# Ferromagnetic and Photoluminescence Properties of Fe doped Indium-Tin- Oxide Nanoparticles Synthesised by Solid State Reaction

Deepannita Chakraborty, N Madhusudhana Rao, G Venugopal Rao, S Hainathbabu, S Kaleemulla, C Krishnamoorthi

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Deepannita Chakraborty, N Madhusudhana Rao, G Venugopal Rao, S Hainathbabu, S Kaleemulla, et al. Ferromagnetic and Photoluminescence Properties of Fe doped Indium-Tin- Oxide Nanoparticles Synthesised by Solid State Reaction. Mechanics, Materials Science & Engineering Journal, 2017, 9, 10.2412/mmse.47.72.37. [https://hal.science/hal-01499399](https://hal.science/hal-01499399)

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# Ferromagnetic and Photoluminescence Properties of Fe doped Indium-Tin-Oxide Nanoparticles Synthesised by Solid State Reaction

Deepannita Chakraborty¹, N. Madhusudhana Rao¹,ᵃ, G. Venugopal Rao², S. HainathBabu¹,
S. Kaleemulla¹, C. Krishnamoorthi¹

1 - Centre for Crystal Growth, School of Advanced Sciences, VIT University, Vellore, Tamilnadu, India

2 - Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamilnadu, India

a - drnmrao@gmail.com

<figure><img src="image_2.png" /></figure>

DOI 10.2412/mmse.47.72.37 provided by [Seo4U.link](https://link.springer.com/10.2412/mmse.47.72.37)

**Keywords:** Fe and Sn codoped Indium Oxide, Dilute magnetic semiconductors, antiferromagnetism.

**ABSTRACT.** Iron and tin codoped indium oxide (In<sub>0.90</sub>Sn<sub>0.05</sub>Fe<sub>0.05</sub>)<sub>2</sub>O<sub>3</sub>) nanoparticles were synthesized by solid state reaction. The synthesized nanoparticles were studied for their structural, surface, chemical, optical, magnetic and photoluminescence properties using respective characterization techniques. The XRD and FE-SEM images confirmed the nanosize of the particles. Raman studies indicated no structural changes in the indium oxide lattice after addition of Fe and Sn into the lattice. From magnetic studies it was observed that the Sn doped indium oxide nanoparticles were ferromagnetic. The ferromagnetic nature is destroyed after codoping of iron and tin in indium oxide lattice. Two broad emission peaks were observed in photoluminescence spectra.

**Introduction.** Currently the dilute magnetic semiconducting (DMS) materials are finding increased interest due to their potential as well as practical applications in the field of spintronics as well as exhibiting ferromagnetism at or above room temperature [1-4]. Till now many transition metal doped oxide semiconductors such as ZnO, TiO<sub>2</sub>, CeO<sub>2</sub> and In<sub>2</sub>O<sub>3</sub> were found to be exhibiting ferromagnetism at room temperature[5-7]. Among them, Indium oxides (In<sub>2</sub>O<sub>3</sub>) have high density of charge carriers, optical transparency and have low impact on the environment. Previous reports suggest that the decrease in crystal size of these oxides in the range of nanoparticles can lead to the change in their physical, chemical and optical properties [8, 9]. The decrease in crystal size can occur by doping the host lattice with another lattice having less ionic radii than the host. So In<sub>2</sub>O<sub>3</sub> is doped with Sn as ionic radii of Sn is less than In. This leads to the formation of one of the best transparent conductive oxides (TCOs) namely indium-tin oxide (ITO). Generally, it has a lattice parameter of *a* = 10.118 Å[10]. Consequently, ITO has high optical transparency, high electrical conductivity and high reflectance. ITO in the form of films has been used as transparent electrodes for flat-panel displays, electrochromic windows, solar panels and transparent coatings for solar-energy heat mirrors [11-14]. A large number of articles regarding transition metal doped In<sub>2</sub>O<sub>3</sub> thin films have been published but there are rarely any reports on magnetic and photoluminescence properties of transition metal and tin codoped indium oxide nanoparticles having uniform sized particles [15, 16].

**Experimental Details.** Commercially available In<sub>2</sub>O<sub>3</sub> (99.999%), SnO<sub>2</sub> (99.99%) and Fe<sub>2</sub>O<sub>3</sub> (99.99%) precursor powders were procured from Sigma-Aldrich (made in Germany) and were used as source materials. The ITO (In<sub>1.95</sub>Sn<sub>0.05</sub>O<sub>3</sub>) and (Fe:Sn) codoped In<sub>2</sub>O<sub>3</sub> powder samples were prepared by mixing stoichiometric molar ratio of In<sub>2</sub>O<sub>3</sub>, SnO<sub>2</sub> and Fe<sub>2</sub>O<sub>3</sub> precursors in Agate mortar and pestle. The mixture was ground for 16 hrs to make it homogeneous fine powder which was then
loaded into a one-end closed quartz tube with 1 cm diameter and 10 cm length. This precursor loaded
quartz tube was further enclosed in a large diameter quartz tube (reaction chamber) with 2.5 cm dia
and 75 cm length. The synthesis procedure was carried out in an optimised pressure of about 2x10⁻³
mbar. The whole setup was then heated at low ramping to reach 800 °C by microprocessor controlled
furnace and then soaked for 6 hrs until it was cooled back to room temperature. The structural,
morphological, optical and magnetic properties of the samples has been studied by using their
corresponding measuring instruments at room temperature.

**Results and Discussions.** Fig. 1 depicts the X-ray diffraction plot of (Fe:Sn) codoped In₂O₃ powder. The diffraction peaks in (Fe:Sn) codoped In₂O₃ profile matches with the JCPDS No. #06-0416 having cubic structure. The lattice constant of (Fe:Sn) codoped In₂O₃ fine powders is calculated as 10.08 Å. This is less than the lattice constant of In₂O₃, as reported in literature as 10.112 Å. The average crystallite size of (Fe:Sn) codoped In₂O₃ is determined as 41 nm by using the Debye-Scherrer formula.

<figure><img src="image_3.png" /><figcaption>Fig. 1. X-ray diffraction of (Fe:Sn) codoped Indium Oxide nanoparticles.</figcaption></figure>

<figure><img src="image_4.png" /><figcaption>Fig. 2. FE SEM micrograph of (Fe:Sn)In₂O₃ nanoparticles.</figcaption></figure>
Fig. 2. shows the morphology of the (Fe:Sn) codoped In₂O₃ powders having average particle size of 47 nm. This is greater than the crystallite size which suggests that the particles are multi-grained. Fig. 3. confirms the presence of appropriate ratios of all elements in the EDAX spectra of (Fe:Sn) codoped In₂O₃ nanoparticles. It has also been confirmed that Fe and Sn ions substitute in the host lattice of In₂O₃.

The Raman spectra of ITO, (Fe:Sn) codoped In₂O₃ as well as the precursors were measured. From Fig. 4. the characteristic Raman peaks of In₂O₃ were observed at 110, 132, 154, 164, 212, 249, 307, 365, 480, 495, 631 cm⁻¹. These peaks perfectly coincide with the reports in the literature[17]. The characteristic Raman peaks of ITO and (Fe:Sn) codoped In₂O₃ perfectly matches with the peaks of In₂O₃. This indicates that (Fe:Sn) codoped In₂O₃ has good lattice order, suggesting that Fe³⁺ions might have been located at substitutional lattice sites of In³⁺ as reported earlier by Harinath et al.[18].

<figure><img src="image_5.png" /><figcaption>Fig. 3. EDAX image of (Fe:Sn) In₂O₃ nanoparticles.</figcaption></figure>

<figure><img src="image_6.png" /><figcaption>Fig. 4. Raman spectra of In₂O₃, SnO₂, ITO and Fe doped ITO powders.</figcaption></figure>
The diffuse reflectance spectra for pure In₂O₃, ITO and Fe doped ITO has been reported earlier by Harinath et al. [18]. The optical band gap of (Fe:Sn) codoped In₂O₃ has been determined by plotting tauc's plot. The (Fe:Sn) codoped In₃O₃ sample undergoes indirect transition with an optical band gap of 2.82 eV.

The ferromagnetic nature of ITO at room temperature has been observed in previous report by Harinath et al. [18]. This may be attributed to the dopant Sn which might have created carrier mediated mechanism or due to formation of oxygen vacancies at the time of synthesis. It has also been observed in previous report by Harinath et al [18] that the doping of Fe in the ITO lattice degraded the magnetic property of ITO.

The temperature dependent magnetization measurements for (Fe:Sn) codoped In₂O₃ have been carried out. The formation of antiferromagnetism and the absence of magnetic cluster formation can be suggested from the plots of zero fields cooled (ZFC) and field cooled (FC) datas.

<figure><img src="image_7.png" /><figcaption>Fig. 5. The photoluminescence plot of ITO and (Fe:Sn) codoped In₂O₃ nanoparticles.</figcaption></figure>

The photolumiscence (PL) plots for the ITO and (Fe:Sn) codoped In₂O₃ nanoparticles were recorded at room temperature. Fig. 5 depicts the UV emission peak at 330 nm and blue-green emission peak at 465 nm for ITO and (Fe:Sn) codoped In₂O₃. The UV emission peak is broad in nature. This is caused by the near band edge (NBE) radiative transitions. The blue-green emission peak occurs due to the various crystalline or surface defects.

**Summary.** Nanoparticles of ITO and (Fe:Sn) codoped In₂O₃ has been synthesized. The ferromagnetic behavior is observed in ITO at room temperature and it is found to decreasing on codoping of Fe ions with Sn ions in In₂O₃ lattice. The optical band gap energy of (Fe:Sn) codoped In₂O₃ is found to be 2.82 eV. The emission peaks has been observed at 329 nm and 466 nm on an excitation wavelength at 300 nm indicating the occurrence of surface defects.

**Acknowledgements.** The authors are highly thankful to the UGC-DAE-CSR, IGCAR, Kalpakkam 603102, Tamilnadu, India, for providing financial (Grant No: CSR-KN/CRS-72/2015-16/809) support to carry out the present work. The authors also thank VIT-SIF for providing XRD, Raman, UV-Vis-NIR and Photoluminescence facilities.

**References**

[1] H. Ohno, H. Munekata, T. Penney, S. von Molnár, L.L. Chang, Magnetotransport properties of p-type (In, Mn)As diluted magnetic III-V semiconductors, Physical Review Letters, 68 (1992) 2664-2667, DOI: 10.1103/PhysRevLett.68.2664.
[2] S.A. Wolf, D.D. Awschalom, R.A. Buhrman, J.M. Daughton, S. von Molnár, M.L. Roukes, A.Y. Chtchelkanova, D.M. Treger, Spintronics: A Spin-Based Electronics Vision for the Future, Science, 294 (2001) 1488, DOI: 10.1126/science.1065389.

[3] K. Sato, H. Katayama-Yoshida, First principles materials design for semiconductor spintronics, Semiconductor Science and TechnologyG, 17 (2002) 367, DOI: 10.1088/0268-1242/17/4/309.

[4] P. Sharma, A. Gupta, F.J. Owens, A. Inoue, K.V. Rao, Room temperature spintronic material—Mn-doped ZnO revisited, Journal of Magnetism and Magnetic Materials, 282 (2004) 115-121, DOI: 10.1016/j.jmmm.2004.04.028.

[5] R. Singhal, A. Samariya, S. Kumar, Y. Xing, D. Jain, U. Deshpande, T. Shripathi, E. Saitovitch, C. Chen, On the longevity of H-mediated ferromagnetism in Co doped: A study of electronic and magnetic interplay, Solid State Communications, 150 (2010) 1154-1157, DOI: 10.1016/j.ssc.2010.03.018.

[6] R. Singhal, A. Samariya, Y. Xing, S. Kumar, S. Dolia, U. Deshpande, T. Shripathi, E.B. Saitovitch, Electronic and magnetic properties of Co-doped ZnO diluted magnetic semiconductor, Journal of Alloys and Compounds, 496 (2010) 324-330, DOI: 10.1016/j.jallcom.2010.02.005.

[7] A. Sundaresan, R. Bhargavi, N. Rangarajan, U. Siddesh, C.N.R. Rao, Ferromagnetism as a universal feature of nanoparticles of the otherwise nonmagnetic oxides, Physical Review B, 74 (2006) 161306, DOI: 10.1103/PhysRevB.74.161306.

[8] P.F. Trwoga, A.J. Kenyon, C.W. Pitt, Modeling the contribution of quantum confinement to luminescence from silicon nanoclusters, Journal of Applied Physics, 83 (1998) 3789-3794, DOI: 10.1063/1.366608.

[9] A. Nakata, M. Mizuhata, S. Deki, Novel fabrication of highly crystallized nanoparticles in the confined system by the liquid phase deposition (LPD) method, Electrochimica Acta, 53 (2007) 179-185, DOI: 10.1016/j.electacta.2007.06.025.

[10] K. Utsumi, H. Iigusa, R. Tokumaru, P.K. Song, Y. Shigesato, Study on In2O3–SnO2 transparent and conductive films prepared by d.c. sputtering using high density ceramic targets, Thin Solid Films, 445 (2003) 229-234, DOI: 10.1016/S0040-6090 (03)01167-2.

[11] S. Deki, S. Iizuka, M. Mizuhata, A. Kajinami, Fabrication of nano-structured materials from aqueous solution by liquid phase deposition, Journal of Electroanalytical Chemistry, 584 (2005) 38-43, DOI: 10.1016/j.jelechem.2004.05.027.

[12] J. George, C.S. Menon, Electrical and optical properties of electron beam evaporated ITO thin films, Surface and Coatings Technology, 132 (2000) 45-48, DOI: 10.1016/S0257-8972 (00)00726-X.

[13] S. Ishibashi, Y. Higuchi, Y. Ota, K. Nakamura, Low resistivity indium-tin oxide transparent conductive films. II. Effect of sputtering voltage on electrical property of films, Journal of Vacuum Science & Technology A, 8 (1990) 1403-1406, DOI: 10.1116/1.576890.

[14] K.R. Prasad, K. Koga, N. Miura, Electrochemical Deposition of Nanostructured Indium Oxide: High-Performance Electrode Material for Redox Supercapacitors, Chemistry of Materials, 16 (2004) 1845-1847, DOI: 10.1021/cm0497576.

[15] S. Kaleemulla, N. Madhusudhana Rao, M. Girish Joshi, A. Sivasankar Reddy, S. Uthanna, P. Sreedhara Reddy, Electrical and optical properties of In2O3:Mo thin films prepared at various Mo-doping levels, Journal of Alloys and Compounds, 504 (2010) 351-356, DOI: 10.1016/j.jallcom.2010.05.068.

[16] S. Kaleemulla, A.S. Reddy, S. Uthanna, P.S. Reddy, Physical properties of In2O3 thin films prepared at various oxygen partial pressures, Journal of Alloys and Compounds, 479 (2009) 589-593, DOI: 10.1016/j.jallcom.2009.01.003.
[17] S. Dussan, M. Singh, A. Kumar, R. Katiyar, Synthesis, Structural and Magnetic Properties of Ni-Doped In2O3 Nanoparticles, Integrated Ferroelectrics, 125 (2011) 155-161, DOI: 10.1080/10584587.2011.574483.

[18] S.H. Babu, N.S. Krishna, S. Kaleemulla, N.M. Rao, C. Krishnamoorthi, G.M. Joshi, I. Omkaram, D.S. Reddy, R. Chitra, S. Bhattacharya, N.K. Sahoo, Raman and FT-IR studies of (In0.90Sn0.05Fe0.05)2O3 nanoparticles, AIP Conference Proceedings, 1731 (2016) 140008, DOI: 10.1063/1.4948174.

Cite the paper

Deepannita Chakraborty, N. Madhusudhana Rao, G. Venugopal Rao, S. HainathBabu, S. Kaleemulla, C. Krishnamoorthi (2017). *Ferromagnetic and Photoluminescence Properties of Fe doped Indium-Tin-Oxide Nanoparticles Synthesised by Solid State Reaction*. Mechanics, Materials Science & Engineering, Vol 9. doi: 10.2412/mmse.47.72.37