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Synthesis and characterization of Ni incorporated titanium dioxide thin films

  • Deepak Kumar (a1), Prasanta Mandal (a2), Anil Singh (a1), Charu Pant (a3) and Sudesh Sharma (a2)...


Thin films of insulating Ti1−xNixO2 (x = 0.00, 0.05, 0.10, and 0.15) are synthesized by the spray pyrolysis technique. All the films are seen to crystallize into polycrystalline anatase phase of TiO2. However, weak signature of the NiTiO3 phase is also observed for the films having higher Ni ion concentration. Optical absorption analysis suggests nonmonotonous band gap decrease from 3.67 to 3.59 eV with respect to added concentration of Ni ions unto ‘x’ = 0.10 in the TiO2 matrix. The presence of ferromagnetic ordering at room temperature in Ni incorporated TiO2 films is revealed by M–H measurements. Calculated values of saturation magnetization indicate that the observed ferromagnetism is not due to the presence of Ni clusters or segregation of other ferromagnetic phase. Electrically insulating nature of the films suggests that the observed FM ordering is most probably due to the ferromagnetic interaction between bound magnetic polarons which formed due to the creation of oxygen vacancies or defects.


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1.Dietl, T., Ohno, H., Matsukur, F., Cibert, J., and Ferrad, D.: Zener model description of ferromagnetism in zinc-blende magnetic semiconductors. Science 287, 1019 (2000).
2.Zutic, I., Fabian, J., and Sarma, S.D.: Spintronics: Fundamentals and applications. Rev. Mod. Phys. 76, 323 (2004).
3.Matsumoto, Y., Murakami, M., Shono, T., Hasegawa, T., Fukumura, T., Kawasaki, M., Ahmet, P., Chikyow, T., Koshihara, S., and Koinuma, H.: Room-temperature ferromagnetism in transparent transition metal doped titanium dioxide. Science 291, 854 (2001).
4.Hoa, N.T.Q. and Huyen, D.N.: Comparative study of room temperature ferromagnetism in undoped and Ni-doped TiO2 nanowires synthesized by solvothermal method. J. Mater. Sci.: Mater. Electron. 24, 793 (2013).
5.Bahadur, N., Pasricha, R., Govind, , Chand, S., and Kotnala, R.K.: Effect of Ni doping on the microstructure and high Curie temperature ferromagnetism in sol–gel derived titania powders. Mater. Chem. Phys. 133, 471 (2012).
6.Cho, J.H., Hwang, T.J., Joh, Y.G., Kim, E.C., Kim, D.H., Lee, K.J., Park, H.W., Ri, H-C., Kim, J.P., and Cho, C.R.: Room-temperature ferromagnetism in highly-resistive Ni-doped TiO2. Appl. Phys. Lett. 88, 092505 (2006).
7.Hong, N.H., Prellier, W., Sakai, J., and Hassini, A.: Fe- and Ni-doped TiO2 thin films grown on LaAlO3 and SrTiO3 substrates by laser ablation. Appl. Phys. Lett. 84, 2850 (2004).
8.Gao, H., Tian, J., Kong, H., Yang, P., Zhang, W., and Chu, J.: Optical and magnetic properties of mixed crystal Ti0.95Ni0.05O2 films deposited on Si substrates by sol–gel method. Surf. Coat. Technol. 228, 162 (2013).
9.Pinto, J.V., Cruz, M.M., da Silva, R.C., Alves, E., and Godinho, M.: Magnetic properties of TiO2 rutile implanted with Ni and Co. J. Magn. Magn. Mater. 294, e73 (2005).
10.Priour, D.J. and Das Sarma, S.: Phase diagram of the disordered RKKY model in dilute magnetic semiconductors. Phys. Rev. Lett. 97, 127201 (2006).
11.Yamasaki, T., Fukumura, T., Yamada, Y., Nakano, M., Uneo, K., Makino, T., and Kawasaki, M.: Co-doped TiO2 films grown on glass: Room-temperature ferromagnetism accompanied with anomalous Hall effect and magneto-optical effect. Appl. Phys. Lett. 94, 102515 (2009).
12.Griffin, K.A., Pakhomov, A.B., Wang, C.M., Heald, S.M., and Krishnan, K.M.: Intrinsic ferromagnetism in insulating cobalt doped anatase TiO2. Phys. Rev. Lett. 94, 157 (2005).
13.Punnoose, A., Seehra, M.S., Park, W.K., and Moodera, J.S.: On the room temperature ferromagnetism in Co-doped TiO2 films. J. Appl.Phys. 93, 7867 (2003).
14.Stampe, P.A., Kennedy, R.J., Xin, Y., and Parker, J.S.: Investigation of the cobalt distribution inTiO2:Co thin films. J. Appl. Phys. 92, 7114 (2002).
15.Xu, Q.Y., Schmidt, H., Zhou, S.Q., Potzger, K., Helm, M., Hochmuth, H., Lorenz, M., Setzer, A., Esquinazi, P., Meinecke, C., and Grundmann, M.: Room temperature ferromagnetism in ZnO films due to defects. Appl. Phys. Lett. 92, 082508 (2008).
16.Venkatesan, M., Fitzgerald, C.B., and Coey, J.M.D.: Thin films: Unexpected magnetism in a dielectric oxide. Nature 430, 630 (2004).
17.Hong, N.H., Sakai, J., Poirot, N., and Brize, V.: Room-temperature ferromagnetism observed in undoped semiconducting and insulating oxide thin films. Phys. Rev. B 73, 132404 (2006).
18.Nguyen, N.H., Prellier, W., Sakai, J., and Ruyter, A.: Substrate effects on the room-temperature ferromagnetism in Co-doped TiO2 thin films grown by pulsed laser deposition. J. Appl. Phys. 95, 7378 (2004).
19.Chambers, S.A., Droubay, T., Wang, C.M., Lea, A.S., Farrow, R.F.C., Folks, L., Deline, V., and Anders, S.: Clusters and magnetism in epitaxial Co-doped TiO2 anatase. Appl. Phys. Lett. 82, 1257 (2003).
20.Kaspar, T.C., Droubay, T., McCready, D.E., Nachimuthu, P., Heald, S.M., Wang, C.M., Lea, A.S., Shutthanandan, V., Chambers, S.A., and Toney, M.F.: Magnetic properties of epitaxial Co-doped anatase TiO2 thin films with excellent structural quality. J. Vac. Sci. Technol., B: Microelectron. Nanometer Struct.–Process., Meas., Phenom. 24, 2012 (2006).
21.Mann, H.S., Lang, B.N., Schwab, Y., Niemelä, J.P., Karppinen, M., and Scarel, G.: The performance of small scale multi-generation technologies. J. Vac. Sci. Technol., A 33, 01A124 (2015).
22.Niemelä, J.P., Yamauchi, H., and Karppine, M.: Conducting Nb-doped TiO2 thin films fabricated with an atomic layer deposition technique. Thin Solid Films 551, 19 (2014).
23.De, R., Haque, S.M., Tripathi, S., Rao, K.D., Singh, R., Som, T., and Sahoo, N.K.: Temperature dependent optical characterization of Ni–TiO2 thin films as potential photocatalytic material. AIP Adv. 7, 095115 (2017).
24.Gole, J.L., Prokes, S.M., and Glembocki, O.J.: Efficient room-temperature conversion of anatase to rutile TiO2 induced by high-spin ion doping. J. Phys. Chem. C 112, 1782 (2008).
25.Kharoubi, A., Bouaza, A., Benrabah, B., Ammari, A., and Khiali, A.: Characterization of Ni-doped TiO2 thin films deposited by dip-coating technique. Eur. Phys. J.: Appl. Phys. 72, 30301 (2015).
26.Renugadevi, R., Venkatachalam, T., Narayanasamy, R., and Kirupha, S.D.: Preparation of Co doped TiO2 nano thin films by sol gel technique and photocatalytic studies of prepared films in tannery effluent. Optik 127, 10127 (2016).
27.Tian, J., Gao, H., Deng, H., Sun, L., Kong, H., Yang, P., and Chu, J.: Structural, magnetic and optical properties of Ni-doped TiO2 thin films deposited on silicon(100) substrates by sol–gel process. J. Alloys Compd. 581, 318 (2013).
28.Suryanarayanan, R., Naik, V.M., Kharel, P., Talagala, P., and Naik, R.: Ferromagnetism at 300 K in spin-coated films of Co doped anatase and rutile-TiO2. Solid State Commun. 133, 439 (2005).
29.Xu, J.P., Wang, J.F., Lin, Y.B., Liu, X.C., Lu, Z.L., Lu, Z.H., Lv, L.Y., Zhang, F.M., and Du, Y.W.: Effect of annealing ambient on the ferromagnetism of Mn-doped anatase TiO2 films. J. Phys. D: Appl. Phys. 40, 4757 (2007).
30.Zielinska, A., Kowalska, E., Sobczak, J.W., Łacka, I., Gazda, M., Ohtani, B., Hupka, J., and Zaleska, A.: Silver-doped TiO2 prepared by microemulsion method surface properties, bio-and photoactivity. Sep. Purif. Technol. 72, 309 (2010).
31.Adomnitel, C., Luca, D., Girtan, M., Sandu, I., Nica, V., Sandu, A.V., and Mardare, D.: Nb-doped TiO2 thin films deposited by spray pyrolysis method. J. Optoelectron. Adv. Mater. 15, 519 (2013).
32.Golego, N., Studenikin, S.A., and Cocivera, M.: Spray pyrolysis preparation of porous polycrystalline thin films of titanium dioxide containing Li and Nb. J. Mater. Res. 14, 698 (1999).
33.Patil, L.A., Suryawanshi, D.N., Pathan, I.G., and Patil, D.M.: Nickel doped spray pyrolyzed nanostructured TiO2 thin films for LPG gas sensing. Sens. Actuators, B 176, 514 (2013).
34.Kuznetsov, A.Y., Machado, R., Gomes, L.S., Achete, C.A., Swamy, V., Mud-dle, B.C., and Prakapenka, V.: Size dependent of rutile TiO2 lattice parameters determined via simultaneous size, strain and shape modeling. Appl. Phys. Lett. 94, 193117 (2009).
35.Wilso, G.J., Matijasevich, A.S., Mitchell, D.R., Schulz, J.C., and Will, G.D.: Modification of TiO2 for enhanced surface properties: Finite ostwald ripening by a microwave hydrothermal process. Langmuir 22, 2016 (2006).
36.Asanuma, T., Matsutani, T., Liu, C., Mihara, T., and Kiuchi, M.: Structural and optical properties of titanium dioxide films deposited by reactive magnetron sputtering in pure oxygen plasma. J. Appl. Phys. 95, 6011 (2004).
37.Tauc, J., Grigorovich, R., and Vancu, A.: Optical properties and electronic structure of amorphous germanium. Phys. Status Solidi 15, 627 (1966).
38.Manifacier, J.C., Gasiot, J., and Fillard, J.P.: A simple method for the determination of the optical constants n, h and the thickness of a weakly absorbing thin film. J. Phys. E: Sci. Instrum. 9, 1002 (1976).
39.Hwang, K.S., Jeong, J.H., Ahn, J.H., and Kim, B.H.: Hydrophilic/hydrophobic conversion of Ni-doped TiO2 thin films on glass substrates. Ceram. Int. 32, 935 (2006).
40.Jing, D., Zhang, Y., and Guo, L.: Study on the synthesis of Ni doped mesoporous TiO2 and its photocatalytic activity for hydrogen evolution in aqueous methanol solution. Chem. Phys. Lett. 415, 74 (2005).
41.Pandiyan, R., Micheli, V., Ristic, D., Bartali, R., Pepponi, G., Barozzi, M., Gottardi, G., Ferrarid, M., and Laidani, N.: Structural and near-infra red luminescence properties of Nd-doped TiO2 films deposited by RF sputtering. J. Mater. Chem. 22, 22424 (2012).
42.Santara, B., Giri, P.K., Dhara, S., Imakita, K., and Fujii, M.: Oxygen vacancy-mediated enhanced ferromagnetism in undoped and Fe-doped TiO2 nanoribbons. J. Phys. D: Appl. Phys. 47, 235304 (2014).
43.Wang, H., Zong, Z., and Yan, Y.: Structural effects of field emission from GaN nanofilms on SiC substrates. J. Appl. Phys. 115, 233909 (2014).
44.Hou, D.L., Meng, H.J., Jia, L.Y., Ye, X.J., Zhou, H.J., and Li, X.L.: Oxygen vacancy enhanced the room temperature ferromagnetism in Ni-doped TiO2 thin films. Phys. Lett. A 364, 318 (2007).
45.Zhang, J., Yun, Q., and Wang, Q.: Room temperature ferromagnetism of Ni-doped SnO2 system. Mod. Appl. Sci. 4, 124 (2010).
46.Chikazumi, S.: Physics of Magnetism (Krieger, Malabar, Florida, 1978); p. 19.
47.Liu, X.J., Zhu, X.Y., Song, C., Zeng, F., and Pan, F.: Intrinsic and extrinsic origins of room temperature ferromagnetism in Ni-doped ZnO films. J. Phys. D: Appl. Phys. 42, 035004 (2009).
48.Hong, N.H., Ruyter, A., Prellier, W., Sakai, J., and Huong, N.T.: Magnetism in Ni-doped SnO2 thin films. J. Phys.: Condens. Matter 17, 6533 (2005).
49.Park, Y.R., li Choi, S., Lee, J.H., Kim, K.J., and Kim, C.S.: Ferromagnetic properties of Ni-doped rutile TiO2−δ. J. Korean Phys. Soc. 50, 638 (2007).
50.Jayaram, V. and Rani, B.S.: Soft chemical routes to the synthesis of extended solid solutions of wurtzite ZnO–MO (M = Mg, Co, Ni). Mater. Sci. Eng., A 304, 800 (2001).
51.Huang, G.J., Wang, J.B., Zhong, X.L., Zhou, G.C., and Yan, H.L.: Synthesis, structure, and room-temperature ferromagnetism of Ni-doped ZnO nano-particles. J. Mater. Sci. 42, 6464 (2007).
52.Pearton, S.J., Heo, W.H., Ivill, M., Norton, D.P., and Steiner, T.: Topical Review: Dilute magnetic semiconducting oxides. Semicond. Sci. Technol. 19, R59 (2004).
53.Kaminski, A. and Sarma, S.D.: Polaron percolation in diluted magnetic semiconductors. Phys. Rev. Lett. 88, 247202 (2002).
54.Coey, J.M.D., Venkateshan, M., and Fitzgerald, C.B.: Donor impurity band exchange in dilute ferromagnetic oxides. Nat. Mater. 4, 173 (2005).
55.Chen, J., Lu, G-H., Cao, H., Wang, T., and Xu, Y.: Ferromagnetic mechanism in Ni-doped anatase TiO2. Appl. Phys. Lett. 93, 172504 (2008).
56.Ogale, S.B.: Thin Film and Heterostructures for Oxide Electronics (Springer Science1Business Media, Inc., New York, New York, 2005); p. 245.
57.Liu, X.F., Gong, W.M., Iqbal, J., He, B., and Yu, R.H.: Structural defects-mediated room-temperature ferromagnetism in Co-doped SnO2 insulating films. Thin Solid Films 517, 6091 (2009).


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Synthesis and characterization of Ni incorporated titanium dioxide thin films

  • Deepak Kumar (a1), Prasanta Mandal (a2), Anil Singh (a1), Charu Pant (a3) and Sudesh Sharma (a2)...


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