Abstract
This research delves into the magnetic, structural, electrical, thermodynamic, and optical characteristics of spinel compounds ASc2O4 (where A = Cd, Zn). By utilizing the power of density functional theory and the full potential linearized augmented plane wave (FP-LAPW) method, we conduct a comprehensive investigation of these materials. Our study reveals that all the compounds under examination exhibit nonmagnetic (NM) behavior. Analysis of the electronic structure indicates the emergence of semiconducting metallic properties in the CdSc2O4 and ZnSc2O4 compounds. Notably, these compounds possess direct band gaps with energies of 2.94 eV and 4.64 eV for CdSc2O4, and 2.98 eV and 4.94 eV for ZnSc2O4, using the GGA and the TB- mBJ methods, respectively. By employing the Debye quasi-harmonic model, we investigate the thermodynamic parameters; including volume, heat capacity, thermal expansion coefficient, and Debye temperature. The thermodynamic results confirm the stability of ASc2O4 even under extremely high pressures and temperatures. Interestingly, our exploration of the optical properties reveals the potential of these compounds as candidates for optoelectronic devices, particularly within the visible to ultraviolet range. These findings present exciting possibilities for their practical applications in this spectral domain.
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References
Al-Qaisi, S., Rai, D. P., Alshahrani, T., Ahmed, R., Haq, B. U., Tahir, S. A., ... & Mahmood, Q. (2021). Structural, elastic, thermodynamic, electronic, optical and thermoelectric properties of MgLu2X4 (X= S, Se) spinel compounds from ab-initio calculations. Materials Science in Semiconductor Processing, 128, 105766. https://doi.org/10.1016/j.mssp.2021.105766
Amiri, B., Lazreg, A., Bensaber, F.A.: Optical and thermoelectric properties of Gd doped wurtzite GaN. Optik 240, 166798 (2021). https://doi.org/10.1016/j.ijleo.2021.166798
Andersen, O.K.: Linear methods in band theory. Phys. Rev. B 12(8), 3060 (1975). https://doi.org/10.1103/PhysRevB.12.3060
Anisimov, V.I., Aryasetiawan, F., Lichtenstein, A.I.: First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA+ U method. J. Phys. Condens. Matter 9(4), 767 (1997). https://doi.org/10.1088/0953-8984/9/4/002
Berri, S.: First-principles investigation of the physical properties of XSb2O6 (X= Ca, Sr, Ba) and YAs2O6 (Y= Mn, Co). Comput. Condens. Matter 22, e00440 (2020a). https://doi.org/10.1016/j.cocom.2019.e00440
Berri, S.: Theoretical analysis of the structural, electronic, optical and thermodynamic properties of trigonal and hexagonal Cs3Sb2I9 compound. Eur. Phys. J. B. 93, 1–12 (2020b). https://doi.org/10.1140/epjb/e2020-10143-1
Berri, S.: Theoretical study of physical properties of Ba3B (Nb, Ta) 2O9 (B= Mg, Ca, Sr, Cd, Hg, Zn, Fe, Mn, Ni, Co) perovskites. Comput. Condens. Matter 29, e00595 (2021a). https://doi.org/10.1016/j.cocom.2021.e00595
Berri, S.: Ab-initio calculations on structural, electronic, half-metallic and optical properties of Co-, Fe-, Mn-and Cr-doped Ba2 LuTaO6 Ba2 LuTaO 6. Pramana 95, 1 (2021b). https://doi.org/10.1007/s12043-020-02026-4
Blaha, P., Schwarz, K., Madsen, G. K., Kvasnicka, D., Luitz, J.: wien2k. An augmented plane wave+ local orbitals program for calculating crystal properties 60(1) (2001). https://www.scholars.northwestern.edu/en/publications/wien2k-an-augmented-plane-wave-plus-local-orbitals-program-for-ca
Blanco, M.A., Francisco, E., Luana, V.: GIBBS: isothermal-isobaric thermodynamics of solids from energy curves using a quasi-harmonic Debye model. Comput. Phys. Commun. 158(1), 57–72 (2004). https://doi.org/10.1016/j.comphy.2003.12.001
Bobrov, V.B., Trigger, S.A., Van Heijst, G.J.F., Schram, P.P.J.M.: Kramers-Kronig relations for the dielectric function and the static conductivity of Coulomb systems. Europhys. Lett. 90(1), 10003 (2010). https://doi.org/10.1209/0295-5075/90/10003/meta
Boujnah, M., Dakir, O., Zaari, H., Benyoussef, A., & El Kenz, A. (2014). Optoelectronic response of spinels CdX2O4 with X=(Al, Ga, In) through the modified Becke–Johnson functional. J. Appl. Phys. 116(12), 4896110. https://doi.org/10.1063/1.4896110
Claisse, A., Klipfel, M., Lindbom, N., Freyss, M., Olsson, P.: GGA+ U study of uranium mononitride: a comparison of the U-ram** and occupation matrix schemes and incorporation energies of fission products. J. Nucl. Mater. 478, 119–124 (2016). https://doi.org/10.1016/j.jnucmat.2016.06.007
Da Rocha, S., Thibaudeau, P.: Ab initio high-pressure thermodynamics of cationic disordered MgAl2O4 spinel. J. Phys. Condens. Matter 15(41), 7103 (2003). https://doi.org/10.1088/0953-8984/15/41/018/meta
Dernier, P.D., Remeika, J.P.: Synthesis and symmetry transformation in the perovskite compounds PbHfO3 and CdHfO3. Mater. Res. Bull. 10(3), 187–192 (1975). https://doi.org/10.1016/0025-5408(75)90154-3
Dulong, P.L., Petit, A.T.: Recherches sur quelques points importans de la theorie de la chaleur. Ann. Chim. Phys. 10, 395–413 (1819). http://www.ffn.ub.es/luisnavarro/nuevo_maletin/Petit--Dulong_1819.pdf
Ghosh, A., Kumari, A., Rajagopalan, M., Thangavel, R.: Electronic structure of spinel oxides ZnSc2O4 and ZnY2O4: a first principle study. In: AIP Conference Proceedings (Vol. 1675, No. 1). AIP Publishing (2015, August). https://doi.org/10.1063/1.4929168
Grimes, R.W., Anderson, A.B., Heuer, A.H.: Predictions of cation distributions in AB2O4 spinels from normalized ion energies. J. Am. Chem. Soc. 111(1), 1–7 (1989). https://doi.org/10.1021/ja00183a001
Gueddim, A., Zerroug, S., Bouarissa, N.: Optical characteristics of ZnTe1− xOx alloys from first-principles calculations. J. Lumin. 135, 243–247 (2013). https://doi.org/10.1016/j.jlumin.2012.10.004
Guermit, Y., Drief, M., Lantri, T., Tagrerout, A., Rached, H., Benkhettou, N.E., Rached, D.: Theoretical investigation of magnetic, electronic, thermoelectric and thermodynamic properties of Fe2TaZ (Z= B, In) compounds by GGA and GGA+ U approaches. Comput. Condens. Matter 22, e00438 (2020). https://doi.org/10.1016/j.cocom.2019.e00438
Guermit, Y., Caid, M., Rached, D., Drief, M., Rekab-Djabri, H., Lantri, T., Benkhettou, N.: Investigation of structural, elastic, electronic, magnetic and thermoelectric proprieties for Mn 2 RhZ (Z= Al, Si and Ge) full-Heusler alloys. Int. J. Thermophys. 42, 1–18 (2021). https://doi.org/10.1007/s10765-021-02841-w
Hachemaoui, M., Khenata, R., Bouhemadou, A., Bin-Omran, S., Reshak, A.H., Semari, F., Rached, D.: Prediction study of the structural and elastic properties for the cubic skutterudites LaFe4A12 (A= P, As and Sb) under pressure effect. Solid State Commun. 150(39–40), 1869–1873 (2010). https://doi.org/10.1002/pssb.200844142
Hill, R. J., Craig, J. R., & Gibbs, G. V. (1979). Systematics of the spinel structure type. Physics and chemistry of minerals, 4(4), 317–339. https://doi.org/10.1007/BF00307535
Hohenberg, P., Kohn, W.: Inhomogeneous electron gas. Phys. Rev. 136(3B), B864 (1964). https://doi.org/10.1103/PhysRev.136.B864
Khan, S.A., Reshak, A.H.: First principle study of electronic structure, chemical bonding and optical properties of 5-azido-1H-tetrazole. Int. J. Electrochem. Sci. 8(7), 9459–9473 (2013). https://doi.org/10.1016/S1452-3981(23)12986-5
Kohn, W., Sham, L.J.: Self-consistent equations including exchange and correlation effects. Phys. Rev. 140(4A), A1133 (1965). https://doi.org/10.1103/PhysRev.140.A1133
Labeau, M., Reboux, V., Dhahri, D., Joubert, J.C.: New mixed oxides as thin film transparent electrodes: spinel phase CdIn2O4. Thin Solid Films 136(2), 257–262 (1986). https://doi.org/10.1016/0040-6090(86)90284-1
Lavrentyev, A.A., Gabrelian, B.V., Vu, V.T., Denysyuk, N.M., Shkumat, P.N., Tarasova, A.Y., Khyzhun, O.Y.: Electronic structure and optical properties of RbPb2Br5. J. Phys. Chem. Solids 91, 25–33 (2016). https://doi.org/10.1016/j.jpcs.2015.12.003
Lintz, H.G.: Réseaux de réactions dans l’oxydation catalytique de composés organiques: utilité et limitations. Oil Gas Sci. Technol. 57(6), 653–663 (2002). https://doi.org/10.2516/ogst:2002045
Mahmood, Q., Rashid, M., Noor, N.A., Ashiq, M.G.B., Ramay, S.M., Mahmood, A.: Opto-electronic and thermoelectric properties of MgIn2X4 (X= S, Se) spinels via ab-initio calculations. J. Mol. Graph. Model. 88, 168–173 (2019). https://doi.org/10.1016/j.jmgm.2019.01.010
Morales, M.R., Barbero, B.P., Cadus, L.E.: Evaluation and characterization of Mn–Cu mixed oxide catalysts for ethanol total oxidation: influence of copper content. Fuel 87(7), 1177–1186 (2008). https://doi.org/10.1016/j.fuel.2007.07.015
Murnaghan, F.D.: The compressibility of media under extreme pressures. Proc. Natl. Acad. Sci. 30(9), 244–247 (1944). https://doi.org/10.1073/pnas.30.9.244
Naseem, M., Aziz, A., Aldaghfag, S.A., Yaseen, M., Neffati, R.: A DFT investigation of Al2XS4 (X= Hg, Mg) for energy harvesting applications. J. Phys. Chem. Solids 171, 110982 (2022). https://doi.org/10.1016/j.jpcs.2022.110982
Nguyen, S.H., Koffyberg, F.P.: Optical band gap and electron affinity of semiconducting CdGa2O4. Solid State Commun. 76(11), 1243–1245 (1990). https://doi.org/10.1016/0038-1098(90)90568-V
Nozik, A.J.: Optical and electrical properties of Cd 2 Sn O 4: a defect semiconductor. Phys. Rev. B 6(2), 453 (1972). https://doi.org/10.1103/PhysRevB.6.453
Otero-de-la-Roza, A., Abbasi-Pérez, D., & Luaña, V.: Gibbs2: A new version of the quasiharmonic model code. II. Models for solid-state thermodynamics, features and implementation. Comput. Phys. Commun. 182(10), 2232–2248 (2011). https://doi.org/10.1016/j.cpc.2011.05.009
Perdew, J.P., Burke, K., Ernzerhof, M.: Generalized gradient approximation made simple. Phys. Rev. Lett. 77(18), 3865 (1996). https://doi.org/10.1103/PhysRevLett.77.3865
Peterson, R.C., Lager, G.A., & Hitterman, R.L.: A time-of-flight neutron powder diffraction study of MgAl2O4 at temperatures up to 1273 K. Am. Mineral. 76(9–10), 1455–1458 (1991). https://pubs.geoscienceworld.org/msa/ammin/article-abstract/76/9-10/1455/105141/A-time-of-flight-neutron-powder-diffraction-study
Quintero, J.M., Torres, C.R., Errico, L.A.: Ab initio calculation of structural, electronic and magnetic properties and hyperfine parameters at the Fe sites of pristine ZnFe2O4. J. Alloys Compd. 741, 746–755 (2018). https://doi.org/10.1016/j.jallcom.2018.01.217
Reshak, A.H., Khan, S.A., Alahmed, Z.A.: Investigation of electronic structure and optical properties of MgAl2O4: DFT approach. Opt. Mater. 37, 322–326 (2014). https://doi.org/10.1016/j.optmat.2014.06.017
Saha, S., Sinha, T.P., Mookerjee, A.: Electronic structure, chemical bonding, and optical properties of paraelectric BaTiO 3. Phys. Rev. B 62(13), 8828 (2000). https://doi.org/10.1103/PhysRevB.62.8828
Salcedo Rodriguez, K.L., Melo Quintero, J.J., RodrÍguez Torres, C.E., Errico, L.A.: Ab initio study of FeAl2O4 and Fe2AlO4: analysis of structural, magnetic and hiperfyne properties (2021). https://doi.org/10.1016/j.jallcom.2018.10.082
Shannon, R.D., Gillson, J.L., Bouchard, R.J.: Single crystal synthesis and electrical properties of CdSnO3, Cd2SnO4, In2TeO6 and Cdln2O4. J. Phys. Chem. Solids 38(8), 877–881 (1977). https://doi.org/10.1016/0022-3697(77)90126-3
Siegel, L.A.: A spinel form of cadmium stannate. J. Appl. Crystallogr. 11(4), 284–286 (1978). https://doi.org/10.1107/S0021889878013321
Tahir, W., Mustafa, G.M., Noor, N.A., Alay-e-Abbas, S.M., Mahmood, Q., Laref, A.: Analysis of optoelectronic and trasnport properties of magnesium based MgSc2X4 (X= S, Se) spinels for solar cell and energy storage device applications. Ceram. Int. 46(17), 26637–26645 (2020). https://doi.org/10.1016/j.ceramint.2020.07.133
Tasca, J.E., Quincoces, C.E., Lavat, A., Alvarez, A.M., González, M.G.: Preparation and characterization of CuFe2O4 bulk catalysts. Ceram. Int. 37(3), 803–812 (2011). https://doi.org/10.1016/j.ceramint.2010.10.023
Thibaudeau, P., Gervais, F.: Ab initio investigation of phonon modes in the MgAl2O4 spinel. J. Phys. Condens. Matter 14(13), 3543 (2002). https://doi.org/10.1088/0953-8984/14/13/312/meta
Tran, F., Blaha, P.: Accurate band gaps of semiconductors and insulators with a semilocal exchange-correlation potential. Phys. Rev. Lett. 102(22), 226401 (2009). https://doi.org/10.1103/PhysRevLett.102.226401
Ueda, N., Omata, T., Hikuma, N., Ueda, K., Mizoguchi, H., Hashimoto, T., Kawazoe, H.: New oxide phase with wide band gap and high electroconductivity, MgIn2O4. Appl. Phys. Lett. 61(16), 1954–1955 (1992). https://doi.org/10.1063/1.1083744
Wei, S.H., Zhang, S.B.: First-principles study of cation distribution in eighteen closed-shell AIIB2IIIO4 and AIVB2IIO4 spinel oxides. Phys. Rev. B 63(4), 045112 (2001). https://doi.org/10.1103/PhysRevB.63.045112
Yang, F.F., Fang, L., Zhang, S.F., Liao, K.J., Liu, G.B., Dong, J.X., Fu, G.Z.: Optical properties of CdIn2O4 thin films prepared by DC reactive magnetron sputtering. J. Cryst. Growth 297(2), 411–418 (2006). https://doi.org/10.1016/j.jcrysgro.2006.10.103
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YG: Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Visualization, Writing—original draft; KH: Conceptualization, Data curation, Formal analysis, Investigation; MD: Visualization, Methodology, Resources; TL: Formal analysis, Data curation; HR-D: ideology, methodology, writing-original copy, revision; AM: Investigation, Methodology; HR: Formal analysis, Investigation, Methodology, Validation, Visualization; DR: ideology, methodology, writing-original copy, revision; NB: Formal analysis, Investigation, Methodology.
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Guermit, Y., Hocine, K., Drief, M. et al. Theoretical investigation of the physical properties of spinel-type catalysts based on Scandium: CdSc2O4 and ZnSc2O4. Opt Quant Electron 56, 537 (2024). https://doi.org/10.1007/s11082-023-06056-1
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DOI: https://doi.org/10.1007/s11082-023-06056-1