tuning of structural, morphological, optical and

10
Tuning of structural, morphological, optical and electrical properties of SnO 2 by indium inclusion GEETA BHATIA 1 , AMAN DEEP ACHARYA 2, *, M M PATIDAR 3 , V K GUPTA 4 , S B SHRIVASTAVA 1 and V GANESAN 3 1 School of Studies in Physics, Vikram University, Ujjain 456010, India 2 Lovely Professional University, Phagwara 144001, India 3 UGC-DAE Consortium for Scientific Research, Indore 452001, India 4 Department of Physics, Govt. Girls P.G. College, Ujjain 456010, India *Author for correspondence ([email protected]) MS received 16 September 2020; accepted 5 February 2021 Abstract. A complete range of indium-doped (In:SnO 2 ) thin films prepared by spray-pyrolysis technique have been studied and characterized by different techniques to get information about structure, surface and electrical properties. The influence of indium filler concentration (i.e., 0–15 wt%) on the properties of SnO 2 has been explored. Structural study reveals that the inclusion of indium after a certain optimum value leads structural distortion which causes the films’ expansion along c-axis direction. The extract of electrical study helps to understand that what should be the optimum value to switch from n- to p-type, which is further confirmed by Hall measurement. A deep analysis of electrical data confirms that the solid solution of indium into SnO 2 should not be completely excluded and its range should not be [ 12 wt% as we got saturation in the electrical behaviour after it. Variable range hopping mechanism has been found to be best fitted for low temperature range and comes out with valuable information that increase in density of states near Fermi level are responsible for decrease in resistivity in case of higher doping and also confirms that 6 wt% is the optimum value to switch from n- to p-type conductivity. Keywords. Indium; SnO 2 ; doping; spray pyrolysis; tuning behaviour. 1. Introduction Tin oxide (SnO 2 ) has been found to be an important transparent conductor for many optoelectronic devices because it has high transparency in the visible part of the spectrum, high reflectivity in IR region and high electrical conductivity along with its wide band gap (3.6–3.9 eV) and thermal stability. The tin oxide films are widely used for various applications, such as in solar cells as transparent electrodes [1], gas sensors [24], diodes [5] and anodes in lithium batteries [6]. Because of oxygen vacancies and interstitial tin atoms (Sn), virgin SnO 2 exhibit n-type con- ductivity [7]. Inclusion of various elements, such as fluorine (F) [8], antimony (Sb) [9] would be useful to modify the properties of the host material. Recently, some authors have professed that p-type SnO 2 has been obtained using new doping elements, such as lithium (Li) [10], aluminium (Al) [11], cobalt (Co) [12], iron (Fe), copper (Cu) [13], platinium (Pt) [14] and tungsten (W) [15]. Chemical vapour deposition [16], sol–gel [17], sputtering [18], pulsed laser deposition [19], spray pyrolysis [20] and electron beam evaporation [21] are the methods which are more often used for depositing films on different substrates. Spray pyrolysis has been emerged as, an excellent, simple, versatile and less expensive method. Along with this, it is a simple method for large-area coating applications, such as window panels, automotive glass and solar cells. In the present study, spray-deposited In:SnO 2 films have been studied for structural, morphological and electrical properties. Also, the effect of varied filler concentration on the properties is the subject of interest and hence, properly investigated. 2. Experimental 2.1 Precursor preparation and deposition parameter In:SnO 2 films with different concentrations of In (i.e., 0, 3, 6, 9, 12 and 15 wt%) were prepared by spray-pyrolysis technique and the films were deposited on the cleaned glass substrates. Desired amount of precursor SnCl 2 2H 2 O was mixed in 5 ml of concentrated hydrochloric acid subject to heating at 90°C for 15 min [22]. The obtained solution was transparent and hence used as precursor. Separately for indium doping, indium trichloride (InCl 3 ) was dissolved in Bull. Mater. Sci. (2021) 44:187 Ó Indian Academy of Sciences https://doi.org/10.1007/s12034-021-02449-8

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Page 1: Tuning of structural, morphological, optical and

Tuning of structural, morphological, optical and electrical propertiesof SnO2 by indium inclusion

GEETA BHATIA1, AMAN DEEP ACHARYA2,*, M M PATIDAR3, V K GUPTA4,S B SHRIVASTAVA1 and V GANESAN3

1 School of Studies in Physics, Vikram University, Ujjain 456010, India2 Lovely Professional University, Phagwara 144001, India3 UGC-DAE Consortium for Scientific Research, Indore 452001, India4 Department of Physics, Govt. Girls P.G. College, Ujjain 456010, India

*Author for correspondence ([email protected])

MS received 16 September 2020; accepted 5 February 2021

Abstract. A complete range of indium-doped (In:SnO2) thin films prepared by spray-pyrolysis technique have been

studied and characterized by different techniques to get information about structure, surface and electrical properties. The

influence of indium filler concentration (i.e., 0–15 wt%) on the properties of SnO2 has been explored. Structural study

reveals that the inclusion of indium after a certain optimum value leads structural distortion which causes the films’

expansion along c-axis direction. The extract of electrical study helps to understand that what should be the optimum

value to switch from n- to p-type, which is further confirmed by Hall measurement. A deep analysis of electrical data

confirms that the solid solution of indium into SnO2 should not be completely excluded and its range should not be

[12 wt% as we got saturation in the electrical behaviour after it. Variable range hopping mechanism has been found to be

best fitted for low temperature range and comes out with valuable information that increase in density of states near Fermi

level are responsible for decrease in resistivity in case of higher doping and also confirms that 6 wt% is the optimum value

to switch from n- to p-type conductivity.

Keywords. Indium; SnO2; doping; spray pyrolysis; tuning behaviour.

1. Introduction

Tin oxide (SnO2) has been found to be an important

transparent conductor for many optoelectronic devices

because it has high transparency in the visible part of the

spectrum, high reflectivity in IR region and high electrical

conductivity along with its wide band gap (3.6–3.9 eV) and

thermal stability. The tin oxide films are widely used for

various applications, such as in solar cells as transparent

electrodes [1], gas sensors [2–4], diodes [5] and anodes in

lithium batteries [6]. Because of oxygen vacancies and

interstitial tin atoms (Sn), virgin SnO2 exhibit n-type con-

ductivity [7]. Inclusion of various elements, such as fluorine

(F) [8], antimony (Sb) [9] would be useful to modify the

properties of the host material. Recently, some authors have

professed that p-type SnO2 has been obtained using new

doping elements, such as lithium (Li) [10], aluminium (Al)

[11], cobalt (Co) [12], iron (Fe), copper (Cu) [13], platinium

(Pt) [14] and tungsten (W) [15].

Chemical vapour deposition [16], sol–gel [17], sputtering

[18], pulsed laser deposition [19], spray pyrolysis [20] and

electron beam evaporation [21] are the methods which are

more often used for depositing films on different substrates.

Spray pyrolysis has been emerged as, an excellent, simple,

versatile and less expensive method. Along with this, it is a

simple method for large-area coating applications, such as

window panels, automotive glass and solar cells.

In the present study, spray-deposited In:SnO2 films have

been studied for structural, morphological and electrical

properties. Also, the effect of varied filler concentration on

the properties is the subject of interest and hence, properly

investigated.

2. Experimental

2.1 Precursor preparation and deposition parameter

In:SnO2 films with different concentrations of In (i.e., 0, 3,

6, 9, 12 and 15 wt%) were prepared by spray-pyrolysis

technique and the films were deposited on the cleaned glass

substrates. Desired amount of precursor SnCl2�2H2O was

mixed in 5 ml of concentrated hydrochloric acid subject to

heating at 90�C for 15 min [22]. The obtained solution was

transparent and hence used as precursor. Separately for

indium doping, indium trichloride (InCl3) was dissolved in

Bull. Mater. Sci. (2021) 44:187 � Indian Academy of Scienceshttps://doi.org/10.1007/s12034-021-02449-8Sadhana(0123456789().,-volV)FT3](0123456789().,-volV)

Page 2: Tuning of structural, morphological, optical and

40 ml of methanol and slowly added to the earlier solution

followed by stirring for 15 min. The precursor solution was

sprayed onto the cleaned glass substrate at 400�C with a

maintained flow rate of 6 ml min-1. After deposition, the

sample was kept at the same temperature for 30 min.

2.2 Films characterization

Structural properties of prepared thin films were carried out

by using grazing incidence X-ray diffraction (GIXRD) D8

Discover system (Bruker). Thin film morphologies were

investigated by using atomic force microscopy (Digital

Instrument Nanoscope E with Si3N4 100 lm cantilever,

0.58 N m-1 force constant) in contact mode at room tem-

perature and by using field emission scanning electron

microscopy (FESEM, FEI Nova Nano SEM 450) FESEM

instrument operated at 18 kV. Compositional analysis of the

films performed by using ‘Bruker’ made X-Flash 6130 EDS

attachment and ‘Esprit’ software. Resistivity measurements

were carried out by conventional four-probe method down

to 2 K and up to 14 T using quantum design physical

property measurement system (PPMS). The Hall effect

measurement is done with the help of Ecopia Hall effect

system (Model No. HMS-3000). The magnetic field during

the measurement was 0.57 Tesla.

3. Results and discussion

3.1 X-ray analysis

X-ray diffraction spectra (figure 1) of the prepared films

with varied concentrations (0–15 wt%) indicate the poly-

crystalline nature having tetragonal structure ((JCPDS card

no. 88-0287) with preferred orientation along the (101) and

(211) planes. No impurity phase corresponding to indium

was detected in the spectra. Poor crystallinity has been

noticed for filler concentrations [6 wt%. It is also noticed

that with increase in the filler amount ([6 wt%), the

intensity of the peak corresponding to (101) plane, dimin-

ishes slightly, whereas a sufficient decrease in the intensity

has been noticed for peak corresponding to (211) plane as

confirmed from FWHM value (table 1). The observed

changes might be because of mismatch in the ionic radii

which lead to the segregation of dopant at grain boundaries

[23]. Moreover, the presence of other peaks, such as (110),

(200), (310), (301), (202), (321), is also noticed for higher

indium concentration ([6 wt%). Assistance of heteroge-

neous nucleation in the presence of indium ion in SnO2

structure could be the possible reason behind the preferred

orientations along (101) plane for higher doping. Decrease

in internal stress and surface energy could also be the

possible reason behind the growth along (101) plane for low

indium concentrations (i.e., \6 wt%) [24]. This suggests

that for low filler concentrations substitution of indium at

the Sn sites helps in the crystalline growth by decreasing the

stress, whereas the higher concentration strongly deteriorate

the crystallinity which might be due to increased strain

caused by ionic radii difference between filler and host

leads the segregation of indium in grain boundaries. Indium

doping further affects the lattice parameter and unit cell

volume.

For tetragonal system, the lattice constants a and c are

determined as follows [25]:

1

d2hkl

¼ h2 þ k2ð Þa2

þ l2

c2: ð1Þ

A slight change in the lattice parameters has been

observed with increase in indium doping concentrations

(figure 2a). However, c/a ratio was found to be almost

constant (table 1). Further, a close look of the XRD spectra

reveals a slight shift in the peaks’ positions towards lower

angle side. Change in the atomic environment because of

indium doping could be the possible reason behind these

crystallographic changes in the structure. This is also

attributed to the substitution of smaller ionic radii Sn4?

atom by larger ionic radii In3? atom. Such results of lattice

distortion have been reported by many authors [26,27]. For

further insight, unit cell volume and micro strain have been

calculated (table 1 and figure 2b). Variation in the values of

a and c results in the decrement of unit cell volume for In/Sn

\9 wt% which led to compression of the lattice. However,

Figure 1. GIXRD pattern of pure and indium-doped thin film for

different indium concentrations.

187 Page 2 of 10 Bull. Mater. Sci. (2021) 44:187

Page 3: Tuning of structural, morphological, optical and

for In concentrations [6 wt%, further increase in unit cell

volume has been observed, might be due to limited solid

solubility of indium in SnO2. Added to this, the increase in

calculated micro strain (using Williamson Hall equation

(equation 2)) with indium concentrations, reveals the lattice

distortion due to mismatch in the dopant radius and host

material, causes the films expansion along c-axis direction

[28].

e ¼ kD sin h

� btan h

: ð2Þ

Crystallite size calculated by Debye–Scherrer formula

(equation 3) is shown in figure 2b, reveals the decreasing

trend with increase in filler concentration [29,30].

D ¼ 0:9kb cos h

: ð3Þ

3.2 Morphological properties

Non-uniform and pinholes free morphology has been

noticed for pure SnO2 films (figure 3a). In 3D view, pyra-

mid type of islands along with boundaries have been

appeared with thin end pointing towards the surface and

thick end within the film surface. As it is evident from the

obtained grain size which sweeps in the range of 1.42–0.29

lm (table 2) that indium doping strongly affects the mor-

phology. For 3 wt% of indium, the pyramid type structure

of the crystallite turns into distinct grains and grain

boundaries having different sizes. Further increase in dop-

ing concentrations, results decrease in grain size drastically.

This result may be particularly useful for gas sensing, as the

sensitivity in gas detection improves with small grain size.

The obtained results are in good agreement with XRD

results and responsible for decrease in surface roughness of

the prepared films. However, minor inconsistency in the

grain size has been observed might be due to the informa-

tion about the surface obtained from AFM, whereas XRD

provides the information about the volume [23]. Among the

Table 1. Structural parameters of prepared In-doped SnO2 thin films for different In concentrations.

Sample 2h (deg.) hkl FWHM (deg.) d space (A)

Lattice constants

c/a Unit cell volume Va (A) c (A)

0 wt% 33.89 101 0.1744 2.6443 4.7377 3.1875 0.6728 71.54

51.79 211 0.2556 1.7646

3 wt% 33.93 101 0.2496 2.6412 4.7289 3.1968 0.6760 71.49

51.75 211 0.2901 1.7659

6 wt% 33.92 101 0.2902 2.6420 4.7116 3.2123 0.6823 71.36

51.76 211 0.4560 1.7656

9 wt% 33.88 101 0.2964 2.6450 4.729 3.2045 0.6777 71.67

51.70 211 0.5439 1.7675

12 wt% 33.86 101 0.3260 2.6465 4.729 3.2045 0.6776 71.66

51.71 211 0.7942 1.7672

15 wt% 33.84 101 0.4660 2.6480 4.7377 3.1918 0.6737 71.64

51.78 211 1.0025 1.7649

Figure 2. Variations of (a) lattice constants (a, c) and (b) crys-

tallite size and microstrain with indium concentration.

Bull. Mater. Sci. (2021) 44:187 Page 3 of 10 187

Page 4: Tuning of structural, morphological, optical and

Figure 3. AFM michrographs of (a) pure SnO2 and (b) In:SnO2

thin films.

Table 2. Grain size and roughness for In-doped SnO2 thin

films.

In doping

(x)

Grain size

(lm)

Roughness

(nm)

0.0 1.421 93.74

0.03 0.745 71.35

0.06 0.292 8.60

0.09 0.418 37.58

0.12 0.456 47.22

0.15 0.289 14.25

Figure 4. FESEM images of pure SnO2 at magnification values

of (a) 10,0009, (b) 40,0009, (c) 3% In:SnO2 and (d) 15% In:SnO2

thin films.

187 Page 4 of 10 Bull. Mater. Sci. (2021) 44:187

Page 5: Tuning of structural, morphological, optical and

entire doping percentages, 6 wt% indium-doped SnO2 film

stands with good surface quality with lower value of

roughness (table 2).

To have a further insight, the SEM analysis has been

performed (figure 4). A magnified close look of pure SnO2

morphology makes an impression that the grain growth

would be more likely in rod shape. But regardless, the

growth has appeared in the form of grains which found to be

more coagulated due to the coalescence of neighbouring

grains for higher doping. A valuable information obtained

from this, is that behind the controlled growth of the films,

interstitial Sn has important contribution. As a result, with

increase in indium concentration, interstitial Sn concentra-

tion has been reduced and due to decrease in diffusivity,

grain growth was inhibited. Another possible explanation

could be the emergence of retarding force due to indium

substitution which hindered the grain growth by resisting

the driving force [31].

3.3 Elemental analysis

Elemental analysis has been performed by energy-disper-

sive X-ray spectrometer (EDX). The obtained results as

shown in figure 5, clearly reflect the presence of Sn, O and

In which confirms the presence of dopant along with host.

However, the presence of C shows the lack of completeness

of pyrolytic reactions [32].

3.4 Electrical measurements

The electrical behaviour of the indium-doped SnO2 has

been studied in detail by using four probe method (figure 6a,

b). The temperature vs. resistivity graph for different indium

concentrations reveals that desirable amount of indium

content is strong enough to tune the electrical properties of

SnO2 effectively. The data is giving us a complete range of

doping concentrations starting from low to high to get the

electrical behaviour in response to the desired application.

In general, SnO2 is known to have n-type conductivity due

to oxygen vacancies and Sn interstitials. Two possible

valence states Sn2? and Sn4? could be the possible reason

behind the dramatic electrical behaviour of Sn. As a whole,

the room temperature resistivity curve shows the semicon-

ducting behaviour of In:SnO2 films. However, the highest

resistivity value is quite visible for 6 wt% of indium con-

tent. Further increase in the indium content favours the

semiconducting nature. The overlapping situation in case of

12 and 15 wt% of indium content clearly reflects the opti-

mum scale of indium doping. This combined n- and p-type

effect is attributed to the position occupied by the dopant

ions in the SnO2 matrix. The increase in the resistivity i.e.,

low n-type conductivity up to 6 wt% of indium might be

due to the failure of the low concentration of indium ion in

occupying the proper lattice position, hence, acts like

acceptors or potential traps for the free electrons and

increases the disorder at interstitial position [33]. Another

possible reason behind low n-type conductivity could be the

substitution of Sn4? by In3? leads to create an electron-

deficient environment. For higher doping concentrations i.e.,

[6 wt%, the decrease in resistivity might be attributed to

occupying oxygen sites by indium in SnO2 lattice and gives

rise to additional donor sites which result in increasing the

carrier concentrations [34,35]. Further, if we move from 12

to 15 wt%, a slight increase in the resistivity has been

observed, which could be understood that due to the

decrease in grain size (table 2), gives rise to small grain

boundaries which act as charge carriers traps and hence,

disturbs the movement of the carriers. However, by looking

into the plot of temperature vs. resistance (figure 6b) for

different indium concentrations, this disturbance of grain

boundaries could be abandoned as we obtained an over-

lapping situation for resistance in case of 12 and 15 wt% of

indium doping. Activation energy is calculated for better

understanding of the conductivity mechanism by using

Arrhenius formula (figure 7a) [36] and found to be in good

agreement with the obtained electrical behaviour of the

films.

q ¼ q0 expEa

KbT

� �; ð4Þ

where q is the resistivity at temperature T, q0 the constant,

Ea the activation energy and Kb is the Boltzmann constant.

Activation energy is found to vary from 2.9 to 52 meV. As

it is well known that activation energy is required to hop the

charges from one site to the other. Lowest activation energy

has been observed for higher dopant concentration. Twelve

wt% indium doping suggests that less energy is required to

transfer the carrier from one grain to the other, which is in

agreement with observed decrease in grain size (table 2).

But the linear fit of the graph reflects that the data is not fit

linearly for entire temperature range. From the graph, it is

found that the data shows linear fit for temperature range

from 200 to 333 K. To have a further insight, we have

applied variable range hopping (VRH) theory suggested by

Ambegaokar et al [37] to acquire the low temperature

behaviour of resistivity and is shown in figure 7b. The VRH

mechanism is governed by Singh and Ramachandra Rao

[38].

qðTÞ ¼ q0 expT0

T

� �1=4

; ð5Þ

where q0 and T0 denote material parameters which do not

depend on temperature. T0 is given by:

T0 ¼ 16a3

kBN EFð Þ½ � ; ð6Þ

where N(EF) is the density of localized electron states at

Fermi level, kB the Boltzmann’s constant and a the inverse

localization length of the localized state. The curve plotted

Bull. Mater. Sci. (2021) 44:187 Page 5 of 10 187

Page 6: Tuning of structural, morphological, optical and

for log(q/q300) vs. (1/T)1/4 shown in figure 7b, gives a

straight line. The value of T0 has been obtained from the

graph for pure and In-doped SnO2 films (table 3). It has

been found that pure SnO2 film follows the VRH theory in

lower temperature range from 13 to 30 K, however, for

other indium-doped SnO2 thin film, the VRH mechanism

gives a good fit at lower temperature range (from 13 to 123

K). The fitting parameter T0 varies with In concentration. It

Figure 5. Energy dispersive X-ray analysis spectra of (a) pure SnO2 and (b) 15% In:SnO2 thin films.

187 Page 6 of 10 Bull. Mater. Sci. (2021) 44:187

Page 7: Tuning of structural, morphological, optical and

shows highest value of T0 for 6 wt% and further, decreases

for higher Indium concentrations (up to 12%). The highest

value of T0 for 6 wt% In-doped SnO2 film, results less

density of state at Fermi level or less carrier concentration

compared to the higher concentrations (i.e., for 9 and 12

wt%). As a whole, overall T0 found to decrease with

increase in doping percentage (table 3), that means the

density of states increases near Fermi level. If increase in

the density of states is considered as filling of energy levels

between conduction band and valence band or increase in

the carrier concentrations, then the results are falling in line.

This suggests that the electronic band gap is getting reduced

and which is in agreement with our electrical properties

where we observed a decreasing trend in resistivity data

with increase in doping concentrations. Further, the highest

value of T0 has been observed for 6 wt% of indium reflects

less density of states leads to carrier deficiency near the

Fermi level and hence, high resistivity has been observed

for the same. This suggests that the VRH mechanism

successfully best fitted for the low temperature range and

corroborating with the results obtained from other

characterizations.

Further, Hall measurement conducted to confirm the type

of conductivity (table 4, figure 8). The obtained value of

carrier concentration clearly reflects that the type of con-

ductivity strongly depends on the In/Sn ratio, which is in

good agreement with our electrical studies.

3.5 Optical studies

The optical transmittance spectra as a function of wave-

length ranging from 300 to 1200 nm of the pure and

In:SnO2 thin films are shown in figure 9. It is found that

pure SnO2 film has very low transmittance in visible and

reach up to 53.3% in near IR region. The reason for very

low transmittance of pure SnO2 film is the thickness of the

film (1.5 lm). In thicker film, when light passes through the

film, it will go through multiple scattering processes

throughout the region of the film which results in more

absorption. These results are in accordance with the findings

Figure 6. (a, b) Temperature-dependent behaviour of resistance

for In:SnO2 thin films.

Figure 7. (a) Variation of ln(q/q300) with 1000/T and (b) vari-

ation of ln(q/q300) with respect to (1/T)1/4 for different concentra-

tions of In:SnO2 thin films.

Bull. Mater. Sci. (2021) 44:187 Page 7 of 10 187

Page 8: Tuning of structural, morphological, optical and

of other authors [39]. Although in In:SnO2 films, small

grain size and smooth surface are observed and produce less

scattering effect, hence, the films have a larger optical

transmittance than those obtained for pure SnO2 films.

Transmittance increases on further indium doping up to 6

wt% and then show fluctuating behaviour for higher

wavelength. Maximum transmittance found for 15 (64%)

and 6 wt% (60%) of In:SnO2 in visible region. The high

average value of transmittance in the visible region is

symptomatic of fairly smooth surface and relatively good

homogeneous films were formed possessing nanometre-

sized small grains. The slight decrease in transmittance at

higher doping concentrations (for 9 and 12 wt%) in visible

region may be due to the scattering of photons by crystal

defects created by doping. This is in agreement with the

AFM data, where roughness of the films found to be

increased again. Films doped with 9–15 wt% indium shows

interference effect. This is a direct evidence of homoge-

neous film with uniform thickness [40].

The variation of the optical absorption coefficient a with

photon energy hm was obtained using the absorbance data

for various films. The absorbance coefficient (a) may be

written as a function of incident photon energy (hm) [41]:

a ¼ A hm� Eg

� �� �=hm; ð7Þ

where A is a constant which is different for different tran-

sitions indicated by different values of n, and Eg the cor-

responding band gap. For direct transitions, n = 1/2 or n =

3/2, while for indirect ones, n = 2 or 3, depending on

whether they are allowed or forbidden, respectively [4].

Many groups have used the above formula to calculate the

band gap of SnO2 films and reported that SnO2 is a direct

band gap material [42–44]. The band gap can be deduced

from a plot of (ahm)2 vs. photon energy (hm). Better linearity

of these plots suggests that the films have direct transition.

The extrapolation of the linear portion of the (ahm)2 vs. hm

Table 3. Resistivity, activation energy and T0 values for In:SnO2 thin films.

In concentration (mol%)

Resistivity (X-m) at

temperature 300 K

Activation energy (meV) fitted for

high temperature region (180–300 K) T0 (K)

SnO2 5.9 9 10-5 2.90 0.24

SnO2–In6% 2.20 52.39 29.41

SnO2–In9% 0.117 51.27 5.22

SnO2–In12% 0.0064 6.50 1.07

SnO2–In15% 0.01496 18.45 5.24

Table 4. Obtained data for carrier concentrations and mobility

for different dopant concentrations.

Doping

concentration (wt%)

Carrier concentration,

Nb (cm-3)

Mobility, u(cm2 V-1 s-1)

0 -7.344 9 1019 18.2

6 ?6.184 9 1016 36.97

9 -2.411 9 1019 0.08

12 -1.212 9 1019 0.1256

15 -2.165 9 1019 0.859

Figure 8. Plot of carrier concentrations and mobility as a

function of different indium concentrations.

Figure 9. Optical transmittance of pure and indium-doped SnO2

thin films as a function of wavelength.

187 Page 8 of 10 Bull. Mater. Sci. (2021) 44:187

Page 9: Tuning of structural, morphological, optical and

plot to a = 0 will give the band gap value of the films [45].

Figure 10 shows the (ahm)2 vs. photon energy (hm) plot for

pure and indium (In)-doped SnO2 films. The linear fits

obtained for these plots are also depicted in figure 10.

Obtained band gap (Eg) values for In:SnO2 thin films with

In/Sn concentrations of 0.0, 0.03, 0.06, 0.09, 0.12, 0.15 wt%

are 3.64, 3.60, 3.59, 3.58, 3.55, 3.60 eV, respectively. It is

observed that band gap shows continuous decrement trend.

4. Conclusions

To confirm the optimized composition for full range of

indium-doped SnO2 thin films was developed by spray-

pyrolysis technique on glass substrates. It is observed that

high concentration of filler causes distortion in the structure

and grain growth was inhibited. Increase in the unit cell

volume for higher concentration, reveals limited solid sol-

ubility of indium in SnO2 beyond a certain limit. Surface

morphology of the prepared films reveals that higher doping

results in coalescence of the neighbouring grain leads to

hindered rod-shape growth. Valuable information obtained

from this, is that behind the controlled growth of the films,

interstitial Sn has important contribution. Among the entire

doping percentages, 6 wt% indium-doped SnO2 film stand

with good surface quality with lower value of roughness. It

has been observed that electrical properties can be effec-

tively tuned by desirable amount of indium content. Six

wt% of indium doping could be considered as the switching

amount from n- to p-type conductivity. Hall measurement

confirms that desired amount of indium concentration was

the strong parameter to tune type of conductivity. As far as

the matter of semiconducting behaviour of the prepared

samples concerned, then optimum limit of the filler has

been found to be 12 wt% beyond which we recorded

overlapped resistance value. VRH mechanism confirms that

decrease in density of states is responsible for high

resistivity value (especially 6 wt%) for low filler concen-

tration, whereas for higher concentration, resistivity is

found to decrease. Optical study reveals that doped film has

more transmittance as compared to the pure film. The cal-

culated band gap found to be decreased with increase in

filler concentrations. In summary, the impact of indium

doping especially on the electrical bahaviour encourages us

to develop the semiconductor material with tunable elec-

trical properties which are useful for optoelectronic devices

especially as opto-isolator, electronic or nano-electronic

device technology.

Acknowledgements

The authors from Ujjain would like to thank the Director

and Center Director of UGC-DAE CSR, Indore, for their

cooperation to avail the experimental facilities. Inter

University accelerator centre (IUAC), New Delhi, is

gratefully acknowledged for allowing them to carry out

Hall measurements.

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