CHAPTER 7

FABRICATION AND CHARACTERIZATION OF

ITO AND ALN SENSORS

Thin film fabrication methods have been used for production of metal

oxide gas sensors. Thin film metal oxide sensors are small, and relatively

inexpensive to fabricate, have lower power consumption than thick film

sensor and can be integrated directly into the measurement circuitry. There are

various electrode designs but the interdigitated structure appears to be the

most common approach. A heating element is printed onto the back of the

substrate to provide the high temperatures required for metal oxides to operate

as gas sensors, typically 200 500 0C. Film thickness ranges from 10 to 300

mm for thick film and 6-1000 nm for thin film [221]. Catalytic metals are

sometimes applied on top of the oxides to improve sensitivity to certain gases.

The same preparative methods are used to apply the catalytic metal [222-224].

In the present chapter, fabrication of ITO thin film as a resistive

semiconducting metal oxide gas sensor has been described. The sensor

response for three different gases; nitrogen dioxide, ethanol and hydrogen, for

different concentration and for different operating temperatures has been

discussed. The fabrication of Aluminum nitride thin films as hydrogen sensor,

203
focusing on the interaction mechanism of hydrogen with the MIS device is

described. The influence of hydrogen on Pd/AlN/Si and Al/AlN/Si structures

have been discussed in detail in this chapter.

7.1 FABRICATION AND GAS SENSING MEASUREMENT OF ITO

SENSOR

After having optimized the deposition parameters for ITO films the

device was fabricated as a resistive type gas sensor. The substrate used was 4

cm x 4 cm size glass microscope slide. The indium tin oxide thin film of

thickness about 0.4 m grown by rf magnetron sputtering at an rf power 150

W was used to fabricate the device. Two thick gold pads of 7 mm X 4 mm

were deposited on two sides of the sensor for ohmic contacts to permit

electrical measurements. The sensor area was kept as 25 mm X 25 mm. The

schematic representation of the ITO sensor device is shown in Figure 7.1. The

SEM image of the layup of the ITO thin film sensor is shown in Figure 7.2.

ITO thin film gas sensors are of a variable resistance type, the resistivity of

which changes in the presence of the gas. Measurement of resistance was

carried out using high impedance electrometer (Keithley, Model No. 614).

The substrate could be kept at a chosen temperature using a Pt-heater and the

values of temperature are measured by the NiCr thermocouple, with an

accuracy of 1 C using a temperature controller. The resistance of the sensor

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Figure 7.1 Schematic representation of the ITO sensor device

Figure 7.2 SEM image of the lay up of ITO film sensor

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 was measured for different temperatures in gasair ambient. The

change in temperature and resistance of sensor were simultaneously measured

when different concentrations of gas were introduced in to the test chamber.

Gas sensors based on ITO utilize selective chemical sensitivities of

their surface to different adsorbed gases [225]. This causes changes to the

electrical resistance of the sensor. Semiconducting metal oxides owe their

conductivity to their deviation from stoichiometry. Defects such as cation or

anion vacancies play an important role in their conductivity. ITO thin film

provides electronic defects that increase the influence of oxygen partial

pressure on electrical conductivity. Because oxygen vacancies on metal-oxide

surfaces exist as electrically and chemically active, these vacancies function

as n-type donors increasing the electrical resistivity of ITO. Upon adsorption

of charge, accepting molecules at the vacancy sites, namely from oxidizing

gases such as NO2, these electrons effectively deplete themselves from the

conduction band of the semiconductor. This leads to a further increase in the

electrical resistance of n-type ITO.

7.1.1 Response of ITO sensor to Nitrogen dioxide gas

The ITO sensor was operated at different concentrations of nitrogen

dioxide in the temperature range 300700 K. Figure 7.3 shows the variation in

sensitivity of the ITO sensor with operating temperature in the presence of

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NO2 gas. The gas concentration was kept constant at 50 ppm. It was observed

that the response of ITO sensor increased with temperature. At 600 K, it was

maximum and then decreases rapidly at 700 K. This reflects that the surface

redox state of the elements changes with temperature, with the highest at 600

K. The ratio of measured resistance before and after exposing the sample

surface to nitrogen dioxide gives the sensitivity of the sensor towards NO2.

The maximum sensitivity was found to be 28, which is higher than the

response of single oxide SnO2, In2O3 and Ga2O3 sensors, reported in literature

[226-228]. Also, the mixing of two different metal phases should be a factor

that imparts higher dispersivity and defectiveness to the material, hence

increasing the response towards NO2. The sensor working temperature that

regulates the adsorption/desorption processes at equilibrium and the

competition of chemisorptions between NO2 and atmospheric oxygen O2 for

the same active surface sites, play an important role in determining the

specific interaction between the gas and sensor [229].

L. Francioso et al. [230] have investigated the nanocrystalline SnO2,

In2O3 and In2O3SnO2 (molar ratio 1:1) thin films prepared by modified sol

gel method. Their performances in the detection of nitrogen dioxide (220

ppm in dry air) by electrical characterization in controlled atmosphere have

been reported. They showed that all the sensors showed high responses to

207
NO2. In general, the best performances in terms of response, sensitivity and

low detection limit were found in In2O3SnO2 based sensor. Gas-sensing

nanocomposites of SnO2In2O3 have been reported by Aifan C et.al [231],

using a chemically controlled co-precipitation method. They reported that

nanocomposites exhibited high sensitivity and selectivity for the detection of

NOx, and the sensitivity depended on the composition of the composites,

calcination temperature and operating temperature. They also showed that the

incorporation of In2O3 as a secondary component suppressed the grain growth

of SnO2, resulting in the increased sensitivity. Particularly, additives of Pd and

Al2O3 as dopants and as surface coating, greatly improved the sensitivity and

selectivity of the optimized nanocomposite.

Figure 7.4 shows the sensitivity of ITO thin film sensors to varying

concentrations of NO2 at two different working temperatures. At a working

temperature of 400 K, ITO sensor had good response over a wide range of

NO2. The sensitivity was linear from 5 ppm to 200 ppm. At 600 K, the sensor

showed enhanced response to NO2, at concentrations lower than 50 ppm. At a

higher concentration, the sensitivity increased slightly. NO2 molecules are

active oxidizing species and may decompose on adsorption sites. If there are

no stable adsorption sites for NO2 on the ITO thin film sensor, some NO2

molecules will decompose and desorb from the sensor, which inhibits the

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further adsorption of NO2. At low temperature, a direct ionosorption at the

active film surface takes place as

NO2, gas NO2, ads . (7.1)

At higher temperature, , ads ions tend to dissociate into two independent

atomic , ads and NO2 molecules start to compete with oxygen for the

available surface sites active for chemisorptions [232]. In this situation, with a

considerable surface coverage of , ads ions, NO2 reacts with , ads ions

forming nitrato complexes , ads,

NO2, gas N , ads . (7.2)

Therefore, higher working temperature will accelerate decomposing and

desorbing of NO2, and we get a higher sensitivity at low concentration. By

suitably changing working temperature, the ITO gas sensor can adapt

applications in both low and high NO2 concentration.

Cantalini et al. [233] produced films of WO3 of 150 nm thickness.

Varying the concentration of the NO2 gas between 0.2 and 5.0 ppm at 623 K

operating temperature, the films demonstrated good sensitivity at all

concentration. The largest responses to NO2 gas were found at working

temperature of 473 K, using the film annealed at 773 K. Comini et al. [234]

showed a film formed by magnetron sputtering of tin oxide to be sensitive to

209
nitrogen dioxide. The response was reported to be obvious at just 1ppm and

are large at 5 ppm and 10 ppm. Mixed oxide (SnIn)O + Pt with various

composition Sn/In = 1:1, 2:1, 5:1 and 10:1 for sensing materials were

prepared by Kap-Duk Song et.al [235]. It was reported that the gas sensing

characteristics had linearity for wide range (0.520 ppm) of gas concentration.

7.1.2 Response of ITO sensor to Ethanol gas

The most widely used metal oxide materials for alcohol detection

are SnO2, ZnO, WO3, TiO2 and Zr2O3. Palladium-doped ZnO nanoparticles,

produced by flame spray pyrolysis of organometallic precursors and mixed

into an organic paste to form thick sensing films, were tested for detection of

ethanol vapors in the 25-250 ppm range in dry air at 400C. A lower

concentration of ethanol was detected by CeO2-doped ZnO thin films,

fabricated using the dip-coating method [236,237]. But owing to the excellent

stability of indium tin oxide (ITO), which is free from drift common in tin

oxide materials, use of ITO is very promising for ethanol detection. To study

the sensing properties of ITO senor for ethanol gas, the chamber was

evacuated to a base pressure of 1.3 Pa using an oil free vacuum pump. Ethanol

was then injected inside the chamber using a calibrated digital micro-pipette,

where in, it was allowed to evaporate naturally and come in contact with the

sensor kept at elevated temperature. A typical 0.4 ml of ethanol corresponds

210
to 10 ppm as reported by Shurmers et al [238]. Before the measurement the

samples were preheated up to 700K and then cooled to 650K. An electric fan

was installed in the container, which improve uniformity of the gas. The

change in resistance of the sensor was measured for different temperatures.

The sensitivity for reducing gases is defined using the relation S = (R a - Rg) /

Rg, where Rg and Ra the resistance of the sensor in the testing gas and in the

air, respectively.

The factors influencing the gas sensing properties of ITO are essential

trapping of electrons at adsorbed molecules and band bending induced by

these charged molecules which is responsible for a change in conductivity.

The negative charge trapped in these oxygen species causes an upward band

bending and thus a reduced conductivity compared to the flat band situation.

As shown in Figure 7.5, when O2 molecules are adsorbed on the surface of

metal oxides, they would extract electrons from the conduction band E c and

trap the electrons at the surface in the form of ions. This will lead a band

bending and an electron depleted region. The electron-depleted region is so

called space-charge layer, of which thickness is the length of band bending

region. Reaction of these oxygen species with reducing gases or a competitive

adsorption and replacement of the adsorbed oxygen by other molecules

decreases and can reverse the band bending, resulting in an increased

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conductivity. O is believed to be dominant at the operating temperature of

573450C [239], which is the working temperature for most metal oxide gas

sensors.

Figure 7.6 shows the variation in resistance Rg of ITO thin film gas

sensor with change in operating temperature upon exposure to ethanol

vapours. The ethanol concentration was kept constant at 900 ppm. It was

observed that the resistance of the sensor Rg decreases with an increase in the

temperature and at 650 K, it was minimum. This proves 650 K to be the

optimum temperature of the ITO sensor for ethanol detection. The reason for a

decrease in the resistance may be due to the oxidation of the ethanol vapour

upon coming in contact with the oxide semiconductor surface, which liberates

free electrons and H2O. Ethanol vapors react with the chemisorbed oxygen

and re inject the carrier thereby reducing the resistance of the material.

The mechanism of the ethanol detection is due to an adsorption of the

ambient oxygen onto the sensitive element of the sensor kept at elevated

temperature. The reaction kinetics is as follows [240].

. (7.3)

. (7.4)

+ 2 . (7.5)

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Oxygen adsorption takes place at high working temperatures of 650 K. In fact,

at lower temperatures, the surface reactions proceed too slowly to be useful, at

the same time as at higher temperatures the increased promotion of electrons

in to the conduction band tends to obscure the effects of the contaminant

reducing gases. The next step is a reaction between ethanol and ionic oxygen

species.

C2H5 H CH3CHO H2 . (7.6)

Figure 7.7 shows the variation in the sensitivity of sensor S, with

concentration of ethanol at a working temperature of 650 K for as deposited

and annealed films. The concentration was varied from 200 ppm to 1400 ppm.

As it is seen, the sensitivity of the sensor increased with an increase in the

concentration, and the response seems to be quite linear in the entire

concentration range. The effect of post deposition annealing induces a surface

stabilization of the ITO film and increases the sensitivity as the concentration

of ethanol increases. Figure 7.8 shows how the response of the sensor changes

with operating temperature for as-deposited and annealed film. The

concentration of ethanol was 900 ppm. It was observed that the closely packed

morphology of the film annealed at 700 K, show enhanced response due to the

interaction of ethanol gas with ITO films, which strengthens the output signal

and sensitivity of the sensor.

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Figure 7.3 Variation of sensitivity of ITO sensor
towards NO2 with operating temperature

Figure 7.4 Variation of sensitivity of ITO sensor with

concentration of NO2

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Figure 7.5 Schematic diagram of band bending
after chemisorptions of charged species

Figure 7.6 Variation of resistance of ITO sensor with

operating temperature towards 900 ppm of ethanol

215
Figure 7.7 Variation of sensitivity of ITO sensor towards
ethanol with operating temperature (a) before annealing and
(b) after annealing

Figure 7.8 Variation of sensitivity of ITO sensor with

concentration of ethanol (a) before annealing and (b) after
annealing

216
7.1.3 Response of ITO sensor to Hydrogen gas

Hydrogen attracts more and more attention as a variable clean fuel and

thus there are extensive research activities in hydrogen storage, generation,

and fuel cells. Since hydrogen is explosive when its concentration in air is

more than 4 vol %, sensitive, selective, and stable sensors are needed to

measure hydrogen concentration. Factors influencing gas sensitivity in thin-

film gas sensors are the nature of gas-sensing materials, microstructure and

thickness of the films, fabrication condition, operating temperature, etc. [241,

242].

Figure 7.9 shows the variation in sensitivity of the ITO sensor with

operating temperature in the presence of H2 gas. The gas concentration was

kept constant at 1000 ppm. It was observed that the sensitivity of ITO sensor

increased with temperature and at 400 K, it was maximum and then decreases

rapidly, with minimum at 700 K. The maximum response was found to be 1.6

at 400 K, which is considered to be the optimum temperature at which ITO

can be operated as a hydrogen gas sensor. Figure 7.10 shows the variation in

the sensitivity S, with concentration of hydrogen gas at a working temperature

of 300 K. The concentration was varied from 1000 ppm to 7000 ppm. As it is

seen, the response of the sensor decreased with an increase in the

concentration. It is maximum at 1000 ppm and gradually decreases, becomes

217
minimum at 5000 ppm and almost remains constant up to 7000 ppm. The

mechanism of hydrogen detection is described as follows [243]. There are two

stages of gas sensing detection. Atmospheric oxygen gets adsorbed on the

surface, removing a carrier from the conduction band of n-type

semiconductor, becomes O2 or O species. This phenomenon reduces the

overall conductance. The reducing gas such as hydrogen will react with

chemi-adsorbed oxygen. This process will reinject the carrier and increase the

sensor conductance. The interaction between a semiconductor surface and H2

(with reducing properties) can be explained in terms of the reaction of H 2

molecules with the preadsorbed O2.

2H2 (g) 2H2 O (g) . (7.7)

H2 (g) H2 O (g) . (7.8)

H2 (g) H2 O (g) . (7.9)

As seen from the above equations, the interaction between chemisorbed O2

and the reducing gas (in this case H2) results in a decrease of surface

chemisorbed O2, and in an increase of electrical conductance. An important

factor to be taken in to account is the presence of water vapor at the sensor

surface, since the formation of hydroxyls is in competition with the O 2

adsorption; the OH group does not influence directly the surface reactions but

affects the reaction rate. Water adsorbing on the metal oxide surface will not

218
Figure 7.9 Variation of sensitivity of ITO sensor towards
H2 with operating temperature

Figure 7.10 Variation of sensitivity of ITO sensor with

concentration of H2

219
donate electrons to sensing layers. Moreover, it will lower the sensitivity of

metal oxide sensors for some reasons as follows [244]. The reaction between

the surface oxygen and the water molecules conduces to a decrease in baseline

resistance of the gas sensor, and results in a decrease of the sensitivity.

Secondly, the adsorption of water molecules leads to less chemisorption of

oxygen species on the ITO surface, due to the decrease of the surface area that

is responsible for the decrease in sensor response.

On the other hand, water molecules also act as a barrier against H2

adsorption. The superficial migration of the H2 atoms on the ITO surface

becomes difficult, thus decreasing the response. Water adsorption will

significantly lower the sensitivity of metal oxide gas sensors, as shown in

Figure 7.9 and 7.10. Furthermore, prolonged exposure to humid environments

leads to the gradual formation of stable chemisorbed OH on the surface

[245], causing a progressive deterioration of the sensitivity of the sensor.

The sensitivity of ITO sensor towards NO2, H2 and ethanol for different

operating temperature shown in Figure 7.3, 7.7 and 7.9, respectively, reveal

that different gases have similar shapes. The response increase and reach their

maximum at a certain temperature, and then decreased rapidly with increasing

temperature. This tendency is commonly observed in many reports [246, 247-

251]. The shape observed resulted from the competition between slow kinetics

220
at low temperatures and enhanced desorption at high temperatures. Typically,

temperature dependence of a metal-oxide sensor signal to the presence of a

given analyte possesses a bell shape with a maximum at a certain temperature

[249]. This dependence arises due to several reasons. First of all, as mentioned

above, the charge of oxygen species adsorbed at the oxide's surface depends

on temperature [252]. Second, since the oxidation reaction is an activated

process, its rate increases with temperature. Finally, all adsorption, desorption,

and diffusion processes are temperature dependent [250]. Thus, temperature

modulation leads to response patterns that are characteristic of the species

present in a gas mixture [251].

7.1.4 CONCLUSION

The gas sensing properties of ITO film towards NO2, ethanol and H2

was investiaged. The ITO thin film sensor showed enhanced sensitivity to

NO2 gas at 600 K especially, at concentrations lower than 50 ppm. The sensor

show a linear response to ethanol gas in the concentration range of 200 to

1400 ppm. Post-deposition annealing of the film at 700 K, ehanced the

response of the ITO senor to ethanol gas. The sensor showed low response to

Hydrogen gas when compared to nitrogen dioxide and ethanol. The maximum

response was found to be 1.6 at 400 K and 1000 ppm of H2.

221
7.2. FABRICATION AND GAS SENSING MEASUREMENT OF AIN
SENSOR
After having optimized the deposition parameters for AlN films, two

different MIS devices were fabricated as gas sensor with Al and Pd as

catalytic layer respectively. Metal-insulator-semiconductor (MIS) structures

were formed by sputter deposition through a metal mask of Al and Pd dots of

1mm in diameter and 150 nm thick on AlN film as top electrode and a

continuous Al film of 150 nm thick, on Si wafer backside as bottom electrode.

The thicknesses of AlN thin film as insulating layer was approximately

50 nm. Figure 7.11 and Figure 7.12 show the schematic representation of

Pd/AlN/Si and Al/AlN/Si devices, respectively. First a 50 nm AlN film was

deposited by magnetron sputtering technique onto an n-type Si (1 0 0) wafer.

This is followed by a circular 1mm diameter and 150 nm thick Pd dot

deposited onto the AlN layer using magnetron sputtering as a top electrode.

An Al film of 150 nm in thickness was deposited onto the back side of the Si

to form a back contact. In the similar, way another MIS structure was

fabricated with the same values of the thickness, but with Al as top electrode.

The response of both the device towards hydrogen gas sensing is investigated.

The MIS structure mounted on a heater was housed within an airtight

chamber. The test gas was injected inside the chamber using two mass flow

controllers one for H2 and other for dry air. The C-V characteristic of the

222
sensor in air and vacuum was measured using an impedance analyzer at 1MHz

frequency at room temperature. Hydrogen is reported to be able to alter the

effective charge at the metal/semiconductor interface or metal/dielectric

interface, resulting in changes in barrier height [253,254]. This effect is

utilized in semiconductor based gas sensors fabricated on various

semiconductor materials such as Si SiC [255] and GaN [256].

Figure 7.11 Schematic representation of the Pd/AlN/Si device.

Figure 7.12 Schematic representation of the Al/AlN/Si device.

223
 The interaction of hydrogen with semiconductor devices has long been

studied, and intensive research led to a model, which attributes the reaction

mechanism of the devices to hydrogen, to the formation of a hydrogen-

induced dipole layer at the metal/dielectric/semiconductor interface [257-262].

Figure 7.13 shows the schematic illustration of the principle of gas sensitive

MOS capacitor. The molecular hydrogen adsorbs on Pd or Pt surface and

dissociates. Hydrogen atoms diffuse through Pd or Pt, and adsorb at the

metaloxide interface forming a dipole layer. The dipole layer is responsible

for the work function change, for example, showing a voltage shift in the C-V

characteristics of the device. The hydrogen atoms at the metal insulator

interface decrease the flat band voltage of the capacitor (the voltage at which

there is no band bending in the semiconductor), which gives a voltage drop,

V, resulting in a shift, V along the voltage axis, of the C-V curve of a

capacitor. The field effect devices also respond to other hydrogen-containing

molecules like hydrocarbons, which deliver hydrogen atoms to the metal-

oxide interface, provided that the molecules are dissociated on the metal

surface [263 - 265]. Oxygen molecules are also dissociated on the catalytic

metal surface. Oxygen and hydrogen gas adsorbed on the surface forms water

which leaves the surface.

224
 Figure 7.13 Schematic illustration of the principle of gas
sensitive MOS capacitor

In the present work, the interaction mechanism of hydrogen with AlN

thin films focusing on the metal/semiconductor interfaces has been

investigated. The electrical properties were evaluated by measuring

capacitance-voltage (C-V) characteristics, obtained from an Impedance

Analyzer operated at 1MHz. The (C-V) characteristics of MOS devices

studied at high frequencies revealed a low capacitance in the case of inversion

and a high capacitance in the case of accumulation. The interaction of gas

molecules with MIS-Si devices gives rise to changes in the (C-V) curves.In

the case of reducing gas H2, the C-V curve is shifted toward negative voltages.

During exposure to gas, the capacitance was held constant by controlling the

bias voltage. The gas response R, which is defined as the difference between

the steady state voltages measured at the test gas exposure and in dry air is

described by the following relation.

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 R= V= VV-Vg (7.12)

where, VV and Vg are the voltage of the sensor in vacuum and in the presence

of gas, respectively. The voltage shift obtained is positive in the case of

reducing gases and negative in the case of oxidizing gases.

7.2.1 Response of Pd/AlN/Si device to Hydrogen gas

The response of Pd/AlN/Si device reveals that, there is a substantial

difference between the capacitance-voltage (CV) curves in dry air and in the

presence of H2 gas. A voltage shift of approximately 0.8 V is observed in the

capacitance voltage curve, as seen in Figure 7.14. In Pd/AlN/Si device, gas-

phase H2 dissociates on the surface of the catalytic metal to form H atoms.

These atoms then rapidly diffuse through the metal film to the metal-insulator

interface, where they are preferentially trapped in stabilized adsorption sites.

The layer of interfacial hydrogen created by this process exists in a dipole layer,

creating an additional voltage drop across the MIS sensor that can be measured

as a voltage shift in the capacitance-voltage (C-V) curve of a capacitor [264]

The Pd/AlN/Si structure behaves as a voltage dependent capacitor. In the

sensing process, the hydrogen molecules are dissociated into hydrogen atoms

on the Pd outer surface. At low concentration, the hydrogen atoms, most

226
probably as protons surrounded by an excess electron charge, diffuse through

the metal to the insulator interface, where they are deposited onto available sites

as protons. The compensating negative charge will remain behind, within the

conduction band of the metal gate. Because the diffusion through the Pd is very

fast, it is assumed that there is a chemical equilibrium between the hydrogen on

the outer surface of the metal gate and the protons at the insulator interface.

When negative voltage is applied to the gate, the conduction electrons in

the n-type semiconductor are repelled from the semiconductor/insulator

interface, forming a capacitive depletion layer, thus the total capacitance of the

device will be a function of the applied voltage. The presence of the extra

charge from the proton layer generates an additional electric field across the

AlN thus changing the potential of the AlN/Si interface, which in turn will

modulate this capacitance as it decreases the thickness of the depletion layer.

This is the source of the electrical response of the device. Thus, at constant

capacitance the presence of hydrogen in the surrounding gas causes a voltage

shift. However, the Pd/AlN/Si device did not show any shift upon exposure to

NO2, indicating that the hydrogen could be a probe in order to investigate the

interface properties of the devices.

227
7.2.2 Response of Al/AlN/Si to Hydrogen gas

Figure 7.15 shows the variation in capacitance of Al/AlN/Si device in dry

air and in the presence of hydrogen gas. The results shown in Figure 7.15 reveal

that the hydrogen-induced dipole layer is not formed in the metaldielectric

interface for MIS Al-AlN-Si device with a AlN dielectric. These C-V

characteristics are quite anomalous and have not been reported yet. Because no

work function change is observed as the work function change should be

reflected in the flatband voltage shifts in the C-V curves. Therefore, it is

obvious that the interface between the metal and the semiconductor plays a

critical role in the interaction of hydrogen with semiconductor devices.

Although the detailed reaction mechanism of MIS (Al-AlN-Si) device to

hydrogen is unknown at present, the plausible mechanisms are described as

follows. First, the hydrogen-induced changes in the electrical properties may be

related to the number of adsorption sites for hydrogen at the

metal/dielectric/semiconductor interface of the devices [265]. Second, hydrogen

could be contained in the SiO2 and AlN dielectrics during the sputter deposition,

and some of the hydrogen molecules trapped at the metal/dielectric interface

may affect the hydrogen detection sensitivity. Third, the AlN is well known to

have a high density of trap states and hence potentially suffer from charge

trapping instabilities [266].

228
Figure 7.14 Variation of capacitance of Pd/AlN/Si
device with voltage

Figure 7.15 Variation of capacitance of Al/AlN/Si

device with voltage

229
7.2.3 CONCLUSION

Gas sensing properties of Pd/AlN/Si and Al/AlN/Si towards H2 was

compared. Al/AlN/Si device showed no response to hydrogen gas, whereas

Pd/AlN/Si device showed a voltage shift of 0.8 V in capacitance-voltage (C-V)

curve, thereby giving an indication of the concentration of hydrogen in the gas

to which the device is exposed. The presence of donor levels in the bandgap of

the AlN layer with a wide range of energy is responsible for the observed shift

in the CV curve of the Pd/AlN/Si. Furthermore, the Pd/AIN/Si device could not

detect even 1000 ppm NO2, suggesting that the realization of chemical

sensitivity of AIN to NO2 is not possible.

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 SUMMARY AND CONCLUSION

Metal oxide and nitride sensors, got remarkable positions in science and

technology, since they allow producing fast, reliable, low cost and low

maintenance devices. In the present work, field effect gas sensors (MIS

capacitors) based on wide band gap Aluminum nitride (AlN), and resistive gas

sensor made of indium tin oxide (ITO) have been developed for the detection

of oxidizing and reducing gases. Optimization of individual ITO and AlN thin

films with regards to the attainment of desirable levels of crystallinity,

preferred orientation was done by dc and rf magnetron sputtering,

respectively. A comprehensive study of the properties of these films using

various characterization techniques helped to understand the sensor

performance. Optimized thin film gas sensing layers were incorporated to

form gas sensing device. A portable and low cost gas sensor chamber was

fabricated and successfully utilized to monitor the electrical response and gas

sensing performance of the material as function of gas concentration. With the

results achieved from this study, the following conclusions can be made:

ITO thin films deposited by rf sputtering revealed that the structural,

electrical and optical properties of the film greatly depended on

231
 deposition conditions. The change in the resistivity of the film with

annealing is very similar to the corresponding change in its sheet

resistance. The average transmittance was above 85% for the as-

deposited and annealed films. XRD patterns confirm the polycrystalline

nature of the film and the intensity of (4 0 0) diffraction peak improved

after annealing. This suggests that there is minimal structural change in

the ITO films followed by annealing. SEM micrograph of the annealed

film shows a uniform and closely packed distribution of polycrystalline

nanoclusters free of microcracks.

By promoting the devation from the stoichiometry and decreasing the

resistance of the films, the performance of ITO material as gas sensor

was improved. The ITO film senor showed enhanced response at 600 K,

especially, at concentrations lower than 50ppm NO2. The ITO sensor

show a linear response to ethanol gas in the concentration range of 200

to 1400 ppm. Post-deposition annealing of the film at 700 K, ehanced

the response of the ITO senor to ethanol gas. Very low sensitivity is

observed towards Hydrogen gas when compared to NO 2 and ethanol.

The maximum response was found to be only 1.6 at 400 K and 1000 ppm

of H2. The results suggest ITO films to be an excellent material for low

concentration, highly sensititive and selective NO2. The similar shape of

232
 the sensitivity curves observed for ITO sensor towards NO2, H2 and

ethanol, resulted from the competition between slow kinetics at low

temperature and enchanced disorption at high temperature.

AlN films prepared by dc reactive magnetron sputtering on Si (100)

substrate for different deposition time revealed that, films prepared at 8

min favored the formation of highly oriented (002) preferential plane

with enhanced crystal quality, which can provide good piezoelectric

response. The band gap increased with the increase in the deposition time

and the values of refractive index were in the range of 1.1-1.2, for the

samples prepared at 8 min of deposition time. The MIS structures

fabricated using AlN for different deposition time showed a significant

improvement of electrical characteristics with deposition time as we go

from 2 min to 8 min.

The gas sensing properties of Al/AlN/Si device showed no response to

hydrogen gas, whereas Pd/AlN/Si device showed a voltage shift of 0.8 V

in capacitance-voltage (C-V) curve. However, the Pd/AlN/Si devices

could not detect even 1000 ppm NO2, suggesting that the realization of

chemical sensitivity of AlN to NO2 is not possible.

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 Future work in this research will involve the development of an

electronic nose with oxide semiconducting material, which could detect

various gases. The more detailed interaction mechanism of hydrogen

with nitride based semiconductor devcies should be studied.

Invesigations varying the gases, measurement temperature, device

structures and measurement methods may lead to the more specific

elucidation of the interaction mechanism.

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