D. TSIULYANU, O.

MOCREAC HYDROGEN SENSING BEHAVIOR OF TELLURIUM THIN

DUMITRU TSIULYANU, Scientific paper

OLGA MOCREAC UDC:620.197.5

Hydrogen sensing behavior of tellurium thin films

studied by A.C. measurements

For the first time it is pointed out that tellurium films exhibit sensitivity to H 2 at room temperature
along with sensitivity to NO2. The hydrogen gas sensing performance of tellurium thin films was
investigated by method of impedance spectroscopy. The impedance spectra are strongly influenced by
gaseous environment but the effect of target gas is mainly due to variation of resistance of the film. It is
assumed that the sensitivity of tellurium films to H2 arises because of reducing effect of oxygen
priory absorbed on the surface of the film from carrier (dry air) gas. The high concentration of oxygen
in carrier gas promotes the formation of a catalytic gate, which can be removed by other gases
including hydrogen. Removing of the priory-adsorbed oxygen results in decreasing of both, hole
concentration and conductivity of the surface and intragrain regions of tellurium film. Due to
impedance change in different direction, reducing H2 may be distinguished from oxidizing NO2, hence
the effective, operating at room temperature H2 sensors can be manufactured using tellurium-based
films.
Key words: Gas sensing, Tellurium, Hydrogen, A.C. measurements

1. INTRODUCTION One of possibilities to obtain a selective detection

Hydrogen (H2) gas is a clean, naturally abundant of gases has been mentioned by Sbeveglieri [6] and
energy resource and presently it has been widely consists in a fast sweeping of sensitivity of a single
implanted in household and transportation applica- sensor at different frequencies. The sensitivity of
tions. To avoid damage to human life and infra- sensor to different gases at different frequencies can
structures, a reliable sensor with accurate and fast H2 be rather different. That is, by monitoring a.c. con-
gas detection is essential to safe H2 gas production, ductance at specific frequencies, the sensitivity to
storage and utilizations. different gas components can be enhanced [7]. More
over, a.c. measurements allow obtaining impedance
The development of hydrogen sensors concerns or admittance spectra of a sensor, to calculate equi-
the research into the new materials that provide valent circuit and to distinguish between contributions
advanced sensitivity, selectivity, stability and low from the surface, bulk or contacts to film conductivity
power consumption. So far, the metal oxide semi- [8].
conductors, such as tin oxide [1] or tungsten trioxide
[2] are the most studied materials for the H2 gas In the present paper the impedance spectra of
detection. Although these materials exhibit good tellurium based thin films with interdigital electrodes
hydrogen sensing characteristic they require evalu- have been investigated in gaseous media H2 as well as
ated (100 - 600 0C) operable temperature. In the NO2 for comparison.
present study we rapport the possibility to detect H2 at
room temperature using tellurium thin films. It is 2. EXPERIMENTAL
known that a number of gases may be easily detected
Tellurium based thin films of 100nm thickness,
at room temperature using these films. First this
were prepared by thermal vacuum evaporation of
possibility has been pointed out for NO2 [3], then
pure tellurium from tantalum boat onto ceramic
have been reported sensors operable at room
substrates with a priory deposited platinum
temperature based on tellurium thin films to detected
interdigital electrodes (Figure 1a). The electrode
CO and propylamine [4] as well as NH3 [5]. Although
structure was structured at SIEMENS AG with
the cross sensitivity to mentioned gases is essential
different, the distinguishing between them becomes electrode width of 15m and interelectrode distances
important. of 45m. The evaporation of tellurium was performed
at the working pressure of 104 Pa . The growing
Author's address: Technical University, bd. Dacia velocity of the film was in the order of 10 nm/ s and
41, Chisinau, MD-2060, Moldova the area of deposition around 10 mm2. The surface
Paper received: 18.02.2013. morphology of the films was investigated, using a

ZATITA MATERIJALA 54 (2013) broj 2 107

D. TSIULYANU, O. MOCREAC HYDROGEN SENSING BEHAVIOR OF TELLURIUM THIN

VEGA TESCAN TS 5130 MM scanning electron is assigned to a sum of Ohmic resistance due to
microscope (SEM). electric connection, but resistance R0 and capacity C
The film was encapsulated in a standard TO 8 are distributed to others contributors, the grain
sockets and then the contacts were thermally bounded boundary resistance and capacity being the main.
to socket pins, using the copper wires. The circle of Nyquist diagram shown in fig. 1b
The sockets with thin film sensing devices were is depressed owing to the dependence of both C and
put into a test cell (of 10ml volume) in which the R on frequency. From the left and right intercepts
gases were injected with a flow rate of 100ml / min , of semi circle with the Re(Z ) axis the values of
parallel to the film surface. R 0 and Rr R R0 can be estimated. Thus, R 0
Hydrogen gaseous media, with concentration 1%
by volume was obtained from cylinders (Linde, was found to be very small, only about 5Ohm . That
Germania). Nitrogen dioxide (NO2) vapors with is the arc practically passes through the origin and the
concentrations of 1,5 ppm were obtained by using right intercept gives the value of Rr 20 kOhm .
calibrated permeation tubes (Vici Metronics, USA),
For a parallel R C circuit the impedance is
which were incorporated subsequent into the
experimental set up. Dry synthetic air was used as given as:
the carrier and reference gas. 1 1
Impedance measurements were carried out in Z ( )
frequency range of 5Hz to 13MHz using a HP 4192
Y ( ) 1
i C
A impedance analyzer. R
R R (1 i C R )
3. RESULTS AND DISCUSSION
3.1 Impedance behavior under dry air 1 i C R 1 ( C R ) 2
(1)
Before checking the effect of different harmful
gases on a.c. conductivity the tellurium films were where Y ( ) is the admittance, i 1 is the
aged by 12 months in normal conditions and the imaginary number , 2f , f -the frequency.
measurements have been performed under synthetic
Thus, the real and imaginary parts of the
dry air. Figure 1b shows the typical complex
impedance are:
impedance diagram in Nyquist plot obtained in pure
synthetic dry air from a thin film device at room R
Re( Z ) (2)
( 22 C ) temperature. 1 2 R2 C2
and
C R
Im( Z ) (3)
1 2 R2 C2
From these system of equations the values of
R and C of the film can be evaluated as:

Im 2 ( Z ) Re 2 ( Z )
R (4)
Re( Z )
Figure 1 - a) Interdigital electrode structure used to and
measure the a.c. conductivity; b) Nyquist diagram of
Im( Z )
C
an aged at 22oC tellurium thin film in pure synthetic
dry air; c) Suggested equivalent circuit
Im ( Z ) Re 2 ( Z )
2
(5)

The diagram shows a slightly depressed semi From equations (4) and (5) the resistance Rm,
circular arc with a center displaced below the real
capacitance Cm and time constant m ( 2f m ) of
1
axis, owing to presence of distributed elements in
tellurium-based device [8]. A simplified equivalent the film can be estimated at characteristic frequency
circuit inserted in Fig. 1 (c) can interpret the Nyquist fm, that is the frequency at which the imaginary part -
plot. The frequency independent serial resistance R0 Im(Z) reaches its maximum value. Because of he-

108 ZATITA MATERIJALA 54 (2013) broj 2

D. TSIULYANU, O. MOCREAC HYDROGEN SENSING BEHAVIOR OF TELLURIUM THIN

terogeneity of the material-electrode system the where fm - is the characteristic frequency at which the
relaxation time (time constant) m , estimated from imaginary part Im(Z) reaches the maximum value,
the complex impedance represents a mean value for Rm and C m are the resistance and capacity of the
the complete thin film device: film at characteristic frequency fm. The characteristic
frequency (fm), impedance (Z) and estimated from
1
m m1 Rm C m (6) equation (6) the time constant ( m ) of the sample in
2f m
dry synthetic air, are listed in Table 1.

Table 1 - Characteristic frequency, impedance and R-C values at different environments.

Environment f m ( kHz ) Z ( kOhm) m 10 7 s R ( kOhm) C (pF)
Dry air 900 13,3 1,8 19,2 9,6
H 2 1% by vol. 600 19,8 2.7 31,7 8,5

1,5 ppm NO2 1500 7,5 1,1 11,8 9,3

3.2. Impedance behavior under mixture of dry air more the addition of NO2 decreases both impedance
with H 2 and NO2 and Rm (at characteristic frequency, which also is gas
influenced) but addition of H2 increases these
Figure 2 reports the complex impedance spectra parameters.
of aged tellurium-based films upon exposure to
different test gases that is NO2 and H2. It is seen that 3.3. Real and imaginary parts of impedance for Te
addition of these gases to dry synthetic air does not films in H 2 and NO2 gaseous media.
change the general shape of curve, i.e. they influences Figure 3 reports the spectra of the real part of
all elements of the equivalent circuit. The values of impedance of tellurium films upon exposure to
characteristic frequency, impedance and time constant different test gases. It is seen that addition of 1,5 ppm
m of the film at this frequency, by indicated concen- of NO2 to dry synthetic air diminishes the real part of
trations of NO2 and H2 at room temperature, are impedance by ~ 10 kOhm in the frequency range 1,0-
summarized in Table 1. 103 kHz. On the contrary, the addition of 1 % of
Listed in this table values of Rm and Cm (the volume of H2 to dry synthetic air enhances the real
resistance and capacity at characteristic frequency) part of impedance by ~7,0 kOhm in the much shorter
have been obtained from Eq. (2) and (3) applied to frequency range: 1,0 100 kHz.
the data of Figure 2.

Figure 2 - Nyquist diagrams of tellurium thin films in

different environmental conditions Figure 3 - Effect of target gas on the real part of
impedance
From this table it is seen that as the environment
is changed from dry air to its mixture with gases in The spectra of imaginary part of impedance
question, the resistance Rm is mainly influenced and exhibits the maximums strongly influenced by harm-
capacitance Cm does not very essentially. What is ful gases species (Fig.4). The NO2 vapors diminish

ZATITA MATERIJALA 54 (2013) broj 2 109

D. TSIULYANU, O. MOCREAC HYDROGEN SENSING BEHAVIOR OF TELLURIUM THIN

the peak of imaginary part of impedance shifting it to Figure 5 shows the sensor sensitivity as a function
higher frequencies but the addition of H2 vapors of the measurement frequency during the exposure to
results in a vice-versa behavior. Analysis of these 1,5 ppm NO2. The sensitivity (here and further) is
spectra help determining the influence of tested defined as absolute variation of measured value
harmful gases on all elements of the equivalent circuit (impedance or imaginary part of impedance) for a
of the sample showed above in the Table 1. selected frequency in mixture of carrier gas with NO2
divided by the measurement value in the carrier gas at
the same frequency, in percents per ppm.
The response curves for either impedance or
imaginary part are nearly independent on frequency
until approximately 300 kHz, then go down, but
sensitivity to NO2 is maintained until 10 MHz. The
sensitivity in d.c. and impedance measurements
amounts to approximately 30 % / ppm, but evaluating
the imaginary part as the sensor response results in an
increasing of sensitivity until ~50 % / ppm. The high
sensitivity, as well as the large frequency range of
response to NO2 supports the early-proposed mecha-
nism of nitrogen dioxide interaction with chalco-
genides [9], which involves strong chemisorption
due to interaction between odd electrons of NO2
molecules and lone pair electrons of tellurium based
Figure 4 - Spectra of imaginary part of impedance chalcogenides.
upon exposure to different test gases
As the response to different gases strongly 3.4.2. Hydrogen
depends of applied frequency, it becomes interesting Figure 6 shows the sensor sensitivity as a function
to analyze the frequency dependences of sensitivity to of measurement frequency using the hydrogen as a
different target gases. test gas. It is observed that sensitivity to hydrogen is
by four orders of magnitude smaller that to NO2, but
3.4. Sensor sensitivity versus applied frequency
also cover a large range of frequencies and can be
3.4.1. Nitrogen dioxide clearly detected. Unlike exposure to NO2 the
D. c. resistance of tellurium films is known to impedance response spectra to hydrogen go down
decrease reversibly in presence of NO2 due to inter- starting with approximately 150 kHz but at 1,0 MHz
action of adsorbed species with lone pair electrons, the sensitivity to H2 practically disappears.
which from the upper part of the valence band [9].
Apparently, by changing from d.c. to a.c. technique
the mechanism of interaction cannot be modified but
the sensitivity (or selectivity) can be increased.
60
Sensitivity , [ % / ppm ]

50

40 NO2

30

20
Im (Z)
IZI
10

0 Figure 6 - Sensitivity to H2 for impedance and its

0 1 2 3 4 imaginary part versus frequency.
lg f, ( kHz ) The last is valid also for the imaginary part taken
as a sensor response, although the resulting value of
Figure 5 - Sensitivity to NO2 for impedance and its sensitivity in this case is more than twice higher.
imaginary part as a function of frequency These peculiarities suggest that mechanism of

110 ZATITA MATERIJALA 54 (2013) broj 2

D. TSIULYANU, O. MOCREAC HYDROGEN SENSING BEHAVIOR OF TELLURIUM THIN

hydrogen tellurium film interaction essentially REFERENCES

differs from interaction of these films with NO2.
[1] Hamaguchi T.,Yabuki n., Uno M., Yamanaka S.,
Elemental hydrogen occurs only as bi atomic Egashira M., Shimzu Y., HUODO T., Synthesis and H2
gas molecules at normal conditions. These molecules properties of tin oxide nanohole arrays with various
do not comprises unpaired (dangling) electrons, i.e. electrodes, Sens. Actuators, B 113,p. 852 - 856, 2006.
cannot be expected the strong chemisorptions of [2] Ippolito S.J., Kandasamy S., Kalantar-Zadeh K.,
hydrogen on the surface or within the tellurium film. Wlodarski W., Hydrogen sensing characteristics of
Perhaps the sensitivity of tellurium films to H2 arise WO3 thin film conductometric sensors activated by Pt
because of reducing effect of oxygen priory and Au catalysts , Sens. Actuators, B 108, p. 154 - 158,
absorbed on the surface of the film from carrier (dry 2005.
air) gas. In our previous paper [9] was shown that [3] Tsiulyanu D., Marian S., Miron V., Liess H - D., High
weak chemisorptions of symmetric molecules of O2 sensitive tellurium based NO2 gas sensor, Sens.
from carrier gas is accompanied by localization of Actuators, B 73, p. 35-39, 2001.
holes near the surface, which results in decreasing the [4] Tsiulyanu D, Marian S, Liess H - D., Sensing properties
film resistance. Besides, the high concentration of of tellurium based thin films to propylamine and carbon
oxygen in carrier gas promotes formation of a oxide, Sens. Actuators, B 85, p. 232238, 2002.
catalytic gate [10], which can be removed by other [5] Sen S., Muthe K.P., Joshi N., Gadkari S.C., Gupta S.K.,
gases. That is why, assuming that molecular hydrogen Roy J.M., DeshpandE S.K., Yakmi J.V., Room tempe-
rature operating ammonia sensor based on tellurium
removes a priory-adsorbed oxygen we can expect the
thin films, Sens. Actuators, B 98, p. 154159, 2004.
decreasing of both, hole concentration and
[6] Sberveglieri G., Recent developments in semicon-
conductivity of the surface and intragrain regions of
ducting thin films gas sensors, Sens. Actuators, B 23,
tellurium film. p.103 -109, 1995.
4. CONCLUSIONS [7] Weimar U., Gopel W., AC measurements of thin oxide
Impedance spectra of tellurium thin films are sensors to improve selectivities and sensitivities, Sens.
Actuators, B 26-27, p.13 18, 1995.
strongly influenced by composition of gaseous envi-
ronment. The effect of harmful gases on impedance is [8] Macdonald J.R., Impedance spectroscopy, Wiley, New
York, p.341, 1987,
mainly due to variation of films resistance but capa-
citance does not very essentially. Addition of H2 [9] Tsiulyanu D., Stratan I., Tsiulyanu A., Liess H.-D,
Eisele I., Investigation of the oxygen, nitrogen and
increases impedance whereas addition of NO2
water vapors cross - sensitivity to NO2 of tellurium
decreases it in a large range of frequencies. based thin films, Sens. Actuators, B 121, p.406 413,
The response curves (sensitivity) for either 2007.
impedance or its imaginary part strongly depend on [10] Landstrom I., Approaches and mechanisms to solid
target gas H2 and NO2 and frequency, because of state based sensing, Sens. Actuators, B 35-36, p.11
different mechanisms of interaction between these 19, 1996.
gases with tellurium films.

IZVOD
PROUAVANJE PONAANJA VODONIKA NA OSETLJIVIM TANKIM
FILMOVIMA OD TELURA POMOU AC MERENJA
Po prvi put je pokazano da su Telurovi tanki filmovi osetljivost na H 2 na sobnoj temperaturi uz osetljivost na
NO2. Reagovanje vodonika na Telurove tanke filmove ispitan je metodom spektroskopske impedanse. Spektri
impedanse su pod jakim uticajem gasovitog okruenju, ali je efekat ciljanog gasa uglavnom zbog varijacija
otpora filma. Pretpostavlja se da osetljivost Telurovih tankih filmova za H 2 nastaje zato - da se smanji
dejstvo kiseonika apsorbovanog na povrini filma od provodnog gasa (suv vazduh). Visoka koncentracija
kiseonika u noseem gasu podstie formiranje katalitikog kapije, koja moe ukloniti druge gasove,
ukljuujui i vodonik.
Uklanjanje apriori apsorbovanog kiseonika smanjenjuje koncentracije i provodljivosti na povrinskim i
intrgranularnim regionima Telurovih tankih filmova. Zbog promene impedanse u drugom pravcu, redukcija
H2 moe se razlikovati od oksidacije NO2, stoga efikasno, rad na sobnoj temperaturi H2 senzora mogu biti
proizvedeni pomou telur osnovnih filmova.
Kljune rei: vodonik, osetljivi tanki filmovi, telur, AC merenja
Rad primljen: 18.02.2013.
Originalni nauni rad

ZATITA MATERIJALA 54 (2013) broj 2 111