The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers
The adsorboelectric effect arising in multilayered semiconductor structures based on the porous Si with catalytically active Pd electrodes due to action of low concentrations of hydrogen containing gases (Н₂, H₂S) at the room temperature is studied. The kinetic dependences of the change in output...
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Solntsev, V.S. Gorbanyuk, T.I. Litovchenko, V.G. Evtukh, A.A. 2017-06-03T05:12:45Z 2017-06-03T05:12:45Z 2008 The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers / V.S. Solntsev, T.I. Gorbanyuk, V.G. Litovchenko, A.A. Evtukh // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2008. — Т. 11, № 4. — С. 381-384. — Бібліогр.: 24 назв. — англ. 1560-8034 PACS 07.07.Df, 68.43.Bc, 68.47.Fg https://nasplib.isofts.kiev.ua/handle/123456789/119080 The adsorboelectric effect arising in multilayered semiconductor structures based on the porous Si with catalytically active Pd electrodes due to action of low concentrations of hydrogen containing gases (Н₂, H₂S) at the room temperature is studied. The kinetic dependences of the change in output signals of the samples upon action of different concentrations of gas molecules are studied using the capacitancevoltage characteristic method. The isotherms of adsorption are derived. A physical model of the adsorption of hydrogen containing gases in these structures is proposed to explain the observed phenomena. This work was supported by Science and Technology Centre in Ukraine, Project № 3819, by National Academy of science, Project № 51 and № 25- 2008, by Ministry of Science and Еducation, Project № M175-2007. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers Article published earlier |
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The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers |
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The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers Solntsev, V.S. Gorbanyuk, T.I. Litovchenko, V.G. Evtukh, A.A. |
| title_short |
The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers |
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The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers |
| title_fullStr |
The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers |
| title_full_unstemmed |
The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers |
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influence of h₂s and h₂ adsorption on characteristics of mis structures with si porous layers |
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Solntsev, V.S. Gorbanyuk, T.I. Litovchenko, V.G. Evtukh, A.A. |
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Solntsev, V.S. Gorbanyuk, T.I. Litovchenko, V.G. Evtukh, A.A. |
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2008 |
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English |
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Semiconductor Physics Quantum Electronics & Optoelectronics |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Article |
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The adsorboelectric effect arising in multilayered semiconductor structures
based on the porous Si with catalytically active Pd electrodes due to action of low
concentrations of hydrogen containing gases (Н₂, H₂S) at the room temperature is
studied. The kinetic dependences of the change in output signals of the samples upon
action of different concentrations of gas molecules are studied using the capacitancevoltage
characteristic method. The isotherms of adsorption are derived. A physical model
of the adsorption of hydrogen containing gases in these structures is proposed to explain
the observed phenomena.
|
| issn |
1560-8034 |
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https://nasplib.isofts.kiev.ua/handle/123456789/119080 |
| citation_txt |
The influence of H₂S and H₂ adsorption on characteristics of MIS structures with Si porous layers / V.S. Solntsev, T.I. Gorbanyuk, V.G. Litovchenko, A.A. Evtukh // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2008. — Т. 11, № 4. — С. 381-384. — Бібліогр.: 24 назв. — англ. |
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2025-11-25T20:35:27Z |
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2025-11-25T20:35:27Z |
| _version_ |
1850523664964911104 |
| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 381-384.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
381
PACS 07.07.Df, 68.43.Bc, 68.47.Fg
Influence of H2S and H2 adsorption on characteristics
of MIS structures with Si porous layers
V.S. Solntsev, V.G. Litovchenko, T.I. Gorbanyuk, A.A. Evtukh
V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine
45, prospect Nauky, 03028 Kyiv, e-mail: sensor@isp.kiev.ua
Abstract. The adsorboelectric effect arising in multilayered semiconductor structures
based on the porous Si with catalytically active Pd electrodes due to action of low
concentrations of hydrogen containing gases (Н2, H2S) at the room temperature is
studied. The kinetic dependences of the change in output signals of the samples upon
action of different concentrations of gas molecules are studied using the capacitance-
voltage characteristic method. The isotherms of adsorption are derived. A physical model
of the adsorption of hydrogen containing gases in these structures is proposed to explain
the observed phenomena.
Keywords: adsorboelectric effect, porous silicon, MIS gas sensor.
Manuscript received 18.06.08; accepted for publication 20.10.08; published online 11.11.08.
1. Introduction
Recently, porous silicon (PS) is suggested as a
perspective material for the formation of microelectronic
solid state gas sensors [1-5]. Semiconductor gas sensors
with a porous Si (PS) layer are advantageous due to (i)
the large internal surface area of PS (up to 200-
500 m2/cm3), which enhances the adsorption properties
of structures, (ii) its high chemical activity, (iii) a simple
and cheap formation technology that is compatible with
silicon CMOS technology, and (iv) the possibility of a
formation of multisensor arrays. At present, sensors with
a porous silicon layer exist for a number of gases such as
О2, H2, СО, СО2, NO, NO2, NH3, etc., water vapour,
organic and biological molecules [6-9]. Porous Si based
sensors use different physical principles and are formed
by several technologies: Shottky diodes, MIS structures,
optical sensors, etc. [10-24].
Study of the physical principles of gas adsorption
on porous silicon enables to extend the research of the
properties of semiconductor materials as well as their
practical application for gas sensing. Study of
adsorboelectric effect in the PS based structures makes it
possible to determine both adsorption and electrical
properties of this material at the same time.
Detection and determination of low concentrations
of ecologically harmful and explosive gases are an
important scientific and technical problem. Hydrogen
sulphide is one example of such gases. The importance
of detection is related to the necessity to monitor and to
control hydrogen and hydrogen sulphide leaks in many
technological processes such as oil and gas production
and conversion, storage and processing in food industry,
and ecological control of surrounding. Therefore, it is
important to have a stable sensor of H2 та H2S gases
with high sensitivity and selectivity.
In this paper, an adsorboelectric effect in the
structures with porous Si layers is studied
experimentally. The peculiarities of the kinetics of signal
change upon the action of different concentrations of
hydrogen and hydrogen sulphide gases are investigated.
The concentration dependences of the influence of gas
on the change of a response signal of structures are
derived. A physical model of gas adsorption in the MIS
structures under investigation is suggested as based on
the obtained experimental results.
2. Experimental
A porous Si layer was obtained by the electrochemical
etching of monocrystalline (100) oriented Si wafers
doped with boron up to the concentration of NA =
4×1015 cm–3. The anodisation current density was within
the range of j = 5-20 mA/cm2. The 4:1 solution of HF
(48 %) and ethanol C2H5OH was used as electrolyte
(HF ~ 80 %). The thickness of the porous Si layers
obtained was determined by profilometry to be 1 µm.
The porosity of layers was 60 to 70 %, according to the
results of gravimetry. An average pore size lay within
the range of 2 to 8 nm, as determined from the low
temperature nitrogen adsorption.
The layers of mesoporous Si were annealed at once
after preparation in weakly oxidising atmosphere
(∼20 % O2+80 % Ar/N2) at 450 °C. Catalytically active
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 381-384.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
382
palladium films with a thickness of ~ 50 nm were
deposited onto the surface of oxidised mesoporous Si by
magnetron sputtering and Al contacts by thermal
vacuum sputtering, respectively. Metal-dielectric-
semiconductor structures of Pd-PS-Si-Al with a top Pd
electrode of 4 mm in diameter were formed (Fig. 1).
Kinetic CFB(t) and capacitance-voltage C(V)
characteristics of Pd-PS-Si-Al structures were measured
using the capacitance-voltage curve tracer АМЦ 1594 at
the frequency of testing signal 1 MHz. The
investigations of the influence of gas on the
electrophysical characteristics of structures were carried
out at room temperature in the concentration range of
10-1000 ppm for hydrogen and 5-80 ppm for hydrogen
sulphide, respectively. During the investigation of gas
adsorption the «injection» regime of start-up of gases
was used. In more details of experiment it is described in
works [4, 24].
3. Results and discussion
Kinetic dependences of the change of the signal of Pd-
PS-Si-Al structures under the action of different
concentrations of gases were measured at fixed voltage
(Ufix) at the flat band level (CFB). The kinetic
dependences, ∆C(t) (∆C = C – C0, C0 being the
capacitance before the gas inlet and C the capacitance
after the gas inlet, respectively) under the action of
different concentrations of hydrogen sulphide (a) and
hydrogen (b) are shown in Fig. 2. It is seen that
hydrogen leads to the decrease of signal measured
(С < С0) and hydrogen sulphide results in the signal
increase (С > С0), i.e. hydrogen shows donor properties
and hydrogen sulphide acceptor properties, respectively.
It was found that even at low gas concentrations the MIS
structures had a high speed of performance and short
times of response ≤ 10 s.
The kinetic dependences reveal the important
peculiarities of adsorption process on the porous surface
of structures under investigation. Namely, the delay in
the signal, which shows the slowing down the motion of
molecules being adsorbed to the internal surface of
semiconductor layer, can be possibly caused by the
spilover effect. This effect appears due to the
discontinuity (micro- and nanostructure) of metal layer
and the gradual migration of adsorbed molecules under
the surface of “metal islands”. It is supported by a weak
dependence of the measured time of the establishment of
a signal of adsorption effect upon changing the gas
concentration in the surrounding (the pressure change is
several orders of magnitude), an exponential character of
the signal as well as a correlation of the time for
formation of initial electric surface layer with the delay
time (of signal) and a considerable increase of this time
for high pressures.
The dependences of the signal of Pd-PS-Si-Al
structures upon adsorption of various concentrations of
gases within the range of 5-1000 ppm are shown in
Fig. 3. Experimental points correspond to various
concentrations. They are compared to the theoretical
curves (curve 1 is for hydrogen sulphide and curve 2 for
hydrogen, respectively). It can be seen that the gas
sensing structure shows a high-level activity even to the
low gas concentrations, ≤ 5 ppm. The isotherms
gradually saturate upon increasing the gas concentration.
Analysis of adsorption isotherms for hydrogen
sulphide and hydrogen on the samples under
investigation demonstrated at least two mechanisms of
gas adsorption. After a theoretical analysis of
experimental data, the isotherms of gas adsorption were
re-plotted (Fig. 4).
Fig. 1. Schematic image of Pd-PS-Si-Al MIS structure.
a
b
Fig. 2. Kinetics of the signal response under action of
various concentrations of gases (hydrogen sulphide (a) and
hydrogen (b)).
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 381-384.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
383
Fig. 3. Isotherms of gas adsorption (1 – hydrogen
sulphide, 2 – hydrogen).
a
b
Fig. 4. Re-plotted isotherms of gas adsorption (hydrogen
sulphide (a) and hydrogen (b)).
It was found that the surface population upon
adsorption of hydrogen sulphide depends on the pressure
as θі ~ Р. The isotherm rectifies in coordinates Р-1 ↔ С-1,
which corresponds to the one-particle adsorption
described by the Langmuir law. Therefore, one may
suppose the molecular adsorption of hydrogen sulphide
and the isotherm maybe expressed as follows:
)]1/([max
)0( PaPaCC pp +∆=∆ , (1)
Fig. 5. Schematic image for mechanisms of hydrogen and
hydrogen sulphide adsorption.
where ∆С(0) is the steady (proportional to adsorption
concentration) state signal at the given pressure P and
temperature T, ∆Сmax is the signal at the highest
concentration of investigated gas, )2exp(~ kT
Ea a
P ,
and Еа is the adsorption heat per molecule, respectively.
Analysis of the adsorption isotherm of hydrogen
demonstrated that the population of surface upon the
pressure corresponds to the dependence θі~Р1/2. The
respective isotherm is rectified in coordinates Р-1/2 ↔
∆С-1 and is described by the following law:
)]1/([ 2\12\1
max
)0( PaPaCC pp +∆=∆ (2)
Such dependence is typical for the dissociative gas
adsorption, i.e. the decomposition of hydrogen molecule
in two hydrogen atoms, Н2 = На + На, takes place here.
The calculation of gas adsorption isotherms has
demonstrated the value of activated energy (Ea) for
hydrogen is 0.096 eV and for hydrogen sulphide –
0.084 eV. In both cases, the value of activation energy is
rather small close to 0.1 eV, which is typical for the
physical adsorption of gases.
The following mechanism of the sensitivity of
structures under investigation to the adsorption of
hydrogen and hydrogen sulphide can be proposed. Gas
molecules adsorb first on the surface of MIS structure
and then diffuse to the interface of Pd/porous Si on the
pore walls and grain boundaries. A molecule polarisation
takes place at the Pd/porous Si interface. With their
dipole moments, the polarised molecules make an
additional contribution to the contact voltage Fig. 5a.
There is change indemnification of electrical charge on
the interface of Pd/porous Si (hydrogen increases it
while hydrogen sulphide decreases). Such influence of
adsorbed molecules leads to respective changes in the
structure capacitance and the shift of C-V curve in the
negative region for hydrogen and in the positive region
for hydrogen sulphide (see Fig. 5).
4. Conclusions
The analysis of adsorption isotherms demonstrated
the molecular adsorption of hydrogen sulphide and the
dissociative adsorption of hydrogen on the surface of
MIS structures with porous Si layer. A testing sample of
b
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2008. V. 11, N 4. P. 381-384.
© 2008, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
384
a sensor was prepared for detecting low concentrations
of hydrogen and hydrogen sulphide at room temperature.
Acknowledgements
This work was supported by Science and
Technology Centre in Ukraine, Project № 3819, by
National Academy of science, Project № 51 and № 25-
2008, by Ministry of Science and Еducation, Project №
M175-2007.
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