Identifying the ground state structures of point defects in solids
Source abstract
Abstract
Abstract Point defects are a universal feature of crystals. Their identification is addressed by combining experimental measurements with theoretical models. The standard modelling approach is, however, prone to missing the ground state atomic configurations associated with energy-lowering reconstructions from the idealised crystallographic environment. Missed ground states compromise the accuracy of calculated properties. To address this issue, we report an approach to navigate the defect configurational landscape using targeted bond distortions and rattling. Application of our workflow to eight materials (CdTe, GaAs, Sb2S3, Sb2Se3, CeO2, In2O3, ZnO, anatase-TiO2) reveals symmetry breaking in each host crystal that is not found via conventional local minimisation techniques. The point defect distortions are classified by the associated physico-chemical factors. We demonstrate the impact of these defect distortions on derived properties, including formation energies, concentrations and charge transition levels. Our work presents a step forward for quantitative modelling of imperfect solids.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Chalcogenide Semiconductor Thin Films · Advanced Semiconductor Detectors and Materials · Machine Learning in Materials Science
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (100+)
Show source-provided references
1. Arrigoni, M. & Madsen, G. K. H. Evolutionary computing and machine learning for discovering of low-energy defect configurations. npj Comput. Mater. 7, 1–13 (2021).10.1038/s41524-021-00537-1 ↗
2. Ong, S. P., Mo, Y. & Ceder, G. Low hole polaron migration barrier in lithium peroxide. Phys. Rev. B 85, 081105 (2012).10.1103/PhysRevB.85.081105 ↗
3. Evarestov, R. A. et al. Use of site symmetry in supercell models of defective crystals: polarons in CeO2. Phys. Chem. Chem. Phys. 19, 8340–8348 (2017).10.1039/C6CP08582B ↗
4. Lany, S. & Zunger, A. Metal-dimer atomic reconstruction leading to deep donor states of the anion vacancy in II-VI and chalcopyrite semiconductors. Phys. Rev. Lett. 93, 156404 (2004).10.1103/PhysRevLett.93.156404 ↗
5. Lindström, A., Mirbt, S., Sanyal, B. & Klintenberg, M. High resistivity in undoped CdTe: carrier compensation of Te antisites and Cd vacancies. J. Phys. D. 49, 035101 (2015).10.1088/0022-3727/49/3/035101 ↗
6. Sokol, A. A., Walsh, A. & Catlow, C. R. A. Oxygen interstitial structures in close-packed metal oxides. Chem. Phys. Lett. 492, 44–48 (2010).10.1016/j.cplett.2010.04.029 ↗
7. Österbacka, N., Ambrosio, F. & Wiktor, J. Charge localization in defective BiVO4. J. Phys. Chem. C. 126, 2960–2970 (2022).10.1021/acs.jpcc.1c09990 ↗
8. Krajewska, C. J. et al. Enhanced visible light absorption in layered Cs3Bi2Br9 through mixed-valence Sn(II)/Sn(IV) doping. Chem. Sci. 12, 14686–14699 (2021).10.1039/D1SC03775G ↗
9. Mosquera-Lois, I. & Kavanagh, S. R. In search of hidden defects. Matter 4, 2602–2605 (2021).10.1016/j.matt.2021.06.003 ↗
10. Kavanagh, S. R., Walsh, A. & Scanlon, D. O. Rapid recombination by cadmium vacancies in CdTe. ACS Energy Lett. 6, 1392–1398 (2021).10.1021/acsenergylett.1c00380 ↗
11. Kehoe, A. B., Scanlon, D. O. & Watson, G. W. Role of lattice distortions in the oxygen storage capacity of divalently doped CeO2. Chem. Mater. 23, 4464–4468 (2011).10.1021/cm201617d ↗
12. Lany, S. & Zunger, A. Metal-dimer atomic reconstruction leading to deep donor states of the anion vacancy in II-VI and chalcopyrite semiconductors. Phys. Rev. Lett. 93, 156404 (2004).10.1103/PhysRevLett.93.156404 ↗
13. Goyal, A. et al. On the dopability of semiconductors and governing material properties. Chem. Mater. 32, 4467–4480 (2020).10.1021/acs.chemmater.9b05126 ↗
14. Pickard, C. J. & Needs, R. J. High-pressure phases of silane. Phys. Rev. Lett. 97, 045504 (2006).10.1103/PhysRevLett.97.045504 ↗
15. Morris, A. J., Pickard, C. J. & Needs, R. J. Hydrogen/silicon complexes in silicon from computational searches. Phys. Rev. B 78, 184102 (2008).10.1103/PhysRevB.78.184102 ↗
16. Morris, A. J., Pickard, C. J. & Needs, R. J. Hydrogen/nitrogen/oxygen defect complexes in silicon from computational searches. Phys. Rev. B 80, 144112 (2009).10.1103/PhysRevB.80.144112 ↗
17. Morris, A. J., Grey, C. P., Needs, R. J. & Pickard, C. J. Energetics of hydrogen/lithium complexes in silicon analyzed using the Maxwell construction. Phys. Rev. B 84, 224106 (2011).10.1103/PhysRevB.84.224106 ↗
18. Mulroue, J., Morris, A. J. & Duffy, D. M. Ab initio study of intrinsic defects in zirconolite. Phys. Rev. B 84, 094118 (2011).10.1103/PhysRevB.84.094118 ↗
19. Coutinho, J., Markevich, V. P. & Peaker, A. R. Characterisation of negative-U defects in semiconductors. J. Condens. Matter Phys. 32, 323001 (2020).10.1088/1361-648X/ab8091 ↗
20. Kavanagh, S. R., Scanlon, D. O., Walsh, A. & Freysoldt, C. Impact of metastable defect structures on carrier recombination in solar cells. Faraday Discuss. 239, 339–356 (2022).10.1039/D2FD00043A ↗
21. Du, M. H. & Zhang, S. B. DX centers in GaAs and GaSb. Phys. Rev. B Condens. Matter 72, 075210 (2005).10.1103/PhysRevB.72.075210 ↗
22. Kundu, A. et al. Effect of local chemistry and structure on thermal transport in doped GaAs. Phys. Rev. Mater. 3, 094602 (2019).10.1103/PhysRevMaterials.3.094602 ↗
23. Du, M.-H. & Zhang, S. B. DX centers in GaAs and GaSb. Phys. Rev. B 72, 075210 (2005).10.1103/PhysRevB.72.075210 ↗
24. Kim, S., Hood, S. N. & Walsh, A. Anharmonic lattice relaxation during nonradiative carrier capture. Phys. Rev. B 100, 041202 (2019).10.1103/PhysRevB.100.041202 ↗
25. Dobaczewski, L., Kaczor, P., Missous, M., Peaker, A. R. & Zytkiewicz, Z. R. Structure of the DX state formed by donors in (Al,Ga)As and Ga(As,P). Int. J. Appl. Phys. 78, 2468–2477 (1995).10.1063/1.360100 ↗
26. Yamaguchi, E., Shiraishi, K. & Ohno, T. First principle calculation of the DX-center ground-states in GaAs, AlxGa1−xAs alloys and AlAs/GaAs superlattices. J. Phys. Soc. Jpn 60, 3093–3107 (1991).10.1143/JPSJ.60.3093 ↗
27. Li, J., Wei, S.-H. & Wang, L.-W. Stability of the DX− center in GaAs quantum dots. Phys. Rev. Lett. 94, 185501 (2005).10.1103/PhysRevLett.94.185501 ↗
28. Saito, M., Oshiyama, A. & Sugino, O. Validity of the broken-bond model for the DX center in GaAs. Phys. Rev. B 45, 13745–13748 (1992).10.1103/PhysRevB.45.13745 ↗
29. Ágoston, P., Erhart, P., Klein, A. & Albe, K. Geometry, electronic structure and thermodynamic stability of intrinsic point defects in indium oxide. J. Condens. Matter Phys. 21, 455801 (2009).10.1088/0953-8984/21/45/455801 ↗
30. Erhart, P., Klein, A. & Albe, K. First-principles study of the structure and stability of oxygen defects in zinc oxide. Phys. Rev. B 72, 085213 (2005).10.1103/PhysRevB.72.085213 ↗
31. Na-Phattalung, S. et al. First-principles study of native defects in anatase Tio2. Phys. Rev. B 73, 125205 (2006).10.1103/PhysRevB.73.125205 ↗
32. Watkins, G. D. Deep levels in semiconductors. Phys. B+C. 117, 9–15 (1983).10.1016/0378-4363(83)90432-1 ↗
33. Watkins, G. D. 35 years of defects in semiconductors: what next? Mater. Sci. Forum 143, 9–20 (1993).10.4028/www.scientific.net/MSF.143-147.9 ↗
34. Watkins, G. D. Intrinsic defects in II-VI semiconductors. J. Cryst. Growth 159, 338–344 (1996).10.1016/0022-0248(95)00680-X ↗
35. Watkins, G. Native defects and their interactions with impurities in silicon. Mater. Res. Soc. Symp. Proc. 469, 139–150 (1997).10.1557/PROC-469-139 ↗
36. Watkins, G. D. Intrinsic defects in silicon. Mater. Sci. Semicond. Process. 3, 227–235 (2000).10.1016/S1369-8001(00)00037-8 ↗
37. Watkins, G. What we have learned about intrinsic defects in silicon: a help in understanding diamond? Phys. Status Solidi A 186, 176 (2001).10.1002/1521-396X(200108)186:2<176::AID-PSSA167>3.0.CO;2-8 ↗
38. Coulson, C. A. & Kearsley, M. J. Colour centres in irradiated diamonds. I. Proc. R. Soc. Lond. 241, 433–454 (1957).
39. El-Maghraby, M. & Shinozuka, Y. Structural change of a tetrahedral four-site system with arbitrary electron occupancy. J. Phys. Soc. Jpn. 67, 3524–3535 (1998).10.1143/JPSJ.67.3524 ↗
40. Stoneham, A. Theory of Defects in Solids: Electronic Structure of Defects in Insulators and Semiconductors 1st edn, (Oxford University Press, 2007).
41. Carvalho, A., Tagantsev, A. K., Öberg, S., Briddon, P. R. & Setter, N. Cation-site intrinsic defects in Zn-doped CdTe. Phys. Rev. B 81, 075215 (2010).10.1103/PhysRevB.81.075215 ↗
42. Lannoo, M. & Bourgeon, J. Point Defects in Semiconductors I: Experimental Aspects, vol. 22 (Springer, 1981).10.1007/978-3-642-81574-4 ↗
43. Lany, S. & Zunger, A. Anion vacancies as a source of persistent photoconductivity in II-VI and chalcopyrite semiconductors. Phys. Rev. B 72, 035215 (2005).10.1103/PhysRevB.72.035215 ↗
44. Chanier, T., Opahle, I., Sargolzaei, M., Hayn, R. & Lannoo, M. Magnetic state around cation vacancies in II–VI semiconductors. Phys. Rev. Lett. 100, 026405 (2008).10.1103/PhysRevLett.100.026405 ↗
45. Schultz, P. A. & von Lilienfeld, O. A. Simple intrinsic defects in gallium arsenide. Model Simul. Mat. Sci. Eng. 17, 084007 (2009).10.1088/0965-0393/17/8/084007 ↗
46. Feichtinger, H. Deep Centers in Semiconductors, chap. 4, 168-223 (Wiley, Weinheim, 2000).
47. Pham, T. D. & Deskins, N. A. Efficient method for modeling polarons using electronic structure methods. J. Chem. Theory Comput. 16, 5264–5278 (2020).10.1021/acs.jctc.0c00374 ↗
48. Wang, Z., Malyi, O. I., Zhao, X. & Zunger, A. Mass enhancement in 3d and s − p perovskites from symmetry breaking. Phys. Rev. B 103, 165110 (2021).10.1103/PhysRevB.103.165110 ↗
49. Huang, M. et al. DASP: Defect and dopant ab-initio simulation package. J. Semicond. 43, 042101 (2022).10.1088/1674-4926/43/4/042101 ↗
50. Gake, T., Kumagai, Y., Takahashi, A. & Oba, F. Point defects in p-type transparent conductive CuMO2 (M = Al, Ga, In) from first principles. Phys. Rev. Mater. 5, 104602 (2021).10.1103/PhysRevMaterials.5.104602 ↗
51. Kumagai, Y., Tsunoda, N., Takahashi, A. & Oba, F. Insights into oxygen vacancies from high-throughput first-principles calculations. Phys. Rev. Mater. 5, 123803 (2021).10.1103/PhysRevMaterials.5.123803 ↗
52. Mosquera-Lois, I., Kavanagh, S. R., Walsh, A. & Scanlon, D. O. ShakeNBreak: Navigating the defect configurational landscape. J. Open Source Softw. 7, 4817 (2022).10.21105/joss.04817 ↗
53. Mosquera-Lois, I., Kavanagh, S. R., Walsh, A. & Scanlon, D. O. ShakeNBreak documentation. https://shakenbreak.readthedocs.io/en/latest/ (2022).
54. Guo, L. et al. Tunable quasi-one-dimensional ribbon enhanced light absorption in Sb2Se3 thin-film solar cells grown by close-space sublimation. Sol. RRL 2, 1800128 (2018).10.1002/solr.201800128 ↗
55. Wang, X., Li, Z., Kavanagh, S. R., Ganose, A. M. & Walsh, A. Lone pair driven anisotropy in antimony chalcogenide semiconductors. Phys. Chem. Chem. Phys. 24, 7195–7202 (2022).10.1039/D1CP05373F ↗
56. Caruso, F., Filip, M. R. & Giustino, F. Excitons in one-dimensional van der Waals materials: Sb2S3 nanoribbons. Phys. Rev. B 92, 125134 (2015).10.1103/PhysRevB.92.125134 ↗
57. Song, H. et al. Highly anisotropic Sb2Se3 nanosheets: gentle exfoliation from the bulk precursors possessing 1D crystal structure. J. Adv. Mater. 29, 1700441 (2017).10.1002/adma.201700441 ↗
58. Yang, W. et al. Adjusting the anisotropy of 1D Sb2Se3 nanostructures for highly efficient photoelectrochemical water splitting. J. Adv. Energy Mater. 8, 1702888 (2018).10.1002/aenm.201702888 ↗
59. Gusmão, R., Sofer, Z., Luxa, J. & Pumera, M. Antimony Chalcogenide van der Waals nanostructures for energy conversion and storage. ACS Sustain. Chem. Eng. 7, 15790–15798 (2019).10.1021/acssuschemeng.9b04415 ↗
60. Wang, X., Ganose, A. M., Kavanagh, S. R. & Walsh, A. Band versus Polaron: Charge Transport in Antimony Chalcogenides. ACS Energy Letters 7, 2954–2960 (2022).10.1021/acsenergylett.2c01464 ↗
61. Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. Crystal orbital hamilton population (COHP) analysis as projected from plane-wave basis sets. J. Phys. Chem. A 115, 5461–5466 (2011).10.1021/jp202489s ↗
62. Dronskowski, R. & Bloechl, P. E. Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations. J. Phys. Chem. 97, 8617–8624 (1993).10.1021/j100135a014 ↗
63. Maintz, S., Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids. J. Comput. Chem. 34, 2557–2567 (2013).10.1002/jcc.23424 ↗
64. Zhang, B. & Qian, X. Competing superior electronic structure and complex defect chemistry in quasi-one-dimensional antimony chalcogenide photovoltaic absorbers. ACS Appl. Energy Mater. 5, 492–502 (2022).10.1021/acsaem.1c03023 ↗
65. Cai, Z., Dai, C.-M. & Chen, S. Intrinsic defect limit to the electrical conductivity and a two-step p-type doping strategy for overcoming the efficiency Bottleneck of Sb2S3-based solar cells. Sol. RRL 4, 1900503 (2020).10.1002/solr.201900503 ↗
66. Savory, C. & Scanlon, D. O. The complex defect chemistry of antimony selenide. J. Mater. Chem. A 7, 10739–10744 (2019).10.1039/C9TA02022E ↗
67. Huang, M., Xu, P., Han, D., Tang, J. & Chen, S. Complicated and unconventional defect properties of the quasi-one-dimensional photovoltaic semiconductor Sb2Se3. ACS Appl. Mater. Interfaces 11, 15564–15572 (2019).10.1021/acsami.9b01220 ↗
68. Liu, X. et al. Enhanced Sb2Se3 solar cell performance through theory-guided defect control. Prog. Photovolt. 25, 861–870 (2017).10.1002/pip.2900 ↗
69. Zhao, R., Yang, X., Shi, H. & Du, M.-H. Intrinsic and complex defect engineering of quasi-one-dimensional ribbons Sb2S3 for photovoltaics performance. Phys. Rev. Mater. 5, 054605 (2021).10.1103/PhysRevMaterials.5.054605 ↗
70. Tumelero, M. A., Faccio, R. & Pasa, A. A. Unraveling the native conduction of trichalcogenides and its ideal band alignment for new photovoltaic interfaces. J. Phys. Chem. C. 120, 1390–1399 (2016).10.1021/acs.jpcc.5b10233 ↗
71. Stoliaroff, A. et al. Deciphering the role of key defects in Sb2Se3, a promising candidate for chalcogenide-based solar cells. ACS Appl. Energy Mater. 3, 2496–2509 (2020).10.1021/acsaem.9b02192 ↗
72. Han, D., Du, M.-H., Dai, C.-M., Sun, D. & Chen, S. Influence of defects and dopants on the photovoltaic performance of Bi2S3: first-principles insights. J. Mater. Chem. A 5, 6200–6210 (2017).10.1039/C6TA10377D ↗
73. Chen, S. & Wang, L.-W. Double-hole-induced oxygen dimerization in transition metal oxides. Phys. Rev. B 89, 014109 (2014).10.1103/PhysRevB.89.014109 ↗
74. Evarestov, R. A., Jacobs, P. W. M. & Leko, A. V. Oxygen interstitials in magnesium oxide: A band-model study. Phys. Rev. B 54, 8969 (1996).10.1103/PhysRevB.54.8969 ↗
75. Kotomin, E. & Popov, A. Radiation-induced point defects in simple oxides. Nucl. Instrum. Methods Phys. Res B 141, 1–15 (1998).10.1016/S0168-583X(98)00079-2 ↗
76. Burbano, M., Scanlon, D. O. & Watson, G. W. Sources of conductivity and doping limits in CdO from hybrid density functional theory. J. Am. Chem. Soc. 133, 15065–15072 (2011).10.1021/ja204639y ↗
77. Scanlon, D. O. & Watson, G. W. On the possibility of p-type SnO2. J. Mater. Chem. 22, 25236–25245 (2012).10.1039/c2jm34352e ↗
78. Godinho, K. G., Walsh, A. & Watson, G. W. Energetic and electronic structure analysis of intrinsic defects in SnO2. J. Phys. Chem. C. 113, 439–448 (2009).10.1021/jp807753t ↗
79. Scanlon, D. O. et al. Nature of the band gap and origin of the conductivity of pbo2 revealed by theory and experiment. Phys. Rev. Lett. 107, 246402 (2011).10.1103/PhysRevLett.107.246402 ↗
80. Keating, P. R. L., Scanlon, D. O., Morgan, B. J., Galea, N. M. & Watson, G. W. Analysis of Intrinsic defects in CeO2 using a Koopmans-Like GGA+U approach. J. Phys. Chem. C. 116, 2443–2452 (2012).10.1021/jp2080034 ↗
81. Scanlon, D. O. Defect engineering of basno3 for high-performance transparent conducting oxide applications. Phys. Rev. B 87, 161201 (2013).10.1103/PhysRevB.87.161201 ↗
82. Walsh, A., Da Silva, J. L. F. & Wei, S.-H. Interplay between order and disorder in the high performance of amorphous transparent conducting oxides. Chem. Mater. 21, 5119–5124 (2009).10.1021/cm9020113 ↗
83. Wilson, D. J., Sokol, A. A., French, S. A. & Catlow, C. R. A. Defect structures in the silver halides. Phys. Rev. B 77, 064115 (2008).10.1103/PhysRevB.77.064115 ↗
84. Agiorgousis, M. L., Sun, Y.-Y., Zeng, H. & Zhang, S. Strong covalency-induced recombination centers in perovskite solar cell material CH3NH3PbI3. J. Am. Chem. Soc. 136, 14570–14575 (2014).10.1021/ja5079305 ↗
85. Whalley, L. D., Crespo-Otero, R. & Walsh, A. H-Center and V-Center defects in hybrid halide perovskites. ACS Energy Lett. 2, 2713–2714 (2017).10.1021/acsenergylett.7b00995 ↗
86. Whalley, L. D. et al. Giant Huang-Rhys factor for electron capture by the iodine intersitial in perovskite solar cells. J. Am. Chem. Soc. 143, 9123–9128 (2021).10.1021/jacs.1c03064 ↗
87. Motti, S. G. et al. Defect activity in lead halide perovskites. Adv. Mater. 31, 1901183 (2019).10.1002/adma.201901183 ↗
88. Kang, J. & Wang, L.-W. High defect tolerance in lead halide perovskite CsPbBr3. J. Phys. Chem. 8, 489–493 (2017).
89. Zhao, Y. et al. Correlations between Immobilizing Ions and Suppressing Hysteresis in Perovskite Solar Cells. ACS Energy Lett. 1, 266–272 (2016).10.1021/acsenergylett.6b00060 ↗
90. Xiao, Z., Meng, W., Wang, J. & Yan, Y. Defect properties of the two-dimensional $${({{{\rm{CH}}}}3{{{\rm{NH}}}}3)}2{{{\rm{Pb}}}}{({{{\rm{SCN}}}})}2{{{{\rm{I}}}}}2$$ perovskite: a density-functional theory study. Phys. Chem. Chem. Phys. 18, 25786–25790 (2016).10.1039/C6CP05302E ↗
91. Meggiolaro, D., Ricciarelli, D., Alasmari, A. A., Alasmary, F. A. S. & De Angelis, F. Tin versus lead redox chemistry modulates charge trapping and self-doping in Tin/Lead Iodide perovskites. J. Phys. Chem. 11, 3546–3556 (2020).
92. Liao, Y. Practical electron microscopy and database. An Online Book (2006).
93. Hiley, C. I. et al. Incorporation of square-planar Pd2+ in fluorite CeO2: hydrothermal preparation, local structure, redox properties and stability. J. Mater. Chem. A 3, 13072–13079 (2015).10.1039/C5TA02007G ↗
94. Hegde, M. & Bera, P. Noble metal ion substituted CeO2 catalysts: Electronic interaction between noble metal ions and CeO2 lattice. Catal. Today 253, 40–50 (2015).10.1016/j.cattod.2015.03.035 ↗
95. Huang, M. et al. More Se vacancies in Sb2Se3 under Se-Rich conditions: an abnormal behavior induced by defect-correlation in compensated compound sSemiconductors. Small 17, 2102429 (2021).10.1002/smll.202102429 ↗
96. Guo, L. et al. Scalable and efficient Sb2S3 thin-film solar cells fabricated by close space sublimation. APL Mater. 7, 041105 (2019).10.1063/1.5090773 ↗
97. Zhang, Z., Qiao, L., Mora-Perez, C., Long, R. & Prezhdo, O. V. Pb dimerization greatly accelerates charge losses in $${{{\rm{MAPbI}}}}{({{{\rm{CH}}}}3{{{\rm{NH}}}}3)}2{{{\rm{Pb}}}}{({{{\rm{SCN}}}})}2{{{\rm{I}}}}{2}3$$: Time-domain ab initio analysis. J. Chem. Phys. 152, 064707 (2020).10.1063/1.5131342 ↗
98. Cai, L., Wang, S., Huang, M., Wu, Y.-N. & Chen, S. First-principles identification of deep energy levels of sulfur impurities in silicon and their carrier capture cross sections. J. Phys. D: Appl. Phys. 54, 335103 (2021).10.1088/1361-6463/abff7d ↗
99. Krasikov, D. & Sankin, I. Beyond thermodynamic defect models: A kinetic simulation of arsenic activation in CdTe. Phys. Rev. Mater. 2, 103803 (2018).10.1103/PhysRevMaterials.2.103803 ↗
100. Yang, J.-H., Shi, L., Wang, L.-W. & Wei, S.-H. Non-radiative carrier recombination enhanced by two-level process: a first-principles study. Sci. Rep. 6, 21712 (2016).10.1038/srep21712 ↗