TiPbO₃ Kristalinin Yapısı ve Özellikleri Hakkında Ab Initio Öngörüleri

Öz

Perovskit malzemeler pek çok uygulama için potansiyeli olan kristal malzemelerdir. Bu nedenle bu çalışmada temel prensip hesaplamalarına dayalı olarak TiPbO3 kübik perovskit kristalinin yapısal, elastik, elektronik ve optik özellikleri araştırılmıştır. Bu özellikleri belirlerken ABINIT programı kullanılmıştır. Hesaplamalar sonucunda TiPbO3 kristalinin örgü parametresi 7.6344 Bohr olarak belirlenmiştir. Ayrıca, TiPbO3 kübik perovskit kristalinin yarıiletken olduğu ve band aralığının 2.39 eV olduğu sonucuna ulaşılmıştır. TiPbO3 kristali için elastik özellikler araştırıldığında elastik sertlik sabitlerinden yola çıkarak elde edilen Poisson oranına bakarak kristalin esnek davranış sergilediği tahmin edilmektedir. Son olarak optik özellikleri incelenerek TiPbO3 kristalinin kompleks dielektrik fonksiyonu, kırılma indisi, soğurma katsayısı, sönüm katsayısı ve yansıtıcılığı hesaplanmıştır.

Anahtar Kelimeler

• Elastik özellikler
• Optik özellikler
• TiPbO3
• Yoğunluk Fonksiyoneli Teorisi

Ab Initio Insights Into The Structure and Properties of TiPbO₃ Crystal

Öz

Perovskite materials are crystalline materials with potential for many applications. Therefore, in this study, the structural, elastic, electronic and optical properties of TiPbO3 cubic perovskite crystal have been investigated based on calculations from first principles. ABINIT programme was used to determine these properties. As a result of the calculations, the lattice parameter of TiPbO3 crystal was determined as 7.6344 Bohr. It was also concluded that TiPbO3 cubic perovskite crystal is a semiconductor and its band gap is 2.39 eV. When the elastic properties are investigated for TiPbO3 crystal, it is estimated that the crystal exhibits flexible behaviour based on the Poisson ratio obtained from the elastic stiffness constants. Finally, the complex dielectric function, refractive index, absorption coefficient, extinction coefficient and reflectivity of TiPbO3 crystal were calculated by examining its optical properties.

Anahtar Kelimeler

• Elastic properties
• Optical properties
• TiPbO3
• Density Functional Theory

Kaynakça

1. Aftab, S., Nawaz, T., &Bilal Tahir, M. (2021). Recent development in shape memory based perovskite materials for energy conversion and storage applications. International Journal of Energy Research, 45(15), 20545-20558. doi:10.1002/er.7151
2. Amisi, S., Bousquet, E., Katcho, K., & Ghosez, P. (2012). First-principles study of structural and vibrational properties of SrZrO 3. Physical Review B—Condensed Matter and Materials Physics, 85(6), 064112. doi:10.1103/PhysRevB.85.064112
3. Bilc, D. I., Orlando, R., Shaltaf, R., Rignanese, G. M., Íñiguez, J., & Ghosez, P. (2008). Hybrid exchange-correlation functional for accurate prediction of the electronic and structural properties of ferroelectric oxides. Physical Review B—Condensed Matter and Materials Physics, 77(16), 165107. doi.org/10.1103/PhysRevB.77.165107
4. Boudali, A., Driss Khodja, M., Armani, B., Bourbie, D., Amara, K.., & Abada, A. (2009). First principles study of structural, elastic, electronic and thermal properties of SrTiO3 perovskite cubic. Physics Letters A, 373, 8-9, 879-884. doi:10.1016/j.physleta.2008.12.017
5. Chen, J., Matsushita, Y., Kolodiazhnyi, T., Belik, A. A., Tsujimoto, Y., Katsuya, Y., Tanaka, M., Su, Y., Shi, Y., & Yamaura, K. (2018). High-Pressure Synthesis, Crystal Structure, and Semimetallic Properties of HgPbO3. Inorganic Chemistry, 57, 7601−7609. doi: 10.1021/acs.inorgchem.8b00482
6. Daga, A., & Sharma, S. (2012). Ab-Initio Structural Study of SrMoO3 Perovskite. Journal of Modern Physics, 3(12), 1891-1894. doi:10.4236/jmp.2012.312238
7. Derkaoui, I., Achehboune, M., Eglitis, R.I., Popov, A.I., & Rezzouk, A. (2023). Overview of the Structural, Electronic and Optical Properties of the Cubic and Tetragonal Phases of PbTiO3 by Applying Hubbard Potential Correction. Materials, 16, 4302. doi:10.3390/ ma16124302
8. Dimos, D., & Mueller, C. H. (1998). Perovskite thin films for high-frequency capacitor applications. Annual Review of Materials Science, 28(1), 397-419. doi:10.1146/annurev.matsci.28.1.397

9. Dixit, A., Dahshan, A., Tripathi, S. K., Srivastava, A., Behera, D., Sharma, R., & Omran, S. B. (2024). Insight into the structural, electronic, optical, thermodynamic and thermoelectric properties of the cubic PbSiO3 Perovskite: a first-principles computation. Chinese Journal of Physics, 92, 1474-1491. doi:10.1016/j.cjph.2023.10.023
10. Fermi, E. (1927). Statistical method to determine some properties of atoms. Rend. Accad. Naz. Lincei, 6(602-607), 5.
11. Fuchs, M., & Scheffler, M. (1999). Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density functional theory. Computer Physics Communications, 119(1), 67-98. doi:10.1016/S0010-4655(98)00201-X
12. Geusic J. E., Kurtz S. K., Vn Uitert L. G., & Wemple S., H. (1964). Electro-Optic Properties of Some Abo3 Perovskites In The Paraelectric Phase, Appl. Phys. Lett., 4, 141–143. doi: 10.1063/1.1754003
13. Ghosez, P., Cockayne, E., Waghmare, U. V., & Rabe, K. M. (1999). Lattice dynamics of BaTiO 3, PbTiO 3, and PbZrO 3: A comparative first-principles study. Physical Review B, 60(2), 836. doi:10.1103/PhysRevB.60.836
14. Gonze, X., Beuken, J. M., Caracas, R., Detraux, F., Fuchs, M., Rignanese, G. M., & Allan, D. C. (2002). First-principles computation of material properties: the ABINIT software project. Computational Materials Science, 25(3), 478-492. doi:10.1016/S0927-0256(02)00325-7
15. Hohenberg, P., & Kohn, W. (1964). Inhomogeneous electron gas. Physical review, 136(3B), B864. Doi:10.1103/PhysRev.136.B864
16. Hossain, M. K., Toki, G. I., Kuddus, A., Rubel, M. H., Hossain, M. M., Bencherif, H., & Mushtaq, M. (2023). An extensive study on multiple ETL and HTL layers to design and simulation of high-performance lead-free CsSnCl3-based perovskite solar cells. Scientific Reports, 13(1), 2521.doi:10.1038/s41598-023-28506-2
17. Hosseini, S. M., Movlarooy, T., & Kompany, A., (2007). First principle calculations of the chosive energy and the electronic properties of PbTiO3. Physica B 391, 316-321. doi:10.1016/j.physb.2006.10.013
18. Ikegami, S., Ueda, I., & Nagata, T. (1971). Elektromechanical properties of PbTiO3 ceramics containing La and Mn. J. Acoust. Soc. Am., 50, 1060-1066. doi:10.1121/1.1912729
19. Jain, A., Ong, S. P., Hautier, G., Chen, W., Richards, W. D., Dacek, S., & Persson, K. A. (2013). Commentary: The Materials Project: A materials genome approach to accelerating materials innovation. APL materials, 1(1). doi:10.1063/1.4812323
20. Jiang, J., Kato, K., Fujimori, H., Yamakata, A., & Sahata, Y. (2020). Investigation on the highly actice SrTiO3 photocatalyst toward overall H2O splitting by doping Na ion. J Catal., 390, 81-89. doi:10.1016/j.jcat.2020.07.025
21. Khandy, S. A., Islam, I., Ganai, Z. S., Gupta, D. C., & Parrey, K. A. (2018). High-Temperature and High-Pressure Study of Electronic and Thermal Properties of PbTaO3 and SnAlO3 Metal Perovskites by Density Functional Theory Calculations. Journal of Electronic Materials, 47, 436- 442. doi: 10.1007/s11664-017-5785-1
22. Khedidji, M., Dahmane, M., & Trari, M. (2025). Dielectric and Dynamical properties of ABO3 (A= Li, Na; B= V, Nb): A Comparative First-Principles Study. Journal of Physics and Chemistry of Solids, 112595. https://doi.org/10.1016/j.jpcs.2025.112595
23. Kim, H., Kim, G., Jeon, Y. U., Lee, W., Lee, B. H., Kim, I. S., & Kim, J. (2024). Perovskite lanthanum‐doped barium stannate: A refractory near‐zero‐index material for high‐temperature energy harvesting systems. Advanced Science, 11(2), 2302410. Doi:10.1002/advs.202302410
24. King-Smith, R. D., & Vanderbilt, D. (1994). First-principles investigation of ferroelectricity in perovskite compounds. Physical Review B, 49(9), 5828. doi.org/10.1103/PhysRevB.49.5828
25. Kohn, W., & Sham, L. J. (1965). Self-consistent equations including exchange and correlation effects. Physical review, 140(4A), A1133. doi:10.1103/PhysRev.140.A1133
26. Li, Y., Liu, Y., Tang, M., Lv, J., Chen, F., Li, Q., ... & Liu, G. (2021). Energy storage performance of BaTiO3-based relaxor ferroelectric ceramics prepared through a two-step process. Chemical Engineering Journal, 419, 129673.doi:10.1016/j.cej.2021.129673
27. Li, Z., Grimsditch, M., Foster, C. M., & Chan, S. K. (1996). Dielectric and elastic properties of ferroelectric materials at elevated temperature. Journal of Physics and Chemistry of Solids, 57(10), 1433-1438. doi.org/10.1016/0022-3697(96)00009-1
28. Longo, J. M., & Kafalas, J. A. (1968). Pressure-induced structural changes in the system Ba1− xSrxRuO3. Materials Research Bulletin, 3(8), 687-692. doi:10.1016/0025-5408(68)90118-9
29. Lv, H., Gao, H., Yang, Y., & Liu, L. (2011). Density functional theory (DFT) investigation on the structure and electronic properties of the cubic perovskite PbTiO3. Applied Catalysis A: General, 404(1-2), 54-58. doi:10.1016/j.apcata.2011.07.010
30. Maizi, R., Ksouri, R., Cheghib, N., Boudjahem, A. G., & Derdare, M. (2023). First-Principles Calculations of Structural, Elastic, Electronic, and Thermodynamic Properties of ATiO3 (A= Ba or Pb) Perovskites. Russian Journal of Inorganic Chemistry, 68(8), 1019-1028.
31. Mishra, V., Sagdeo, A., Kumar, V., Warshi, M. K., Rai, H. M., Saxena, S. K., ... & Sagdeo, P. R. (2017). Electronic and optical properties of BaTiO3 across tetragonal to cubic phase transition: An experimental and theoretical investigation. Journal of Applied Physics, 122(6).doi:10.1063/1.4997939
32. Momma, K., & Izumi, F. (2011). VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. Applied Crystallography, 44(6), 1272-1276. doi:10.1107/S0021889811038970
33. Monkhorst, H. J., ve Pack, J. D. (1976). Special points for Brillouin-zone integrations. Physical review B, 13(12), 5188. doi:10.1103/PhysRevB.13.5188
34. Mouhat, F., & Coudert, F. X. (2014). Necessary and sufficient elastic stability conditions in various crystal systems. Physical review B, 90(22), 224104.
35. Nazir, G., Ahmad, A., Khan, M. F., & Tariq, S. (2015). Putting DFT to the trial: First principles pressure dependent analysis on optical properties of cubic perovskite SrZrO. Computational Condensed Matter, 4, 32-39. doi:10.1016/j.cocom.2015.07.002
36. Noor, N. A., Mahmood, Q., Rashid, M., Haq, B. U., Laref, A., & Ahmad, S. A. (2018). Ab-initio study of thermodynamic stability, thermoelectric and optical properties of perovskites ATiO3 (A=Pb, Sn). Journal of Solid State Chemistry, 263, 115-122. doi:10.1016/j.cocom.2015.07.002
37. Nye, J. F. (1985). Physical properties of crystals: their representation by tensors and matrices. Oxford university press.
38. Ortega-San-Martin H. (2020) Correction to: Introduction to Perovskites: A Historical Perspective, in Revolut. Perovskite, ed. N. S. Arul, and V. D. Nithya, Springer Singapore, Singapore, pp. C1. doi: 10.1007/978-981-15-1267-4_12
39. Paris, E. C., Gurgel, M. F. C., Boschi, T. M., Joya, M. R., Pizani, P. S., Souza, A. G., ... & Longo, E. (2008). Investigation on the structural properties in Er-doped PbTiO3 compounds: A correlation between experimental and theoretical results. Journal of alloys and compounds, 462(1-2), 157-163.doi:10.1016/j.jallcom.2007.07.107
40. Peng, C. H., Chang, J. F., & Desu, S. (1992). Optical Properties of PZT, PLZT, and PNZT Thin Films. vol. 243, Materials Research Society. doi:10.1557/PROC-243-21
41. Perdew, J. P., Burke, K., & Ernzerhof, M. (1996). Generalized gradient approximation made simple. Physical review letters, 77(18), 3865. doi:10.1103/PhysRevLett.77.3865
42. Piskunov, S., Heifets, E., Eglitis, R. I., & Borstel, G. (2004). Bulk properties and electronic structure of SrTiO3, BaTiO3, PbTiO3 perovskites: an ab initio HF/DFT study. Computational Materials Science, 29(2), 165-178. doi.org/10.1016/j.commatsci.2003.08.036
43. Rao, C. N., Dua, P., Kuchhal, P., Lu, Y., Kale, S. N., & Cao, P. (2019). Enhanced sensitivity of magneto-optical sensor using defect induced perovskite metal oxide nanomaterial. Journal of Alloys and Compounds, 797, 896-901. doi:10.1016/j.jallcom.2019.05.118
44. Roknuzzaman, M., Ostrikov, K., Wang , H., Du, A., & Tesfamichael, T. (2017) Towards lead-free perovskite photovoltaics and optoelectronics by ab-initio simulations, Sci. Rep., 7 , 14025. doi: 10.1038/s41598-017-13172-y
45. Rouf, S. A., Hussain, M. I., Mumtaz, U., Majeed, A., M., & Masood, H. T. (2021). A density functional theory study of the structural, electronic, and optical properties of XGaO3 (X = V, Nb) perovskites for optoelectronic applications, J. Comput. Electron., 20, 1484–1495. doi: 10.1007/s10825-021-01718-3
46. Saikot, M. S. H., Rafiu, R., Apon, I. A., El-Rayyes, A., Rahman, M. A., Shkir, M., ... & Marnadu, R. (2025). First-principles investigation of structural, electronic, optical, mechanical, and phonon properties of Pb-and Sn-based cubic oxide perovskites for optoelectronic applications. RSC advances, 15(46), 39071-39091. DOI: 10.1039/D5RA06065F
47. Samara, G. A. (2003). The relaxational properties of compositionally disordered ABO3 perovskites. J. Phys.:Condens. Matter, 2003, 15, R367–R411.doi: 10.1088/0953-8984/15/9/202
48. Scrimshire, A., Lobera, A., Bell, A. M. T., Jones, A. H., Sterianou, I., Forder S. D. & Bingham, P.A. (2018). Determination of Debye temperatures and Lamb–Mössbauer factors for LnFeO3 orthoferrite perovskites (Ln = La, Nd, Sm, Eu, Gd). Journal of Physics: Condensed Matter, 30, 105704. doi:10.1088/1361-648X/aaab7d
49. Selmani, Y., Labrim, H., & Bahmad, L. (2025). Structural, electronic, optical and thermoelectric properties of LaMO3 (M= Ga or In) cubic perovskites: DFT study. Modern Physics Letters B, 39(16), 2450464. doi:10.1142/S0217984924504645
50. Syue, Y. K., Hsu, K. C., Fang, T. H., Lee, C. I., & Shih, C. J. (2022). Characteristics and gas sensor applications of ZnO-Perovskite heterostructure. Ceramics International, 48(9), 12585-12591. doi:10.1016/j.ceramint.2022.01.126
51. Szafraniak, B., Fuśnik, Ł., Xu, J., Gao, F., Brudnik, A., & Rydosz, A. (2021). Semiconducting metal oxides: SrTiO3, BaTiO3 and BaSrTiO3 in gas-sensing applications: A review. Coatings, 11(2), 185.doi:10.3390/coatings11020185
52. Tariq, S., Ahmed, A., Saad, S., & Tariq, S. (2015). Structural, electronic and elastic properties of the cubic CaTiO3 under pressure: A DFT study. AIP Advances 5, 077111. doi:10.1063/1.4926437
53. Thomas, L. H. (1927). The calculation of atomic fields. In Mathematical proceedings of the Cambridge philosophical society (Vol. 23, No. 5, pp. 542-548). Cambridge University Press. doi:10.1017/S0305004100011683
54. Troullier, N., & Martins, J. L. (1991). Efficient pseudopotentials for plane-wave calculations. Physical review B, 43(3), 1993. doi:10.1103/PhysRevB.43.1993
55. Uludoğan, M., Guarin, D. P., Gomez, Z. E., Cagın, T., & Goddard, W. A. (2008). DFT Studies on Ferroelectric Ceramics and Their Alloys; BaTiO3, PbTiO3, AgNbO3, AgTaO3, PbxBa1-xTiO3 and SrxBa1-xTiO3, CMES, 24, 3, 215-238. doi:10.3970/cmes.2008.024.215
56. Wang, S., Tang, S., Gao, H., Chen, X., Liu, H., Yu, C., ... & Yang, H. (2021). Microstructure, optical, photoluminescence properties and the intrinsic mechanism of photoluminescence and photocatalysis for the BaTiO3, BaTiO3/TiO2 and BaTiO3/TiO2/CeO2 smart composites. Optical Materials, 118, 111273.doi:10.1016/j.optmat.2021.111273
57. Yan, S. Y., Xie, Y., Liu, T., & Yu, H. T. (2010). Electronic structures and ferroelectric instabilities of cubicAV O3 (A= Sr, Ba, and Pb) perovskites by first-principles calculations. Journal of Physics: Condensed Matter, 22(12), 125501. doi:10.1088/0953-8984/22/12/125501
58. Yoshiasa, A., Nakatani, T., Nakatsuka, A., Okube, M., Sugiyama, K., & Mashimo, T. (2016). High-temperature single-crystal X-ray diffraction study of tetragonal and cubic perovskite-type PbTiO3 phases. Structural Science, 72(3), 381-388. doi.org/10.1107/S2052520616005114
59. Yu, B., Shi, J., Li, Y., Tan, S., Cui, Y., Meng, F., ... & Meng, Q. (2025). Regulating three-layer full carbon electrodes to enhance the cell performance of CsPbI3 perovskite solar cells. Nature Communications, 16(1), 3328. doi:10.1038/s41467-025-58672-y
60. Zhang, L., Pu, Y., Chen, M., Peng, X., Wang, B., & Shang, J. (2023). Design strategies of perovskite energy-storage dielectrics for next-generation capacitors. Journal of the European Ceramic Society, 43(14), 5713-5747. doi:10.1016/j.jeurceramsoc.2023.06.037