Abstract
A semiconductor double perovskite oxide Y2CuTiO6 with a wide band gap was synthesized by solid-state reaction. The compound was characterized by x-ray diffraction, scanning electron microscopy, energy-dispersive x-ray spectroscopy, thermogravimetric analysis, UV–visible diffuse reflectance spectroscopy, photoluminescence excitation and emission spectroscopy. Rietveld refinement of x-ray diffraction pattern using the General Structure Analysis System-II indicated a hexagonal structure with space group P63cm (#185) with lattice parameters a = b = 6.199(2) Å and c = 11.516(4) Å. Trigonal bi-pyramidal Ti(IV)/Cu(II)O5 is arranged randomly in the B sites of Y2CuTiO6. Microscopic measurements confirmed a dense microstructure with Y:Cu:Ti = 2:1:1. Thermogravimetric analysis showed high thermal stability of this compound, which is desired for optical applications. UV–VIS DRS spectra displayed wide band absorption in the visible region with a band gap of 2.98 eV as commonly seen in wide-band-gap semiconductors. From the photoluminescence excitation spectra, maximum excitation was observed around 365 nm, so the compound was excited by a 355 nm laser to study the emission properties. A broad emission spectrum is observed in the visible range from the photoluminescence emission study. The lead-free double perovskite with high material stability against temperature showing huge absorption and emission in the visible region without any intrinsic doping is unique and interesting for a wide range of applications.
Graphic Abstract
Similar content being viewed by others
References
A. Hossain, P. Bandyopadhyay, and S. Roy, An overview of double perovskites A2B′B″O6 with small ions at A site: synthesis, structure and magnetic properties. J. Alloys Compd 740, 414 (2018).
S. Vasala and M. Karppinen, A2B′B″O6 perovskites: a review. Prog. Solid. State Ch. 43, 1 (2015).
D. Li, J. Zheng, and Z. Zou, Band structure and photocatalytic properties of perovskite-type compound Ca2NiWO6 for water splitting. J. Phys. Chem. Solids 67, 801 (2006).
M. Lv, Y. Wang, L. Lu, R. Wang, S. Ni, G. Liu, and X. Xu, Structural dependence of the photocatalytic properties of double perovskite compounds A2InTaO6 (A = Sr or Ba) doped with nickel. Phys. Chem. Chem. Phys. 18, 21491 (2016).
M.D.I. Bhuyan, S. Das, and M.A. Basith, Sol–gel synthesized double perovskite Gd2FeCrO6 nanoparticles: structural, magnetic and optical properties. J. Alloys Compd 878, 160389 (2021).
Z. Xiao, Z. Song, and Y. Yan, From lead halide perovskites to lead-free metal halide perovskites and perovskite derivatives. Adv. Mater. 31, 1803792 (2019).
X. Yang, Y. Wang, J. Jiang, M. Li, Z. Tang, H. Cai, F. Zhang, and X. Wu, Composition effects on structure and optical properties in double perovskite derivatives semiconductors Cs2SnI6−xBrx (x = 0–6). APL Mater. 8, 021102 (2020).
A.N. Romanov, E.V. Haula, D.P. Shashkin, and V.N. Korchak, Broadband Near-IR photoluminescence of trigonal-bipyramidal coordinated Cu2+ impurity center in YGaO3, YInO3 and GdInO3 hexagonal phases. J. Lumin. 228, 117652 (2020).
T. Zheng, L. Luo, P. Du, S. Lis, U.R. Rodríguez-Mendoza, V. Lavín, and M. Runowski, Highly-efficient double perovskite Mn4+-activated Gd2ZnTiO6 phosphors: a bifunctional optical sensing platform for luminescence thermometry and manometry. Chem. Eng. J. 446, 136839 (2022).
A.M. Idris, T. Liu, J.H. Shah, H. Han, and C. Li, Sr2CoTaO6 double perovskite oxide as a novel visible-light-absorbing bifunctional photocatalyst for photocatalytic oxygen and hydrogen evolution reactions. ACS Sustain. Chem. Eng. 8, 14190 (2020).
M.B. Gray, S. Hariyani, T.A. Strom, J.D. Majher, J. Brgoch, and P.M. Woodward, High-efficiency blue photoluminescence in the Cs2NaInCl6:Sb3+ double perovskite phosphor. J. Mater. Chem. C 8, 6797 (2020).
E.W.J.L. Oomen, G.J. Dirksen, W.M.A. Smit, and G. Blasse, On the luminescence of the Sb3+ ion in Cs2NaMBr6, (M = Sc, Y, La). J. Phys. C Solid State Phys. 20, 1161 (1987).
G. Volonakis, N. Sakai, H.J. Snaith, and F. Giustino, Oxide analogs of halide perovskites and the new semiconductor Ba2AgIO6. J. Phys. Chem. Lett. 10, 1722 (2019).
A.S. Thind, S. Kavadiya, M. Kouhnavard, R. Wheelus, S.B. Cho, L.-Y. Lin, C. Kacica, H.K. Mulmudi, K.A. Unocic, A.Y. Borisevich, G. Pilania, P. Biswas, and R. Mishra, KBaTeBiO6: a lead-free, inorganic double-perovskite semiconductor for photovoltaic applications. Chem. Mater. 31, 4769 (2019).
N. Floros, J.T. Rijssenbeek, A.B. Martinson, and K.R. Poeppelmeier, Structural study of A2CuTiO6 (A = Y, Tb-Lu) compounds. Solid State Sci. 4, 1495 (2002).
D. Choudhury, A. Hazarika, A. Venimadhav, C. Kakarla, K.T. Delaney, P.S. Devi, P. Mondal, R. Nirmala, J. Gopalakrishnan, N.A. Spaldin, U.V. Waghmare, and D.D. Sarma, Electric and magnetic polarizabilities of hexagonal Ln2CuTiO6 (Ln = Y, Dy, Ho, Er, and Yb). Phys. Rev. B 82, 134203 (2010).
K. Singh, N. Kumar, B. Singh, S.D. Kaushik, N.K. Gaur, S. Bhattacharya, S. Rayaprol, and C. Simon, Magnetic and dielectric properties of R2CuTiO6 compounds (R = Y, La, Pr and Nd). J. Supercond. Nov. Magn. 24, 1829 (2011).
B.H. Toby, and R.B. Von Dreele, GSAS-II: the genesis of a modern open-source all purpose crystallography software package. J. Appl. Crystallogr. 46, 544–549 (2013).
S. Kundu, A. Hossain, S. Pranava Keerthi, R. Das, M. Baenitz, P.J. Baker, J.-C. Orain, D.C. Joshi, R. Mathieu, P. Mahadevan, S. Pujari, S. Bhattacharjee, A.V. Mahajan, and D.D. Sarma, Signatures of a spin-1/2 cooperative paramagnet in the diluted triangular lattice of Y2CuTiO6. Phys. Rev. Lett. 125, 117206 (2020).
M. Sharma, A. Yangui, V.R. Whiteside, I.R. Sellers, D. Han, S. Chen, M.-H. Du, and B. Saparov, Rb4Ag2BiBr9: a lead-free visible light absorbing halide semiconductor with improved stability. Inorg. Chem. 58, 4446 (2019).
G. Pozza, D. Ajo, G. Chiari, F. De Zuane, and M. Favaro, Photoluminescence of the inorganic pigments Egyptian blue, han blue and han purple. J. Cult. Herit. 1, 393 (2000).
Acknowledgments
Authors would like to thank Dr. P.K. Ajikumar, SND, MSG, IGCAR for TGA measurements.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Saha, P., Nithya, R. & Sen, S. Lead-Free Stable Wide-Band-Gap Double Perovskite with Absorption in the Visible Region. J. Electron. Mater. 52, 2971–2976 (2023). https://doi.org/10.1007/s11664-023-10262-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11664-023-10262-8