. 101 (2004)
One of the authors (B.L.) acknowledges the Statutory Project for 183–190.
Science for 2012 at the Department of Electronics AGH–UST. [30] L.L.W. Chow, M.M.F. Yuen, P.C.H. Chan, A.T. Cheung, Reactive sputtered TiO2
thin film humidity sensor with negative substrate bias, Sens. Actuators B Chem.
76 (2001) 310–315.
References [31] M.C. Carotta, V. Guidi, C. Malagu, B. Vendemiatia, A. Zanni, G. Martinelli, M.
Sacerdoti, S. Licoccia, M.L. Di Vona, E. Traversa, Vanadium and tantalum-doped
[1] N. Yamazoe, New approaches for improving semiconductor gas sensors, Sens. titanium oxide (TiTaV): a novel material for gas sensing, Sens. Actuators B
Actuators B Chem. 5 (1991) 7–19. Chem. 108 (2005) 89–96.
[2] E. Comini, Metal oxide nano-crystals for gas sensing, Anal. Chim. Acta 568 [32] A. Ruiz, G. Dezanneau, J. Arbiol, A. Cornet, J.R. Morante, Study of the influence of
(2006) 28–40. Nb content and sintering temperature on TiO2 sensing films, Thin Solid Films
[3] O.K. Varghese, D. Gong, M. Paulose, K.G. Ong, C.A. Grimes, Hydrogen sensing 436 (2003) 90–94.
using titania nanotubes, Sens. Actuators B Chem. 93 (2003) 338–344. [33] C.-H. Han, D.-W. Hong, I.-J. Kim, J. Gwak, S.-D. Han, K.C. Singh, Synthesis of Pd or
[4] K.E. La Flamme, C.A. Grimes, Non-carbon nanotubes hydrogen sensors based on Pt/titanate nanotube and its application to catalytic type hydrogen gas sensor,
TiO2 , in: F.J. Arregui (Ed.), Sensors Based on Nanostructed Materials, Springer, Sens. Actuators B Chem. 128 (2007) 320–325.
2009, pp. 29–57, and references herein. [34] L. Francioso, A.M. Taurino, A. Forleo, P. Siciliano, TiO2 nanowires array fabrica-
[5] M.-H. Seo, M. Yuasa, T. Kida, J.-S. Huh, K. Shimanoe, N. Yamazoe, Gas sensing tion and gas sensing properties, Sens. Actuators B Chem. 130 (2008) 70–76.
characteristics and porosity control of nanostructured films composed of TiO2 [35] R.-J. Wu, Y.-L. Sun, C.-C. Lin, H.-W. Chen, M. Chavali, Composite of TiO2
nanotubes, Sens. Actuators B Chem. 137 (2009) 513–520. nanowires and Nafion as humidity sensor material, Sens. Actuators B Chem.
[6] E. Comini, G. Faglia, G. Sberveglieri, Stable and highly sensitive gas sen- 115 (2006) 198–204.
sors based on semiconducting oxide nanobelts, Appl. Phys. Lett. 81 (2002) [36] J. Moon, J.-A. Park, S.-J. Lee, T. Zyung, I.-D. Kim, Pd-doped TiO2 nanofiber
1869–1871. networks for gas sensor applications, Sens. Actuators B Chem. 149 (2010)
[7] A. Kolmakov, D.O. Klenov, Y. Lilach, S. Stemmer, M. Moskovits, Enhanced gas 301–305.
sensing by individual SnO2 nanowires and nanobelts functionalized with Pd [37] J.-A. Park, J. Moon, S.-J. Lee, S.H. Kim, T. Zyung, H.Y. Chu, Structure and CO
catalyst particles, Nano Lett. 5 (2005) 667–673. gas sensing properties of electrospun TiO2 nanofibers, Mater. Lett. 64 (2010)
[8] E. Comini, G. Faglia, M. Ferroni, A. Ponzoni, A. Vomiero, G. Sberveglieri, Metal 255–257.
oxide nanowires: preparation and application in gas sensing, J. Mol. Catal. A [38] M. Epifani, A. Helwig, J. Arbiol, R. Dıaz, L. Francioso, P. Siciliano, G. Mueller, J.R.
Chem. 305 (2009) 170–177. Morante, TiO2 thin films from titanium butoxide: synthesis, Pt addition, struc-
[9] R. Yoshida, Y. Suzuki, S. Yoshikawa, Syntheses of TiO2 (B) nanowires and TiO2 tural stability, microelectronic processing and gas-sensing properties, Sens.
anatase nanowires by hydrothermal and post-heat treatments, J. Solid State Actuators B Chem. 130 (2008) 599–608.
Chem. 178 (2005) 2179–2185. [39] Z. Wen, L. Tian-mo, Hydrogen sensing characteristics and mechanism of nano-
[10] S.A. Hooker, Nanotechnology advantages applied to gas sensors development, sized TiO2 doped with metallic ions, Physica B 405 (2010) 564–568.
in: The Nanoparticles 2002 Conference Proceedings, Norwalk, CT, USA, Business [40] P.G. Hu, G.J. Du, W.J. Zhou, J.J. Cui, J.J. Lin, H. Liu, D. Liu, J.Y. Wang, S.W. Chen,
Communications Co., Inc., 2002, pp. 1–7. Enhancement of ethanol vapor sensing of TiO2 nanobelts by surface engineer-
[11] W. Göpel, T.A. Jones, M. Kleitz, J. Lundsröm, T. Seiyama (Hrsg), Chemical and ing, Appl. Mater. Interfaces 2 (11) (2010) 3263–3269.
biochemical sensors, in: W. Göpel, K.D. Schierbaum (Eds.), Sensors, vol. 2, Verlag [41] A. Bernasik, M. Radecka, M. Rekas, M. Sloma, Electrical properties of Cr- and
VCH, 1991. Nb-doped TiO2 thin films, Appl. Surf. Sci. 65/66 (1993) 240–245.
172 B. Lyson-Sypien et al. / Sensors and Actuators B 175 (2012) 163–172

[42] R.K. Sharma, M.C. Bhatnagar, Improvement of the oxygen gas sensitivity in scientist at the Faculty of Electrical Engineering, Automatics, Computer Science and
doped TiO2 thick films, Sens. Actuators B Chem. 56 (1999) 215–219. Electronics at the AGH University of Science and Technology. Her current research
[43] K. Zakrzewska, M. Radecka, M. Rekas, Effect of Nb, Cr, Sn additions on gas interests concern gas sensing and photocatalytic properties of TiO2 –SnO2 nanocrys-
sensing properies of TiO2 thin films, Thin Solid Films 310 (1997) 161–166. talline ceramics.
[44] A. Teleki, N. Bjelobrk, S.E. Pratsinis, Flame-made Nb- and Cu-doped TiO2 sensors
for CO and ethanol, Sens. Actuators B Chem. 130 (2008) 449–457. P. Gwizdz received his master degree in electronics in 2010 from the Faculty of
[45] R.K. Sharma, M.C. Bhatnagar, G.L. Sharma, Mechanism of highly sensitive and Electrical Engineering, Automatics, Computer Science and Electronics, AGH Univer-
fast response Cr doped TiO2 oxygen gas sensor, Sens. Actuators B Chem. 45 sity of Science and since that time he has been a Ph.D. student at the same faculty.
(1997) 209–215. His research interests include gas sensor arrays, pattern recognition and intelligent
[46] I. Alessandri, E. Comini, E. Bontempi, G. Faglia, L.E. Depero, G. Sberveglieri, Cr- electronic sensors systems with a goal to construct an electronic nose based on
inserted TiO2 thin films for chemical gas sensors, Sens. Actuators B Chem. 128 nanosensors.
(2007) 312–319.
K. Schneider received her Ph.D. in physics from the Institute of Nuclear Physics
[47] A.M. Ruiz, G. Sakai, A. Cornet, K. Shimanoe, J.R. Morante, N. Yamazoe, Cr-doped
Polish Academy of Sciences, Kraków, Poland in 2004 working on neutron trans-
TiO2 gas sensor for exhaust NO2 monitoring, Sens. Actuators B Chem. 93 (2003)
port. Currently she is a regular staff member at the Faculty of Electrical Engineering,
509–518.
Automatics, Computer Science and Electronics at AGH University of Science and
[48] Y. Li, W. Wlodarski, K. Galatsis, S.H. Moslih, J. Cole, S. Russo, N. Rockelmann, Gas
Technology. Her research interests concern nanopowders and thin films for the
sensing properties of p-type semiconducting Cr-doped TiO2 thin films, Sens.
photocatalytic applications.
Actuators B Chem. 83 (2002) 160–163.
[49] A. Lebrun, J.-L. Carpentier, F. Perdu, P. Tellier, Comparative study of elec- K. Zakrzewska received her Ph.D. in technical physics from AGH-University of Sci-
tronic conduction between pure and weakly chromium-doped rutile at 1273 K, ence and Technology, Kraków, Poland in 1986 working on transparent conductive
Comptes Rendus de L’Academie des Sciences Serie II Mecanique Physique oxides TCO. In 1986–1988 she was employed as a member of staff at the Center
Chimie Sciences de L’Univers Sciences de la Terre 304 (1987) 629–632. of Laser Studies at the University of Southern California. Since 1989, she has been
[50] J.L. Carpentier, A. Lebrun, F. Perdu, Point defects and charge transport in pure given a permanent position at the Department of Electronics, AGH-University of
and chromium-doped rutile at 1273 K, J. Phys. Chem. Solids 50 (1989) 145–151. Science and Technology. In 2004 she has presented her habilitation on the applica-
[51] M. Radecka, M. Rekas, Defect structure and electrical properties of Cr- and Nb- tion of titanium dioxide thin films for gas sensors and photonic devices. Since 2007,
doped TiO2 thin films, Solid State Phenom. 39-40 (1994) 135–138. she has been appointed a professor of AGH. K. Zakrzewska is currently a head of
[52] P. Kofstad, Nonstoichiometry, Diffusion and Electrical Conductivity in Binary the research team that works actively in several scientific projects concerning thin
Metal Oxides, Willey-Interscience Inc., 1972, pp. 203–212. film deposition, studies of the resulting thin film properties and gas sensing appli-
[53] S. Music, M. Maljkovic, S. Popowic, R. Trojko, Formation of chromia from amor- cations with the emphasis on the titanium compounds (oxides and nitrides). The
phous chromium hydroxide, Croatia Chem. Acta 72 (1999) 789–802. technological efforts of this team concentrate at the reactive ion sputtering.
[54] A. Małecki, B. Małecka, R. Gajerski, S. Łabus, Thermal decomposition of
chromium(III) nitrate(V) nanohydrate, J. Therm. Anal. Calorim. 72 (2003) K. Michalow received her master degree in materials science from AGH University
135–144. of Science and Technology in 2005. She studied in the International PhD School
[55] O.W. Florke, C.W. Lee, Phase diagram of TiO2 –Cr2 O3 , J. Solid State Chem. 1 Switzerland–Poland and obtained her Ph.D. degree in chemical science in the field
(1969) 445–446. of chemistry from AGH University of Science and Technology in 2010. Since 2009
[56] J.A. Pedraza-Avella, R. López, F. Martinez-Ortega, E.A. Páez-Mozo, R. Gómez, she is employed as a Postdoc scientist in Laboratory for High Performance Ceramics
Effect of chromium doping on visible light absorption of nanosized titania at Empa Materials Science and Technology, Switzerland. Her main research interests
sol–gel, J. Nano Res. 5 (2009) 95–104. cover synthesis and properties of doped titanium dioxide nanoparticles as well as
[57] R. López, R. Gómez, S.Oros-Ruiz, Photophysical and photocatalytic properties application of nanoparticles in photocatalysis of the pollution in water and air.
of TiO2 –Cr sol–gel prepared semiconductors, Catal. Today 166 (2011) 159–165.
[58] K. Zakrzewska, Gas sensing mechanism of TiO2 -based thin films, Vaccum 74 T. Graule received his Ph.D. in analytical chemistry from the University of Dortmund
(2004) 335–338. and MPI for Metals Research, Germany, in 1988. After conducting research in the
[59] A. Trenczek-Zajac, M. Radecka, M. Jasinski, K.A. Michalow, M. Rekas, E. Kusior, K. field of nanotechnology at the Fraunhofer Institute for Applied Materials Research,
Zakrzewska, A. Heel, T. Graule, K. Kowalski, Influence of Cr on the structural and Bremen, Germany (1988) and in ceramics technology at the Swiss Federal Institute of
optical properties of TiO2 :Cr nanopowders prepared by flame spray synthesis Technology (ETH) Zurich (1989–1994), he joined Katadyn Products Inc., Wallisellen,
(FSS), J. Power Sources 194 (2009) 104–111. Switzerland, in 1995 as Head of Production and Development. In 1999, he became
[60] M. Radecka, M. Rekas, E. Kusior, K. Zakrzewska, A. Heel, K.A. Michalow, T. Head of the Laboratory for High Performance Ceramics at Empa Materials Science
Graule, TiO2 -based nanopowders and thin films for photocatalytic applications, and Technology.
J. Nanosci. Nanotechnol. 10 (2010) 1032–1042.
A. Reszka received her B.Sc. degree in Applied Informatics (2006) and graduated
[61] K.K. Akurati, A. Vital, J.-P. Dellemann, K. Michalow, T. Graule, D. Ferrim, A.
in Physics (2010) at the Faculty of Mathematics and Natural Sciences, Cardinal S.
Baiker, Flame-made WO3 /TiO2 nanoparticles: relation between surface acidity,
Wyszynski University in Warsaw. Since 2009 she has been working in the Divi-
structure and photocatalytic activity, Appl. Catal. B 79 (2008) 53–62.
sion of Solid State Spectroscopy, Institute of Physics Polish Academy of Sciences,
[62] B.D. Cullity, Elements of X-ray Diffraction, Reading, UK, Addison–Wesley, 1978.
focusing on scanning electron microscopy and cathodoluminescence spectroscopy
[63] M. Radecka, B. Łysoń, M. Lubecka, A. Czapla, K. Zakrzewska, Photocatalytical
of semiconducting nanostructures.
decomposition of contaminants on thin film gas sensors, Acta Phys. Polon. A
117 (2010) 415–419. M. Rekas received his PhD and habilitation degrees in physical chemistry from the
[64] R.D. Shannon, Revised effective ionic radii and systematic studies of interatomic AGH University of Science and Metallurgy, Krakow, Poland in 1972 and 1986, respec-
distances in halides and chalcogenides, Acta Crystallogr. A 32 (1976) 751–767. tively. In 1983 he was a vesting scientist in the School of Mining in Saint-Etienne,
[65] D.A. Hanaor, C.C Sorrell, Review of the anatase to rutile phase transformation, France, where he worked on electrochemical gas sensors. In 1987 he joined the sen-
J. Mater. Sci. 46 (2011) 855–874. sor group in the Max-Planck-Institute for Solid State Research in Stuttgart. Between
[66] K.K. Akurati, A. Vital, G. Fortunato, R. Hany, F. Nueesch, T. Graule, Flame syn- 1994 and 2002 he worked at the Materials Division of the Australian Nuclear Science
thesis of TiO2 nanoparticles with high photocatalytic activity, Solid State Sci. 9 and Organisation (4 years) and then at the School of Materials Science and Engineer-
(2007) 247–257. ing, the University of New South Wales in Sydney. He is currently full professor of
[67] A. Rothschild, Y. Komem, The effect of grain size on the sensitivity of nanocrys- chemistry at the Faculty of Materials Science and Ceramics, AGH University of Sci-
talline metal-oxide gas sensors, J. Appl. Phys. 95 (2004) 6374–6380. ence and Metallurgy in Krakow, Poland. His research interests are the physics and
[68] N. Barsan, U. Weimar, Conduction model of metal oxide gas sensors, J. Electro- chemistry of solids, particularly electrochemistry of solids, fuel cells and chemical
ceram. 7 (2001) 143–167. gas sensors

A. Lacz received her Ph.D. degree in chemistry form the AGH University of Science
Biographies and Technology, Kraków, Poland in 2007. Since her masters studies she has been
interested, and involved in application of the thermal analysis methods and the
mass spectrometry, especially related to the thermal decomposition of solids. Cur-
B. Lyson-Sypien received her master degree in physics from the Pedagogical Uni- rently she is a regular staff member of the Department of Inorganic Chemistry, AGH
versity of Kraków, Poland in 2008. Since 2008 she has been a Ph.D. student at Faculty University of Science and Technology.
of Physics and Applied Computer Science at AGH University of Science and Technol-
ogy, Kraków, Poland. Her scientific research concern nanomaterials for resistive gas M. Radecka received her Ph.D. and habilitation degree in chemistry from the
sensors. AGH University of Science and Technology, Kraków, Poland in 1993 and 2004,
respectively. She is currently full professor of chemistry at the Faculty of Mate-
A. Czapla received his Ph.D. degree in physics from the AGH University of Science rials Science and Ceramics, AGH University of Science and Metallurgy in Krakow,
and Technology, Kraków, Poland in 1973. Being employed as a member of staff at the Poland. Her research interests include development of semiconducting gas sensors
Faculty of Electrical Engineering, Automatics, Computer Science and Electronics at and photoelectrochemical cells, experimental studies of the electrical and struc-
the AGH University of Science and Technology, he has been involved in the research tural properties of ceramic oxides and thin films as well as the electron transport
concerning gas sensing characteristics and optical properties of mixed oxide thin mechanisms in oxide semiconductors. Her research works tend to understand the
films and nanopowders. correlation between the defect structure of crystals and physico-chemical properties
of nonstoichiometric compounds.
M. Lubecka received her Ph.D. degree in physics from the AGH University of Sci-
ence and Technology, Kraków, Poland in 1971. She has worked as a senior research