Abstract
Single-phase samples of InCr1−xTixO3+x/2 with x = 3/4, 5/7 and 2/3 compositions were synthesized by the solid-state reaction method, and optical, dielectric and magnetic properties were explored for the first time. Crystal structure analysis showed a complete Cr3+/Ti4+ solubility, and the monoclinic crystal structure was successfully characterized. The optical bandgap was obtained by both Kubelka–Munk function and Tauc plot method. The Cr3+/Ti4+ composition has a little effect in the direct bandgap taking values of 2.09 eV for x = 3/4 and 1.97 eV for x = 2/3, respectively. We found that the permittivity shows a peak strongly dependent on the frequency, which is typical of relaxor behavior. In addition, the relaxor peak is dependent on the Cr3+/Ti4+ composition. The AC conductivity analysis showed that main charge carriers to participate in the electric conductivity are associated with small polarons with Eact ~ 0.40 eV. Diluted magnetic or paramagnetic behavior was found in the magnetization studies. Accordingly, we found that the compositional disordered Cr3+/Ti4+ cations randomly distributed among equivalent sites into Cr/Ti–O layer explain both the dielectric relaxor and magnetic features.
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R.L. Hoffman, B.J. Norris, J.F. Wager, ZnO-based transparent thin-film transistors. Appl. Phys. Lett. 82(5), 733–735 (2003). https://doi.org/10.1063/1.1542677
K. Nomura, H. Ohta, A. Takagi, T. Kamiya, M. Hirano, H. Hosono, Room-temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors. Nature 432(7016), 488–492 (2004). https://doi.org/10.1038/nature03090
L. Petti, N. Münzenrieder, C. Vogt et al., Metal oxide semiconductor thin-film transistors for flexible electronics. Appl. Phys. Rev. 3(2), 021303 (2016). https://doi.org/10.1063/1.4953034
Z. Chen, W. Li, R. Li, Y. Zhang, G. Xu, H. Cheng, Fabrication of highly transparent and conductive indium-tin oxide thin films with a high figure of merit via solution processing. Langmuir 29(45), 13836–13842 (2013). https://doi.org/10.1021/la4033282
V.G. Kytin, V.A. Kulbachinskii, O.V. Reukova et al., Conducting properties of In2O3:Sn thin films at low temperatures. Appl. Phys. A 114(3), 957–964 (2014). https://doi.org/10.1007/s00339-013-7799-8
S. Jeong, Y.-G. Ha, J. Moon, A. Facchetti, T.J. Marks, Role of gallium doping in dramatically lowering amorphous-oxide processing temperatures for solution-derived indium zinc oxide thin-film transistors. Adv. Mater. 22(12), 1346–1350 (2010). https://doi.org/10.1002/adma.200902450
H. Yabuta, M. Sano, K. Abe et al., High-mobility thin-film transistor with amorphous InGaZnO4 channel fabricated by room temperature rf-magnetron sputtering. Appl. Phys. Lett. 89(11), 112123 (2006). https://doi.org/10.1063/1.2353811
J. Zhou, G. Wu, L. Guo, L. Zhu, Q. Wan, Flexible Transparent junctionless TFTs with oxygen-tuned indium-zinc-oxide channels. IEEE Electron. Device Lett. 34(7), 888–890 (2013). https://doi.org/10.1109/LED.2013.2260819
N. Kimizuka, E. Takayama, Survey of the phase formation in the Yb2O3–Ga2O3–MO and Yb2O3–Cr2O3–MO systems in air at high temperatures (M: Co, Ni, Cu, and Zn). J. Solid State Chem. 43(3), 278–284 (1982). https://doi.org/10.1016/0022-4596(82)90241-9
N. Kimizuka, T. Mohri, Spinel, YbFe2O4, and Yb2Fe3O7 types of structures for compounds in the In2O3 and Sc2O3–A2O3–BO systems [A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn] at temperatures over 1000°C. J. Solid State Chem. 60(3), 382–384 (1985). https://doi.org/10.1016/0022-4596(85)90290-7
M. Nakamura, N. Kimizuka, T. Mohri, M. Isobe, Phase equilibria in the system In2O3–M2ZnO4–ZnO at 1350 °C (M: Fe, Ga, Al) and crystal chemical consideration of InMO3 (ZnO)m phases with LuFeO3 (ZnO)m-type structures. J Alloys Compd. 192(1–2), 105–107 (1993). https://doi.org/10.1016/0925-8388(93)90200-7
M. Nakamura, N. Kimizuka, T. Mohri, The phase relations in the In2O3–Ga2ZnO4–ZnO system at 1350°C. J Solid State Chem. 93(2), 298–315 (1991). https://doi.org/10.1016/0022-4596(91)90304-Z
Y. Ogo, H. Yanagi, T. Kamiya, K. Nomura, M. Hirano, H. Hosono, Epitaxial film growth, optical, electrical, and magnetic properties of layered oxide In3FeTi2O10. J. Appl. Phys. 101(10), 103714 (2007). https://doi.org/10.1063/1.2734953
H.-W. Zan, W.-W. Tsai, C.-H. Chen, C.-C. Tsai, Effective mobility enhancement by using nanometer dot doping in amorphous IGZO thin-film transistors. Adv. Mater. 23(37), 4237–4242 (2011). https://doi.org/10.1002/adma.201102530
F. Brown, M.J. Flores, N. Kimizuka et al., Phase relations in the system In2O3–TiO2–Fe2O3 at 1100 °C in Air. J. Solid State Chem. 144(1), 91–99 (1999). https://doi.org/10.1006/jssc.1998.8123
F. Brown, N. Kimizuka, Y. Michiue et al., New compounds In3Ti2AO10, In6Ti6BO22, and their solid solutions (A: Al, Cr, Mn, Fe, or Ga; B: Mg, Mn Co, Ni, Cu, or Zn): synthesis and crystal structures. J. Solid State Chem. 147(2), 438–449 (1999). https://doi.org/10.1006/jssc.1999.8358
N. Kimizuka, F. Brown, M.J.R. Flores, M. Nakamura, Y. Michiue, T. Mohri, The phase relations in the system In2O3–TiO2–MgO at 1100 and 1350 °C. J. Solid State Chem. 150(2), 276–280 (2000). https://doi.org/10.1006/jssc.1999.8591
Y. Michiue, M. Onoda, F. Brown, N. Kimizuka, Modulated structure of the composite crystal InCr1−xTixO3+x/2. J. Solid State Chem. 177(8), 2644–2648 (2004). https://doi.org/10.1016/j.jssc.2004.04.033
Y. Michiue, F. Brown, N. Kimizuka, M. Watanabe, M. Orita, H. Ohta, Orthorhombic InFe 0.33 Ti 0.67 O 3.33. Acta Crystallogr. Sect. C Cryst. Struct. Commun. 55(11), 1755–1757 (1999). https://doi.org/10.1107/S0108270199009038
F.F. Castillón-Barraza, A. Durán, M.H. Farías et al., Phase stability, microstructure, and dielectric properties of quaternary oxides In12Ti10A2 BO42 (A: Ga or Al; B: Mg or Zn). J. Am. Ceram. Soc. 102(1), 320–330 (2019). https://doi.org/10.1111/jace.15920
T.J.B. Holland, S.A.T. Redfern, Unit cell refinement from powder diffraction data: the use of regression diagnostics. Miner. Mag. 61(404), 65–77 (1997). https://doi.org/10.1180/minmag.1997.061.404.07
Y. Michiue, F. Brown, N. Kimizuka et al., Crystal structure of InTi 0.75 Fe 0.25 O 3.375 and phase relations in the pseudobinary system InFeO3–In2Ti2O7 at 1300 °C. Chem. Mater. 12(8), 2244–2249 (2000). https://doi.org/10.1021/cm000189d
R.D. Shannon, Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Sect. A 32(5), 751–767 (1976). https://doi.org/10.1107/S0567739476001551
P. Kubelka, New contributions to the optics of intensely light-scattering materials part II: nonhomogeneous layers*. J. Opt. Soc. Am. 44(4), 330 (1954). https://doi.org/10.1364/JOSA.44.000330
L. Yang, B. Kruse, Revised Kubelka–Munk theory I theory and application. J. Opt. Soc. Am. A 21(10), 1933 (2004). https://doi.org/10.1364/JOSAA.21.001933
J. Tauc, Optical properties and electronic structure of amorphous Ge and Si. Mater. Res. Bull. 3(1), 37–46 (1968). https://doi.org/10.1016/0025-5408(68)90023-8
D.C. Hays, B.P. Gila, S.J. Pearton, F. Ren, Energy band offsets of dielectrics on InGaZnO 4. Appl Phys Rev. 4(2), 021301 (2017). https://doi.org/10.1063/1.4980153
A.A. Bokov, Z.-G. Ye, Dielectric relaxation in relaxor ferroelectrics. J. Adv. Dielectr. 02(02), 1241010 (2012). https://doi.org/10.1142/S2010135X1241010X
N.W. Thomas, A new framework for understanding relaxor ferroelectrics. J. Phys. Chem. Solids 51(12), 1419–1431 (1990). https://doi.org/10.1016/0022-3697(90)90025-B
O. Raymond, R. Font, N. Suárez-Almodovar, J. Portelles, J.M. Siqueiros, Frequency-temperature response of ferroelectromagnetic Pb(Fe1/2Nb1/2O3) ceramics obtained by different precursors. Part I. Structural and thermo-electrical characterization. J. Appl. Phys. 97(8), 084107 (2005). https://doi.org/10.1063/1.1870099
M.A. Tena, G. Garcia-Belmonte, J. Bisquert, P. Escribano, M.T. Colomer, J.R. Jurado, Impedance spectroscopy studies of orthorhombic FeNbO4. J. Mater. Sci. 31(8), 2043–2046 (1996). https://doi.org/10.1007/BF00356624
A. Durán, E. Verdin, R. Escamilla, F. Morales, R. Escudero, Mechanism of small-polaron formation in the biferroic YCrO3 doped with calcium. Mater. Chem. Phys. 133(2–3), 1011–1017 (2012). https://doi.org/10.1016/j.matchemphys.2012.02.008
A. Durán, F.C. Meza, G.G.C. Arizaga, Hydroxide precursors to produce nanometric YCrO3: characterization and conductivity analysis. Mater. Res. Bull. 47(6), 1442–1447 (2012). https://doi.org/10.1016/j.materresbull.2012.02.043
C. Ang, Z. Yu, L.E. Cross, Oxygen-vacancy-related low-frequency dielectric relaxation and electrical conduction in Bi:SrTiO3. Phys. Rev. B. 62(1), 228–236 (2000). https://doi.org/10.1103/PhysRevB.62.228
M. Imlau, H. Badorreck, C. Merschjann, Optical nonlinearities of small polarons in lithium niobate. Appl. Phys. Rev. 2(4), 040606 (2015). https://doi.org/10.1063/1.4931396
D. Adler, J. Feinleib, Electrical and optical properties of narrow-band materials. Phys. Rev. B 2(8), 3112–3134 (1970). https://doi.org/10.1103/PhysRevB.2.3112
Acknowledgements
A.D. thanks PAPIIT-UNAM project IN101919. The author thanks to R. Escamilla for the fruitful disccusion on the crystal structure analysis. V.E.A.M. also thanks to General Direction of Higher Education (Prodep-dgesu-SEP) Project UNISON-PTC-296. The technical assistance of the M en C. P. Casillas is acknowledged
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Durán, A., Martínez-Aguilar, E., Conde-Gallardo, A. et al. Dielectric and magnetic properties of InCr1−xTixO3+x/2 (x = 3/4, 5/7 and 2/3) solid solution. Appl. Phys. A 126, 575 (2020). https://doi.org/10.1007/s00339-020-03618-y
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DOI: https://doi.org/10.1007/s00339-020-03618-y