Structural, optical and electrical transport properties of Sn doped In2O3

doi:10.1016/j.solidstatesciences.2020.106436

Solid State Sciences

Volume 109, November 2020, 106436

https://doi.org/10.1016/j.solidstatesciences.2020.106436 Get rights and content

Highlights

•
Solid state reaction method was used for the synthesis of Sn doped indium oxide nanocrystalline samples.
•
Transport measurements showed the n-type conductivity with low electrical resistivity for optimized sample (x = 0.1).
•
Insulator to metal transition was observed in each sample.

Abstract

Present study focuses on the structural, morphological, optical and electrical transport properties of Sn substituted In₂O₃ (In_2-x Sn_xO₃; 0.0 $\leq$ x $\leq$ 0.25) synthesized by solid state reaction method. X-ray diffraction patterns and selected area electron diffraction from high resolution transmission electron microscopy substantiated the pure cubic bixbyite structure with high crystallinity. Raman analysis confirmed the cubic like phonon modes in each sample and their noticeable phase was revealed by the presence of tin doping. The band gap widening of all nanocrystalline samples were well explained by Burstein-Moss model, due to the filling of the strongly dispersing conduction band by doped electrons and the decrease in oxygen vacancies were confirmed by deconvoluted emission spectra. Hall measurements showed the n-type conductivity with low electrical resistivity (1.3011 $\times$ 10⁻⁴ $Ω$ -cm) along with high carrier concentration (7.523 $\times$ 10²⁰ cm⁻³), mobility (63.85 cm²/V-s) and electron mean free path (11.183 nm) for x = 0.1, optimizing it as a suitable candidate for optoelectronic applications.

Graphical abstract

Introduction

Indium oxide (In₂O₃), also well known as transparent semiconducting oxide (TSO) has been widely studied as semiconductor material for many years and most of the scientific endeavours have been pointed towards its widespread use in optoelectronic applications [1, 2]. It has excellent electrical and optical properties since it is transparent ( $~$ 85-90 %) in the visible region due to its wide band gap (E_g = 3.5-4.0 eV) at room temperature (RT) along with very low electrical resistivity (ρ $~$ 10^-4 $Ω$ -cm) [3, 4].

Tin doped indium oxide (ITO) is the most prominent among the transparent conducting oxide (TCO) and is an industrial standard material. Among many TCO material ITO only, is an advanced semiconducting material due to its benchmark electrical conductivity and high optical transparency with potential optoelectronic applications like touch screens, touch panel contacts, electro-chromic displays, electrodes for LCD, gas sensor and anti fogging aircraft windows [5, 6, 7, 8]. Different forms of ITO powder with low dimension and large surface area such as nanocrystalline materials [5], nanoparticles [9], nanorods [6] and nanowires [10] have been good technological interest for electronic devices whereas very few researchers had published their research on the bulk and nanocrystalline powder. However, stable cubic bixbyite phase of ITO nanocrystalline material is only attributed to high electrical conductivity. Again, the electrical behavior of ITO nanocrystalline material especially at low temperatures and amazingly the insulator to metal transitions still makes a scope for further researchers to study and know the low temperature behavior of these materials [11, 12].

It is noticed from the above context that the most of the researchers extensively focused on thin films and different nanostructures of Sn doped In₂O₃ but very few articles have been reported on the nanocrystalline powder and bulk to use in optoelectronic applications. In this perspective, our motivation in accomplishing this study was to synthesize In_2-xSn_xO₃ (0.0 $\leq$ x $\leq$ 0.25) nanocrystalline material using simple solid state reaction method with multiple calcination and sintering process at high temperature. Henceforth, the structural, morphological, optical and electrical transport properties of this system are well investigated. The insulator to metal transition are determined from temperature dependent four probe resistivity measurement.

Section snippets

Experiments

Nanocrystalline powders for the compositions In_2-xSn_xO₃ (x = 0.0, 0.05, 0.1, 0.15, 0.2, and 0.25) were successfully prepared by solid state reaction method. In₂O₃ and SnO₂ (Sigma-Aldrich, 99.999% pure) powders were mixed in required stoichiometry and grounded for 6 h with acetone in mortar and pestle, then calcined at 900^oC for 11 h. After calcination, the samples were regrinded for 6 h for proper mixing and again calcined at 900^oC for 8 h. The resultant samples were again grinded for 2 h to

Structural and Morphological properties

The Rietveld fitted XRD patterns of In_2-xSn_xO₃ (x = 0.0-0.25) powder samples are well represented in Fig. 1. It is observed that the crystal structure of all synthesized samples fits in cubic bixbyite geometry of pure In₂O₃ with I a -3 (206) space group and also coordinated with card number 76-0152 (ICDD-JCPDS), in which every unit cell contains eight formula units of In₂O₃. The bixbyite structure of In₂O₃ contains 80 atoms in a conventional cell and 40 atoms in a primitive unit cell. In₂O₃ has

Conclusion

In summary, Sn substitution in In_2-xSn_xO₃ (x = 0.0-0.25) nanocrystalline samples cause systematic structural changes in a and V along with bond lengths of In0-O2/Sn0-O2 & In1-O2/Sn1-O2. The crystallite sizes of all samples, calculated by using Debye-Scherrer formula are comparable with the results obtained from Williamson-Hall method, also support the results observed from TEM whereas the particle sizes are found to be 81.72 nm and 79.17 nm for x = 0.1 and 0.2 respectively. Rietveld refined XRD

Credit author statement

Afroz Khan: Writing - original draft, Data curation, Investigation, Formal analysis. F. Rahman: Supervision. Razia Nongjai: writing - review & editing. K. Asokan: Resources.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgment

The authors thank to IUAC, New Delhi for providing the financial support with research project (Project Code: UFR-61305). AK acknowledges Ram Charan Meena and Ambuj Mishra, IUAC, New Delhi for their help during transport and TEM/HRTEM/SAED measurements, respectively. AK wants special thank to Saif A. Khan, IUAC, New Delhi for providing SEM and EDX facilities. V. Sathe from UGC-DAE, CSR, Indore are also thanked for arranging the Raman facility.

References (53)

H.-R. Xu et al.
Synthesis of tin-doped indium oxide nanoparticles by an ion-exchange and hydrothermal process
Mater. Lett.
(2006)
C.-H. Han et al.
Synthesis of indium tin oxide (ito) and fluorine-doped tin oxide (fto) nano-powder by sol–gel combustion hybrid method
Mater. Lett.
(2007)
J. Hu et al.
A room temperature indium tin oxide/quartz crystal microbalance gas sensor for nitric oxide
Sens. Actuators, B
(2003)
M. Nisha et al.
Effect of substrate temperature on the growth of ito thin films
Appl. Surf. Sci.
(2005)
M. Alam et al.
Investigation of annealing effects on sol–gel deposited indium tin oxide thin films in different atmospheres
Thin Solid Films
(2002)
Y. Huo et al.
All-solid-state artificial z-scheme porous g-c3n4/sn2s3-deta heterostructure photocatalyst with enhanced performance in photocatalytic co2 reduction
Appl. Catal., B
(2019)
Z. Wang et al.
Construction of z-scheme ag3po4/bi2wo6 composite with excellent visible-light photodegradation activity for removal of organic contaminants
Chin. J. Catal.
(2017)
Y.S. Jung et al.
Development of indium tin oxide film texture during dc magnetron sputtering deposition
J. Cryst. Growth
(2003)
N.S. Krishna et al.
Structural, optical, and magnetic properties of fe doped in2o3 powders
Mater. Res. Bull.
(2015)
A. Khan et al.
Investigation of transport phenomenon and magnetic behavior of fe doped in2o3
Phys. B Condens. Matter
(2020)

G. Liu

Synthesis, characterization of in2o3 nanocrystals and their photoluminescence property

Int. J. Electrochem. Sci

(2011)

W.B. White et al.

Vibrational spectra of oxides with the c-type rare earth oxide structure

Spectrochim. Acta Mol. Spectros

(1972)

W.B. White et al.

Vibrational spectra of oxides with the c-type rare earth oxide structure

Spectrochim. Acta Mol. Spectros

(1972)

T. Konry et al.

Physico-chemical studies of indium tin oxide-coated fiber optic biosensors

Thin Solid Films

(2005)

M. Batzill et al.

The surface and materials science of tin oxide

Prog. Surf. Sci.

(2005)

R. Ferro et al.

Chemical composition and electrical conduction mechanism for cdo: F thin films deposited by spray pyrolysis

Mater. Sci. Eng., B

(2001)

L. Liu et al.

A novel step-scheme bivo4/ag3vo4 photocatalyst for enhanced photocatalytic degradation activity under visible light irradiation

Chin. J. Catal.

(2021)

T. Hu et al.

Noble-metal-free ni2p modified step-scheme snnb2o6/cds-diethylenetriamine for photocatalytic hydrogen production under broadband light irradiation

Appl. Catal.

(2020)

H. Cao et al.

Indium vacancy induced d0 ferromagnetism in li-doped in2o3 nanoparticles

J. Magn. Magn Mater.

(2018)

Y. Ohhata et al.

Optical properties of rf reactive sputtered tin-doped in2o3 films

Thin Solid Films

(1979)

B. Thangaraju

Structural and electrical studies on highly conducting spray deposited fluorine and antimony doped sno2 thin films from sncl2 precursor

Thin Solid Films

(2002)

A. Yildiz et al.

Anomalous temperature dependence of the electrical resistivity in in0. 17ga0. 83n

Solid State Commun.

(2009)

P. Gutruf et al.

Transparent functional oxide stretchable electronics: micro-tectonics enabled high strain electrodes

NPG Asia Mater.

(2013)

A. Hakimi et al.

Origin of magnetism in cobalt-doped indium tin oxide thin films

Phys. Rev. B

(2010)

C. O'Dwyer et al.

Bottom-up growth of fully transparent contact layers of indium tin oxide nanowires for light-emitting devices

Nat. Nanotechnol.

(2009)

J. Stankiewicz et al.

Magnetic behavior of sputtered co-doped indium-tin oxide films

Phys. Rev. B

(2007)

Cited by (22)

Engineering the heterojunction between TiO<inf>2</inf> and In<inf>2</inf>O<inf>3</inf> for improving the solar-driven hydrogen production
2024, International Journal of Hydrogen Energy
Nanostructured In₂O₃ was grown on TiO₂ NPs by thermal treatment of the solids mixture of TiO₂ with the parent In(OH)_3. The effect of calcination temperature in the range between 400 °C and 700 °C was investigated and peculiar changes both in the structure and in the catalytic activity of the TiO₂/In₂O₃ heterostructure were revealed. It was found out that T = 600 °C is the best operating temperature for hydrogen production and in combination with 3.5 wt% In₂O₃ the H₂ production from water reached the value of 3.5 mmol/h^.g irradiating in the UV–Vis region. Once 5.0 wt% Cu₂O nanoparticles were loaded on TiO₂/In₂O₃, the photocatalytic activity boosted to 9.6 mmol/h^.g of H₂, overcoming the hydrogen production of pristine TiO₂ by a factor of 48. This result can be attributed to the formation of a highly efficient heterojunction that assures a synergistic cooperation among the three semiconductors yielding an improved charge separation and faster charge transport, as evidenced by Mott-Schottky, PL and EIS measures.
Magnetically separable and visible light-driven photocatalytic activity of graphene oxide based α-Fe<inf>2</inf>O<inf>3</inf> nanocomposite
2024, Materials Chemistry and Physics
This work investigates the impact of graphene oxide (GO) on the structural, morphological, optical, and photocatalytic investigations of Fe₂O₃, an excellent photocatalyst for industrial wastewater treatment. Using the straightforward and inexpensive sol-gel auto-combustion, hummer's method and sonication method, Fe₂O₃ nanoparticle (NPs), GO nanosheet, and GO-based Fe₂O₃ (GO/Fe₂O₃) nanocomposite have been synthesized, respectively. The XRD patterns, Raman spectra, and FTIR spectroscopy were used for the structural analysis, which verifies the single phase hexagonal geometry of Fe₂O₃ NPs. The average size of the crystallites is seen to have reduced from 50 nm to 44 nm for Fe₂O₃ and GO/Fe₂O₃. The SEM along with EDS were applied to investigate the surface morphology and confirm the existence of the elements Fe and O in pure Fe₂O_3, and C, Fe and O in GO/Fe₂O₃. From UV–vis absorbance spectra, the decrease in optical band gap (2.5 eV–1.9 eV) caused by GO incorporation has been inferred, as clearly displayed in the Tauc plots. X-ray photoelectron spectroscopy (XPS) confirms the presence of Fe²⁺/Fe⁺³ ionic states and large oxygen vacancies in the GO/Fe₂O₃ nanocomposite. The photocatalytic properties of both materials for the toxic MB (methylene blue) dye photodegradation in an aqueous solution was evaluated while being exposed to sunlight. It makes an excellent choice for wastewater treatment due to the high photocatalytic activity of magnetically separable GO/Fe₂O₃ nanocomposite for decomposing the MB dye.
Structural, morphological, optical and UV-light driven enhanced photocatalytic properties of Fe-doped NiO nanoparticles
2023, Materials Chemistry and Physics
This work comprehensively investigates the effects of iron (Fe) doping on structural, morphological, optical, and photocatalytic properties of nickel oxide (NiO) nanoparticles. The Ni $_{1 - x}$ Fe $_{x}$ O (0.0 $\leq$ x $\leq$ 0.1) nanoparticles (NPs) have been prepared by using simple and low cost sol–gel auto-combustion method. The Rietveld refined x-ray diffraction patterns, FT-IR spectra, high-resolution transmission electron microscopy (HRTEM) images and Raman spectroscopy were employed for structural investigations, which confirm the single cubic phase geometry of NiO NPs. The average crystallite size of each sample is found to be decreased from 40 nm to 29 nm for x $=$ 0.0 to x $=$ 0.1. Surface morphology was examined using scanning electron microscopy (SEM), and the presence of Ni, Fe, and O was confirmed using energy dispersive x-ray spectroscopy (EDS). From the UV–Vis absorption spectra, we may deduce that the optical band gap has increased slightly due to Fe doping. Tauc plot analysis reveals that band gap widens as a result of doping. Photocatalytic properties of each sample were evaluated under the ultra-violet light irradiation for the photodegradation of toxic methylene blue (MB) dye in an aqueous medium. The high photocatalytic activity of x $=$ 0.1 sample for MB dye degradation makes it a promising wastewater treatment candidate.
Enhanced conductivity of infrared transparent Bi<inf>2</inf>Se<inf>3</inf> thin films as anti-interference coatings for infrared detectors
2023, Optical Materials
Infrared transparent conductive coatings are extensively utilized in both military and civilian infrared detectors due to their superior infrared transmission and electromagnetic shielding properties. It is a major scientific challenge to find a solution to the contradiction between high transmittance and low conductivity in the area of wide-band infrared transparent conductive film research. This study utilized new material systems and film preparation technologies to clarify the problem. A higher c-axis preferred orientation infrared transparent conducting Bi₂Se₃ thin film on a p-Si (111) substrate was developed using plasma-enhanced chemical vapor deposition (PECVD) technology. At room temperature, the film exhibited n-type conductivity, with high surface mobility of 2565 cm²/V·s and low surface resistivity of 2.6 × 10⁻⁵ Ω cm. In the mid-IR and far-IR regions, the produced Bi₂Se₃ thin film displayed transparency of 90% and 80%, respectively. To the best of our knowledge, this n-type conductive thin film created using chemical vapor deposition is the best IR-transparent thin film to date. Using this film, a Bi₂Se₃/p-Si heterojunction diode with a maximum voltage of 0.7 V was created. Young's modulus and hardness were determined to be 80 ± 5.5 GPa and 15 ± 2.2 GPa, respectively, for the film. It demonstrates the film's resistance to wear and deformation. The findings imply that Bi₂Se₃ film may be used as an anti-interference coating for infrared detectors and other optoelectronic devices throughout a wide wavelength range, from the mid-IR to the far-IR, due to its good optical transparency and electrical conductivity.
Synthesis and antibacterial activity of nanoenhanced conjugate of Ag-doped ZnO nanorods with graphene oxide
2023, Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Citation Excerpt :
The selected area electron diffraction was also carried out and the obtained ring patterns corresponds to the different Miller planes, which indicates the polycrystalline nature of the samples, as displayed in the Fig. 4(c) and Fig. 4(f), respectively. The value of d-spacing attributed to different Miller planes obtained from HRTEM and SAED analysis could be ascribed to the hexagonal wurtzite structure of ZnO, which has decent agreement with the outcomes of XRD analysis [49]. SEM and EDX analysis were utilized to investigate the surface morphology and elemental composition of Zn0.95Ag0.05O and Zn0.95Ag0.05O/GO, respectively.
In this paper, we report a successful synthesis of ZnO nanorods using the microwave-assisted technique, solid-state reaction method was utilized for the preparation of Zn_1-xAg_xO (x = 0.05, 0.1), Hummer’s modified method for graphene oxide (GO) along with the sonication method to prepare GO-based Ag-doped ZnO (Zn_1-xAg_xO/GO: x = 0.05, 0.1) nanocomposites. These nanorods and nanocomposites were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FTIR), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy for structural properties, scanning electron microscopy (SEM) along with energy dispersive X-ray (EDX) spectroscopy for morphological analysis, and UV–Vis spectroscopy for optical properties. XRD, FTIR, and Raman measurements substantiated that each sample is well crystallized in the single-phase polycrystalline wurtzite hexagonal structure of ZnO. The average crystallite size is found to be in decreasing order ranges 40 nm to 29 nm, respectively, along with a significant reduction in the optical bandgap. The SEM images showed a clear evidence of nanorods of ZnO, while the EDX spectra verified the presence of Zn, Ag, O, and C elements in the synthesized samples with their nominal percentage. Furthermore, the prepared nanocomposites effectively inhibited the growth of Staphylococcus aureus and Escherichia coli. In comparison to pure ZnO nanorods, GO-based Ag-doped ZnO nanorods showed improved antibacterial activity against both S. aureus and E. coli.
Probing the interaction of zinc oxide nanorods with human serum albumin: A spectroscopic approach
2023, Journal of Biotechnology
Citation Excerpt :
UV-Vis absorption spectrum of ZONRs is shown in Fig. 2(a), performed at room temperature, which manifests a strong absorption peak at about ∼380 nm. The optical energy band gap (Eg) of ZONRs can be deliberated by using the Tauc plot (Khan et al., 2021, 2020b, 2020a), which is shown in the inset of Fig. 2(a). We can easily find out Eg by plotting the graph between (αhν)2 versus hν, using the absorption data.
Bio-functionalized metal oxide nanoparticles (NPs) have been taken great importance in biomedical fields. The use of nanoparticles as delivery agents of therapeutic molecules led the researchers to emphasize the potential impact of these NPs on bio-macromolecules as protein–nanoparticle complexes, which also extended their importance as vehicles in targeted drug delivery systems due to increased ease of administration, firmness, reduced toxic side effects, and half-life of drugs. Since human serum albumin is the blood protein responsible for transporting materials in the blood system, the interaction of these particles with HSA is essential to be understood before considering the nanoparticles for any individual biomedical application. In the present study, we synthesized zinc-oxide nanorods (ZONRs) using a microwave-assisted synthesis technique, and characterized them by XRD, FTIR, Raman, SEM-EDX, UV-Vis spectroscopy, and photoluminescence (PL) spectroscopy methods. The interaction studies were carried out using fluorescence spectroscopy, and the change in secondary structure was analyzed using CD spectroscopy. The results of MTT cell viability assay demonstrated that the ZONRs has potential cytotoxic properties.

View all citing articles on Scopus

View full text

Structural, optical and electrical transport properties of Sn doped In2O3

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Experiments

Structural and Morphological properties

Conclusion

Credit author statement

Declaration of competing interest

Acknowledgment

Mater. Lett.

Mater. Lett.

Sens. Actuators, B

Appl. Surf. Sci.

Thin Solid Films

Appl. Catal., B

Chin. J. Catal.

J. Cryst. Growth

Mater. Res. Bull.

Phys. B Condens. Matter

Int. J. Electrochem. Sci

Spectrochim. Acta Mol. Spectros

Spectrochim. Acta Mol. Spectros

Thin Solid Films

Prog. Surf. Sci.

Mater. Sci. Eng., B

Chin. J. Catal.

Appl. Catal.

J. Magn. Magn Mater.

Thin Solid Films

Thin Solid Films

Solid State Commun.

Transparent functional oxide stretchable electronics: micro-tectonics enabled high strain electrodes

NPG Asia Mater.

Origin of magnetism in cobalt-doped indium tin oxide thin films

Phys. Rev. B

Bottom-up growth of fully transparent contact layers of indium tin oxide nanowires for light-emitting devices

Nat. Nanotechnol.

Magnetic behavior of sputtered co-doped indium-tin oxide films

Phys. Rev. B

Structural, optical and electrical transport properties of Sn doped In₂O₃