Gridded Gate Pt-SiO2-Si MOS Sensor For Detection of Hydrogen
Gridded Gate Pt-SiO2-Si MOS Sensor For Detection of Hydrogen
Gridded Gate Pt-SiO2-Si MOS Sensor For Detection of Hydrogen
6205
I. I NTRODUCTION
N THE recent years the several impact on the environment
due to the burning of fossil fuels has attracted the modern
world for clean energy source; Hydrogen is being used as a
clean energy source in many industries like chemical, food,
semiconductor, petroleum, research laboratory etc [1], [2].
It is well known fact that hydrogen is inflammable, explosive
as well as hazardous gas. So due to safety reasons, its
continuous monitoring is required. Hydrogen sensors form an
integral part of any such systems incorporating hydrogen as
a fuel [2]. The MOS structure is also sensitive to hydrogen
containing molecules like ethylene, ethanol and hydrogen sulphide [3], [4]. If the metal film is made thin and discontinuous
nature, an increased response to several gases notably NH3 is
observed [7]. The selectivity pattern of MOS device depends
on the choice of catalytic metal gate, the structure of metal gate
and operating temperature [5][8]. Surface and interface states
1558-1748 2016 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
6206
IEEE SENSORS JOURNAL, VOL. 16, NO. 16, AUGUST 15, 2016
Fig. 2.
TABLE I
VARIOUS RF P LASMA D EPOSITION PARAMETERS
(iv)
(v)
(vi)
(vii)
(viii)
oxygen flow are kept same for all the eight samples.
The details of various deposition parameters for all
eight samples have been provided in Table I.
After RF oxygen plasma treatment of SiO2 film surface,
photolithography technique is used for retaining front
side oxide and removing the oxide from the back side
of all the sensors.
Subsequently, Pt is deposited on the front face of all
nine sensors (including S1sensor) of thickness 420
by thermal evaporation method (model no. 12A4D,
Hind Hivac Co. Ltd., India, make).
For the required gridded gate structure a standard mask
is used which has been reported elsewhere [4]. The
outer diameter and inner diameter of gate structure are
kept 1.5 mm and 0.3 mm, respectively. The necessary
photolithography using lift off technique has been performed to have proper dimensions of MOS structure.
Aqua Regia is used for platinum metal etching.
The ohmic contact to the back side of Si substrate is
made by evaporating Al metal.
Annealing at 450 C in N2 ambient atmosphere for
7 minutes is performed to have proper ohmic contacts.
KUMAR et al.: EFFECT OF RF PLASMA ON GRIDDED GATE Pt/SiO2 /Si MOS SENSOR FOR DETECTION OF HYDROGEN
6207
TABLE II
C OMPARATIVE S TUDY OF VARIOUS MOS S ENSORS
reveals the micro porous and granular nature of the SiO2 film.
The surface roughness and grain size of SiO2 film of all nine
sensors have been evaluated from AFM micrograph and shown
in Table II.
C. Electrical Characterization of the Device
The C-V measurements of fabricated gridded Pt/SiO2 /Si
MOS capacitor sensors (all nine samples) have been carried out in air, in a closed chamber towards hydrogen
(250-3500 ppm) at 25 Khz at room temperature by fully
automated C-V analyzer using precision LCR meter (Model
No. HP-4284A, frequency range of 20 Hz to 1 MHz). The
schematic of experimental setup used to study the C-V
response of the fabricated device has already been reported
elsewhere [4].
III. R ESULT AND D ISCUSSION
The surface morphology of SiO2 films of all nine sensors has been investigated through AFM study shown in
Fig. 4(a) to Fig. 4(f). Moreover, the film surface of all plasma
treated sensors (S2-S9) comprising of micro porous structures
which may lead to improved sensing behavior of the device
which is shown in Fig. 4(b) to 4(f). It has been observed that
very small porosities are found in non plasma treated SiO2
film of S1 sensor which is shown in Fig. 4(a). Fig. 5(a) shows
the C-V characteristics of S1 sensor and Fig. 5(b) to Fig. 5(i)
show the C-V characteristics of all eight MOS sensors (S2-S9)
Fig. 3. (a) SEM image of Pt gate film of sample S3. (b) SEM image of
Pt gate film of sample S4. (c) SEM image of Pt gate film of sample S5.
treated at 40 W and 50 W RF oxygen plasma power for different durations (2 min., 4 min., 8 min. and 12 min.) upon exposure to various concentrations of hydrogen (250-3000 ppm)
at 25 KHz. It has been observed that with increase in the
hydrogen concentration the entire C-V curve shifts towards the
negative side of the voltage axis [22], [24], [25]. The change in
capacitance with H2 concentration is converted into percentage
sensitivity (%) through the formula [24]
S(%) = ((Cair Cgas )/Cair ) 100
(1)
6208
IEEE SENSORS JOURNAL, VOL. 16, NO. 16, AUGUST 15, 2016
Fig. 4. (a) AFM images of Non plasma treated SiO2 film (S1). (b) Surfaces treated with O2 plasma at 40W RF power for 4 minutes (S3). (c) Surfaces
treated with O2 plasma at 40W RF power for 8 minutes (S4). (d) Surfaces treated with O2 plasma at 40W RF power for 12 minutes (S5). (e) Surfaces treated
with O2 plasma at 50W RF power for 4 minutes (S7). (f) Surface treated with O2 plasma at 50W RF power for 8 minutes (S8).
(2)
KUMAR et al.: EFFECT OF RF PLASMA ON GRIDDED GATE Pt/SiO2 /Si MOS SENSOR FOR DETECTION OF HYDROGEN
6209
Fig. 5. (a) C-V response of Non plasma treated gridded gate Pt/SiO2 /Si MOS sensor (S1) in air at room temperature. (b) C-V response of O2 RF plasma
treated at (40 W, 2 min.) gridded gate Pt/SiO2 /Si MOS sensor (S2) in air, at room temperature. (c) C-V response of O2 RF plasma treated at (40 W, 4 min.)
gridded gate Pt/SiO2 /Si MOS sensor (S3) in air, at room temperature. (d) C-V response of O2 RF plasma treated at (40 W, 8 min.) gridded gate Pt/SiO2 /Si
MOS sensor (S4) in air, at room temperature. (e) C-V response of O2 RF plasma treated at (40 W, 12 min.) gridded gate Pt/SiO2 /Si MOS sensor (S5) in
air, at room temperature. (f) C-V response of O2 RF plasma treated at (50 W, 2 min.) gridded gate Pt/SiO2 /Si MOS sensor (S6) in air, at room temperature.
(g) C-V response of O2 RF plasma treated at (50 W, 4 min.) gridded gate Pt/SiO2 /Si MOS sensor (S7) in air, at room temperature. (h) C-V response of
O2 RF plasma treated at (50 W, 8 min.) gridded gate Pt/SiO2 /Si MOS sensor (S8) in air, at room temperature. (i) C-V response of O2 RF plasma treated at
(50 W, 12 min.) gridded gate Pt/SiO2 /Si MOS sensor (S9) in air, at room temperature.
Fig. 6.
(a) Variation of sensitivity vs concentration of Non plasma treated gridded gate Pt/SiO2 /Si MOS sensor (S1) in air, at room temperature
at 0.3 V Bias. (b) Variation of sensitivity vs concentration of O2 RF plasma treated at 40 W RF plasma power gridded gate Pt/SiO2 /Si MOS sensors
(S2-S5) for different durations in air, at room temperature, Bias Voltage = 0.4 and 0.1V for S2-S4 and S5, respectively. (c) Variation of sensitivity vs
concentration of plasma treated at 50 W RF plasma power gridded gate Pt/SiO2 /Si MOS sensors (S6-S9) for different durations in air, at room temperature,
Bias Voltage = 0.2V for S6 and S8 and 0.4V for S7 and S9.
6210
IEEE SENSORS JOURNAL, VOL. 16, NO. 16, AUGUST 15, 2016
Fig. 7. (a) Variation of fixed oxide charge density vs concentration of Non plasma treated sample (S1) in air, at room temperature. (b) Variation of fixed oxide
charge density vs concentration of O2 RF plasma treated at 40 W RF plasma power gridded gate Pt/SiO2 /Si MOS sensors (S2-S5) for different durations
(2 min., 4 min., 8 min., and 12 min.) in air at room temperature. (c) Variation of fixed oxide charge density vs concentrations of O2 RF plasma treated at
50 W RF plasma power gridded gate Pt/SiO2 /Si MOS sensors (S6-S9) for different durations (2 min., 4 min., 8 min., and 12 min.) in air, at room temperature.
TABLE III
TABLE IV
(3)
where,
is an effective method to increase the oxide barrier by changing the oxide stoichiometry and consequently improves the
electrical properties of the surface. It had been observed that
sensor made up by porous gate metal film as well as SiO2 film
posses higher gas sensitivity due to the increase in effective
surface area [4], [30]. When the effective surface area of the
sensor increases, it results in an increase of the oxygen species
available for reaction with reducing gas in contact with the
sensor. This results in an increase in sensitivity [31].
The gas sensing mechanism of SiO2 sensor is based on
surface reaction between the oxygen species and the reducing
gas in contact with the sensor [32][34]. Oxygen plasma
constitutes single and multiple species like O , O2 , O3 ,
O4 , O+4 , O3+ , O2+ , O+ etc and e [35], [36]. When these
species interact with each other, the no. of adsorption sites
inside the device also get modulated, accordingly. On the
exposure of reducing gases like hydrogen the adsorbed gas
molecules (in this case H2 ) interact with these species (single
or multiple) which are present at the SiO2 surface due to
plasma treatment, and can exchange electrons with SiO2
Ci Cmin
1
U F = 1.16 + 2.17 ln
Ci Cmin
A
(4)
(5)
KUMAR et al.: EFFECT OF RF PLASMA ON GRIDDED GATE Pt/SiO2 /Si MOS SENSOR FOR DETECTION OF HYDROGEN
concentration for non plasma treated sensor (S1). The increasing tendency of fixed charge density with increase in hydrogen
concentration for non plasma treated gridded gate Pt/SiO2 /Si
MOS sensor had already been reported elsewhere [37].
Fig. 7(b) and Fig. 7(c) illustrate the effect of plasma
treatment on fixed charge density at 40 W and 50 W
RF plasma power, respectively. In case of 40 W of plasma
power, the value of fixed charge density varies with H2
concentration and has been found to be maximum for plasma
exposure time of 8 minutes but for higher duration (12 min.)
at 40 W and higher plasma power (50 W) the fixed charge
density decreases, due to surface sputtering [21], [27].
The response and recovery times of sample S1-S9 are shown
in Table IV.
IV. C ONCLUSION
From Fig. 6(a) to Fig. 6(c) it has been observed that
all plasma treated gridded gate Pt/SiO2 /Si MOS sensors
exhibit a better sensitivity except S5,S8 and S9 as compared
to non plasma treated gridded gate Pt/SiO2 /Si MOS sensor (S1) (73%) towards hydrogen. Sensor S4 out of all nine
sensors exhibits highest sensitivity (91%) as compared to
other samples. In present case, the better response of the sensor
is attributed to the following reasons: (i) Due to the gridded
gate structure and large porosity found in the gate metal film
as well as SiO2 film, effective surface area of the sensor
increases which results in an increase of the oxygen species
available for reaction. This results in an increase in sensitivity [4], [31], (ii) Oxygen plasma comprises of single and multiple species like O , O2 , O3 , O4 , O+4 , O3+ , O2+ , O+ etc
and e [35], [36], When these species interact with each other,
a number of adsorption sites inside the device also gets modulated and hence sensitivity of the device increases, (iii) Spillover mechanism, inner side wall and outer side wall diffusion
and better chemical absorption of hydrogen in air ambient [4],
[39], [40], (iv) Large grain size and high surface roughness,
found in the SiO2 film are few other reasons which are also
responsible for improvement in sensitivity. However, there are
few practical disadvantages to the use of microwave frequencies; plasma is often difficult to initiate and can be unstable.
The Plasmon must be shielded as microwaves are hazardous
and scaling up the plasma to enable large area film to be
grown is difficult. Whereas, capacitive coupled RF plasma
does not suffer these drawbacks and have found widespread
applications in other thin film growth environments [28]. Thus,
it is concluded that RF oxygen plasma treated gridded gate
Pt/SiO2 /Si MOS capacitor may be technologically a better and
preferred choice for hydrogen detection.
ACKNOWLEDGMENT
The authors are thankful to Dr. Sushil Kumar, Principal
Scientist, NPL, New Delhi, and Dr. G. V. Ganesan, Centre
Director, UGC-DAE consortium for Scientific Research,
Indore, India to access the Plasma facility and AFM measurement facility, respectively.
R EFERENCES
[1] K.-W. Lin et al., A hydrogen sensing Pd/InGaP metal-semiconductor
(MS) Schottky diode hydrogen sensor, Semicond. Sci. Technol., vol. 18,
no. 7, pp. 615619, 2003.
6211
6212
IEEE SENSORS JOURNAL, VOL. 16, NO. 16, AUGUST 15, 2016
Vinod Kumar received the B.E. degree in electronics engineering from Nagpur University, Nagpur, in
1998, the M.Tech. degree in microelectronics from
the Indian Institute of Technology (Banaras Hindu
University) (IIT-BHU), Varanasi, India, in 2008, and
the Ph.D. degree from the Department of Electronics Engineering, IT-BHU, in 2016. He is currently an Associate Professor with the Department
of Electronics and Communication Engineering,
R. K. G. I. T., Ghaziabad, India. His research areas
of interest include MOS sensors, plasma processed
materials and devices, and thin-film devices.