p-type gas sensing behaviour in high energy ion beam irradiated un-doped SnO2

thin films
1
Sanju Rani, 2Somnath C Roy, 1M C Bhatnagar and 3D Kanjilal
1
Thin Film Laboratory, Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016 India. 2 Materials Research Laboratory, The
Pennsylvania State University, University Park, 16802 USA
3
Inter University Accelerator Centre (IUAC), Aruna Asaf Ali Marg, New Delhi 110067, India
Email: sanjuiitd@gmail.com

Abstract -We report novel p-type behaviour in undoped SnO2 thin films In this paper, we report a novel p-type behaviour in
irradiated with 75 MeV Ni+ ion beam. Gas response of the irradiated the high-energy ion beam irradiated undoped SnO2 thin films.
films with NH3 (reducing) and NO2 (oxidizing) gases shows an increase Gas sensing studies on the irradiated films with ammonia
and decrease in resistance respectively indicating p-type conduction that
also increases with increase in ion fluence. Photoluminescence
(NH3) gas showed an increase in resistance indicating p-type
spectroscopy of the irradiated films shows strong yellow peak behaviour. Photoluminescence (PL) spectroscopy has been
corresponding to interstitial oxygen ions. The observed p-type used to identify acceptor levels associated with the p-type
conductivity is attributed to holes generated by these interstitial oxygen behaviour. In addition, X-ray photoelectron spectroscopy
ions. Presence of interstitial oxygen ions is also supported by x-ray
photoelectron spectroscopy.
(XPS) has been carried out to investigate the surface ionic
species responsible for p-type conductivity.
I. Introduction
II. Experimental details
Undoped SnO2 thin films, which show n-type
100 nm thick SnO2 films were deposited on corning glass
behaviour due to oxygen vacancy generated charge carriers,
substrates by sol-gel dip coating technique. The sol was
are usually modified with different dopants to tailor optical,
prepared by dissolving SnCl45H2O in appropriate quantity of
electrical, and gas sensing properties. The immense
propanol. Layer-by-layer deposition followed by drying was
technological importance keeps SnO2 thin films under active
carried out till the desired thickness was achieved. The as-
focus of the research community and new techniques to
deposited films were finally annealed in air at 600oC for 2
modify the properties and behaviour are being continually
hours to obtain the desired crystalline phase. These SnO2 thin
investigated [1-5].
films were irradiated with 75MeV Ni+ ion beam at the Inter-
Irradiation of materials with high-energy ion beam or
University Accelerator Center, New Delhi, India. The fluence
‘swift heavy ion (SHI) irradiation’ - as it is commonly known,
was varied as 1x1011, 1x1012, and 1x1013 ions/cm2. Gas
is one of such techniques that effectively induce structural and
sensing experiments on the irradiated films were carried out
micro-structural modifications in materials. The high Se
by placing the sensor and heater arrangement inside of an
released by the ion beams in a very short interval of time
indigenously designed chamber equipped with Tylan® mass
produces significant excitation of the lattice, introducing
flow controllers (MFCs) for quantifying flow at the ppm level.
defect levels that cause fundamental changes in the electronic
PL spectroscopy was performed with a Perkin-Elmer LS-55
structure and properties of materials. The usefulness of this
PL spectrometer using a 488 nm laser source. XPS was
technique has been widely investigated in recent times on
performed in a SPECS system operating at a base pressure of
different oxide thin films, such as HfO2, SiO2, CeO2, ZnO, and
4 x 10-7 Pa.
Fe2O3 [6-9]. However, very few studies reported ion beam
induced modifications of undoped SnO2 thin films.
III. Results and discussion
Fig. 1 shows the variation of sensitivity factor ‘s’
350 50

0
Gas inject
Un irradiated 200 Unirradiated with respect to time in response to 1000 ppm ammonia (NH3)
Sensitivity (Rg - R0)/R0(%))

gas at 250oC for SnO2 thin films irradiated at different ion

Sensitivity (Rg - R0)/R0(%))

Gas eject
11 2 -50

1X10 ions/cm 11
10 ions/cm
2
300 12 2
-100
50
1X10 ions/cm -150
12
10 ions/cm
2
100
Sensitivity (Rg - R0)/R0(%))
Sensitivity (Rg - R0)/R0(%))

13 2
1X10 ions/cm 13
10 ions/cm
2

fluence. For comparison, ammonia response of un-irradiated

-200

-250
250 Gas eject
-300
0 Gas inject
0 50 100 150 200 250 300 0 50 100 150 200 250 300

film is shown as inset. If Rg and Ro denote resistance of

Time (Sec) Time (Sec)
0
200

sample in presence of gas and in air respectively, then

Gas inject

150
Gas eject
-50
100 sensitivity factor is defined as
Gas eject
50
-100

0
0 50
Gas inject

100 150 200 250 300 350 0 20 40 60 80 100 120

s = (Rg – Ro)/ Ro (1)
Time (sec) Time (Sec)

A positive value of s in irradiated SnO2 thin films for

Fig1. Response of SnO2 thin films Fig2. Response of SnO2 thin films
with different ion fluences at with different ion fluences at all fluence indicates increase in resistance upon exposure to
250oC temperature with 250oC temperature with 1000 ppm
1000ppm of ammonia gas (NH3) of Nitrogen dioxide gas (NO2)

1-4244-2581-5/08/$20.00 ©2008 IEEE 886 IEEE SENSORS 2008 Conference

 NH3 gas. Furthermore, the maximum value of s, which luminescence in 540-570 nm regions, the intensity of which
represents maximum change in resistance in response to NH3 increases with increasing ion fluence. In comparison, the
spectrum for un-irradiated film appears with a low intensity
530.15
530.85
Unirradiated
11
1x10 ions/cm
2
Un-irradiated
13
1x10 ions/cm
2
Gas Temperature Temperature Temperature
200oC 250oC 300oC
12 2
1x10 ions/cm
13
1x10 ions/cm
2
concentration
PL intensity (a.u.)

Intensity (A.U.)
(Sensitivity %) (Sensitivity %) (Sensitivity %)
NH3 NO2 NH3 NO2 NH3 NO2
500ppm 52 1.66 98 12 284 23
1000ppm 126 5 237 40 516 56
500 550 600 650 700 525 530 535
2000ppm 332 16 649 53 882 162
Wavelength (nm) Binding energy (eV)
Table.1. Sensitivity table for SnO2 thin films irradiated with 1x 1012 ions/cm2
Fig. 3. Photoluminescence (PL) Fig. 4. Oxygen 1s (O1s) XPS exposed to different concentration of gas and at different
spectra of un-irradiated and spectra for un-irradiated and operating temperatures
irradiated SnO2 thin films irradiated (at 1x1013 ions/cm2)
SnO2 thin films
peak centered around 500 nm. In oxide materials, swift heavy
ions create oxygen point defects, namely, oxygen vacancies
gas, increases from 80 to 320 with increase in ion fluence. In and interstitial oxygen ions that are characterized by different
general, gas sensing in oxide materials is explained by oxygen PL emission. Oxygen vacancies show a well-known PL band
adsorption model [10]. According to this model, oxygen ions in the wavelength region close to 500nm, [11-13] that
from ambient atmosphere are chemisorbed on the surface of corresponds to green emission. On the other hand, yellow
the material trapping electrons from the conduction band. emission is a characteristic of interstitial oxygen ions. [14-16]
Exposure to a reducing gas such as NH3 leads to surface In this case, therefore, the yellow emission is attributed to
reactions that result in these trapped charges being released interstitial oxygen ions generated by the oxygen ions knocked
back to the semiconductor. In case of an n-type off from their regular lattice position by high energy Ni+
semiconductor, release of electrons back to the material cause beam. As more and more interstitial oxygen ions are generated
an increase in the number of majority carriers that leads to with increase in ion fluence, the intensity of yellow PL
decrease of resistance upon exposure to a reducing gas. For a emission increases.
p-type material, holes are the majority carriers; hence release Let us now analyze the contribution of interstitial
of electrons from surface reactions into the material causes oxygen ions to p-type behaviour of ion irradiated SnO2 films.
recombination, resulting in a decrease in the majority carriers When oxygen atoms take up interstitial positions they become
and increase of resistance. In our case, the observed increase ionized according to the process [17]
of resistance therefore indicates p-type behaviour of the ion ½ Olattice = Oint- + e+ (2)
irradiated SnO2 thin films. To further confirm the p-type
behaviour, irradiated films were also exposed to an oxidizing Here Olattice is the oxygen at regular lattice position,
gas NO2 and corresponding variation in the sensitivity factor Oint the interstitial oxygen ion, and e+ is the associated hole
is shown in Fig. 2 with the inset showing response of un- (positively charged). As shown in the PL spectra, the surface
irradiated film. In this case, negative value of s for irradiated of ion irradiated un-doped SnO2 thin films are dominated by
films represents decrease of resistance upon exposure to the interstitial oxygen ions, the concentration of which increases
oxidizing gas, confirming p-type behaviour of the irradiated with increasing fluence. This result in a corresponding
SnO2 thin films. increment in hole density that dominates over the electron
In the present case, we found an increase in density at the film surface. This causes the observed p-type
sensitivity with increasing gas concentration (shown in Table behaviour in ion-irradiated undoped SnO2 thin films. Similar
1) indicating oxygen-induced band bending not responsible p-type behaviour originating from interstitial oxygen ions has
for the observed p-type behaviour in SnO2 thin films. In our also been reported recently for TeO2 nanowires. [18] Since the
case, the observed p-type behaviour of undoped SnO2 thin hole concentration increases with ion fluence, the resultant gas
films must therefore be related to acceptor states created sensitivity also increases.
intrinsically by the high-energy ion irradiation. To further confirm the presence of interstitial oxygen
To identify the origin of p-type behaviour, room ions we carried out x-ray photoelectron spectroscopy (XPS) of
temperature PL measurements were performed. Fig. 3 shows oxygen core level (O1s) for un-irradiated and irradiated SnO2
the room temperature PL spectra of un-irradiated and thin films; representative O1s spectra for film irradiated with
irradiated SnO2 thin films. A common feature of the PL 1x1013 ions/cm2 fluence and that for un-irradiated film are
spectra of irradiated films is the broadband yellow shown in Fig.4. All the peaks positions were corrected with

887
respect to C 1s peak position at 284.6 eV. The O1s peak in un-
irradiated film observed at 529 eV corresponds to O-Sn4+ bond
and represents oxygen ion at its regular lattice position [19-
22]. In comparison, the O1s spectra of the film irradiated at
1x1013 ions/cm2 shows peak at 530.9 eV. A shift towards
higher binding energy for oxygen core level position indicates
the presence of surface oxygen either as adsorbed species or
as interstitial ions. In our case, the ion irradiation experiment
was performed in ultra-high vacuum ambience; the possibility
of oxygen adsorption on the surface of irradiated films
therefore does not exist. This confirms the presence of
interstitial oxygen ions on the surface of high-energy ion
irradiated SnO2 thin films.
IV. Conclusions
In summary, gas-sensing characteristics of high-
energy Ni+ ion irradiated un-doped SnO2 thin films shows
novel p-type behaviour that increases with increase in ion
fluence. PL spectroscopy indicates that surface of these
irradiated films are dominated by interstitial oxygen ions
emitting strong yellow luminescence. Origin of the p-type
behaviour is attributed to holes generated by the interstitial
oxygen ions, the density of which increases with increasing
ion fluence. Presence of interstitial oxygen ions is also
supported by XPS studies.
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