碱金属掺杂碘化亚铜缺陷性质的第一性原理研究

doi:10.15541/jim20260093

摘要/Abstract

摘要： 透明半导体γ相碘化铜(γ-CuI)是一种极具应用前景的新一代光电器件材料,碱金属掺杂被视为能提高其电学和光学性能的调控手段。本研究基于第一性原理计算,系统研究了碱金属(Na、K和Cs)掺杂CuI引入的缺陷性质。研究发现,Na掺杂倾向于形成点缺陷和简单缺陷簇,而原子半径更大的K和Cs则倾向于形成更复杂的缺陷簇。此外,Na掺杂引入的缺陷浓度比CuI本征缺陷浓度更高,进而增强CuI的p型导电性。相较之下,K和Cs掺杂引入的缺陷浓度远低于本征缺陷,对CuI导电性的调控作用有限。在红外吸收方面,碱金属掺杂引入的高浓度缺陷并没有在禁带中形成缺陷能级,相反部分低浓度缺陷可以在禁带中引入缺陷能级进而吸收红外光子,表明缺陷能级吸收对γ-CuI的红外透射率的影响可以忽略不计。这项工作揭示了碱金属掺杂在提高碘化亚铜p型电导性的同时,不会引起由缺陷能级引起的不可控的红外光子吸收。这为开发需要同时优化电学和光学性能的基于CuI的器件提供了理论基础。

关键词: γ-碘化亚铜, 碱金属掺杂, 第一性原理, 缺陷性质, 红外透射率

Abstract: The transparent semiconductor γ-CuI is a highly promising material for next-generation optoelectronic devices. To further enhance its electrical and optical performance, intentional doping with alkali metals has been identified as a critical and effective strategy. In this study, the defect properties induced by doping with alkali metals (Na, K, and Cs) in CuI are systematically investigated using first-principles calculations. It is found that Na doping tends to form point defects and defect clusters, whereas the larger atomic radii of K and Cs promote the formation of more complex defect clusters. Furthermore, Na doping can result in defect concentrations higher than those of intrinsic defects, thereby significantly enhancing p-type conductivity. In contrast, the defect concentrations introduced by K and Cs doping are much lower than those of the intrinsic defects, and their effect on enhancing p-type conductivity is limited. Regarding the infrared absorption, high-concentration defects do not possess in-bandgap defect energy levels capable of absorbing infrared photons, whereas certain low-concentration defect clusters exhibit such absorption. Carrier absorption through defect energy levels has a negligible effect on the infrared transmittance of γ-CuI. This work predicts that alkali metal doped CuI is advantageous that p-type conductivity can be improved without causing uncontrollable infrared photon absorption caused by defect energy levels. This provides a theoretical basis for developing CuI-based devices that require simultaneous optimization of electrical and optical properties.

Key words: γ-CuI, alkali metal doping, first-principles calculations, defect properties, infrared transmittance

中图分类号:

TQ174

任若天, 白锐荣, 陈肖健, 林振南, 杨长, 吴宇宁. 碱金属掺杂碘化亚铜缺陷性质的第一性原理研究[J]. 无机材料学报, DOI: 10.15541/jim20260093.

REN Ruotian, BAI Ruirong, CHEN Xiaojian, LIN Zhennan, YANG Chang, WU Yuning. Defect Properties of Alkali Metal Doped γ-CuI: A First-principles Perspective[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260093.

参考文献

[1] KIM B H, STALLER C M, CHO S H, et al. High mobility in nanocrystal-based transparent conducting oxide thin films. ACS Nano, 2018, 12(4): 3200.
[2] VAN HEST M F A M, DABNEY M S, PERKINS J D,et al. Titanium-doped indium oxide: a high-mobility transparent conductor. Applied Physics Letters, 2005, 87(3): 032111.
[3] YAN Y D, DUAN B W, RU M,et al. Toward flexible and stretchable organic solar cells: a comprehensive review of transparent conductive electrodes, photoactive materials, and device performance. Advanced Energy Materials, 2025, 15(7): 2404233.
[4] AFRE R A, SHARMA N, SHARON M,et al. Transparent conducting oxide films for various applications: a review. Reviews on Advanced Materials Science, 2018, 53(1): 79.
[5] BARATON M-I.The future of TCO materials: stakes and challenges.Mater. Res. Soc. Symp. Proc., 2010, 1209(P03): 6.
[6] PROFICIENCY MUNSAKA P B. Mid-infrared gas absorption spectroscopy using a silicon germanium waveguide based chirped supercontinuum.Vibrational Spectroscopy, 2024, 133(10): 103705.
[7] PICCARDO M, TAMAGNONE M, SCHWARZ B,et al. Radio frequency transmitter based on a laser frequency comb. Proceedings of the National Academy of Sciences, 2019, 116(19): 9181.
[8] LUBEZKY I, MARCOVITCH O, Z KLEIN,et al. Activation reaction evaporation of transparent conductive coatings in the infrared region. Thin Solid Films, 1986, 148(1): 83.
[9] HU C Q, ZHOU Z J, ZHANG X Y,et al. Far-infrared transparent conductors. Light-Science & Applications, 2023, 12(1): 98.
[10] CUI C, DING Q M, YU S Y,et al. Strategies to break the trade-off between infrared transparency and conductivity. Progress in Materials Science, 2023, 136(10): 101112.
[11] YANG C, KNEISS M, LORENZ M,et al. Room-temperature synthesized copper iodide thin film as degenerate p-type transparent conductor with a boosted figure of merit. Proceedings of the National Academy of Sciences of the United States of America, 2016, 113(46): 12929.
[12] ZHANG K H L, DU Y G, PAPADOGIANNI A,et al. Perovskite Sr‐doped LaCrO₃ as a new p‐type transparent conducting oxide. Advanced Materials, 2015, 27(35): 5191.
[13] GUNNING B, LOWDER J, MOSELEY M,et al. Negligible carrier freeze-out facilitated by impurity band conduction in highly p-type GaN. Applied Physics Letters, 2012, 101(8): 082106.
[14] LIU D, CAI Z, WU Y-N,et al. First-principles identification of V_I+Cu_i defect cluster in cuprous iodide: origin of red light photoluminescence. Nanotechnology, 2022, 33(19): 195203.
[15] SIRIMANNE P M, SOGA T, KUNST M.Observation of microwave conductivity in copper iodide films and relay effect in the dye molecules attached to CuI photocathode.Journal of Solid State Chemistry, 2005, 178(10): 3010.
[16] KEEN D A, HULL S.The high-temperature structural behaviour of copper (I) iodide.Journal of Physics: Condensed Matter, 1995, 7(29): 5793.
[17] YAMADA N, INO R, NINOMIYA Y.Truly transparent p-Type γ-CuI thin films with high hole mobility.Chemistry of Materials, 2016, 28(14): 4971.
[18] PARK J S, KIM S, XIE Z,et al. Point defect engineering in thin-film solar cells. Nature Reviews Materials, 2018, 3(7): 194.
[19] OBA F K Y. Design and exploration of semiconductors from first principles: a review of recent advances.Applied Physics Express, 2018, 11(6): 060101.
[20] LI M C, ZHANG Z, ZHAO Q,et al. Electronic structure and optical properties of doped γ-CuI scintillator: a first-principles study. Rsc Advances, 2023, 13(14): 9615.
[21] MATSUZAKI K, TSUNODA N, KUMAGAI Y,et al. Hole-doping to a Cu(I)-based semiconductor with an isovalent cation: utilizing a complex defect as a shallow acceptor. Journal of the American Chemical Society, 2022, 144(36): 16572.
[22] KOHN W, SHAM L J.Self-consistent equations including exchange and correlation effects.Physical Review, 1965, 140(4A): A1133.
[23] HOHENBERG P, KOHN W.Inhomogeneous electron gas.Physical Review, 1964, 136(3B): B864.
[24] KRESSE G, FURTHMULLER J.Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set.Computational Materials Science, 1996, 6(1): 15.
[25] MOMMA K, IZUMI F.VESTAβ3 for three-dimensional visualization of crystal, volumetric and morphology data.Journal of Applied Crystallography, 2011, 44(6): 1272.
[26] GALI A.Recent advances in the ab initio theory of solid-state defect qubits.Nanophotonics, 2023, 12(3): 359.
[27] ERNZERHOF M, SCUSERIA G E.Assessment of the Perdew-Burke-Ernzerhof exchange-correlation functional.The Journal of Chemical Physics, 1999, 110(11): 5029.
[28] BLÖCHL P E. Projector augmented-wave method.Physical Review B, 1994, 50(24): 17953.
[29] KRESSE G, JOUBERT D.From ultrasoft pseudopotentials to the projector augmented-wave method.Physical Review B, 1999, 59(3): 1758.
[30] HEYD J, SCUSERIA G E, ERNZERHOF M.Hybrid functionals based on a screened Coulomb potential.Journal of Chemical Physics, 2003, 118(18): 8207.
[31] DRESSELHAUS G.Spin-orbit coupling effects in zinc blende structures.Physical Review, 1955, 100(2): 580.
[32] MANCHON A, KOO H C, NITTA J,et al. New perspectives for Rashba spin-orbit coupling. Nature Materials, 2015, 14(9): 871.
[33] GALITSKI V, SPIELMAN I B.Spin-orbit coupling in quantum gases.Nature, 2013, 494(7435): 49.
[34] MONKHORST H J, PACK J D.Special points for Brillouin-zone integrations.Physical Review B, 1976, 13(12): 5188.
[35] CHEN H, WANG C-Y, WANG J-T, et al. First-principles study of point defects in solar cell semiconductor CuI. Physica B: Condensed Matter, 2013, 413(1): 116.
[36] MAKOV G, SHAH R, PAYNE M C.Periodic boundary conditions in ab initio calculations. II. Brillouin-zone sampling for aperiodic systems.Physical Review B, 1996, 53(23): 15513.
[37] LANY S, ZUNGER A.Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: case studies for ZnO and GaAs.Physical Review B, 2008, 78(23): 235104.
[38] FREYSOLDT C, GRABOWSKI B, HICKEL T,et al. First-principles calculations for point defects in solids. Rev. Mod. Phys., 2014, 86(1): 253.
[39] LIU D R, HAN D, HUANG M L,et al. Theoretical study on the kesterite solar cells based on Cu₂ZnSn(S,Se)₄ and related photovoltaic semiconductors. Chinese Physics B, 2018, 27(1): 018806.
[40] YANG J-H, PARK J-S, KANG J,et al. Tuning the fermi level beyond the equilibrium doping limit through quenching: the case of CdTe. Physical Review B, 2014, 90(24): 245202.
[41] MA J, WEI S H, GESSERT T A,et al. Carrier density and compensation in semiconductors with multiple dopants and multiple transition energy levels: Case of Cu impurities in CdTe. Physical Review B, 2011, 83(24): 245207.
[42] SLATER J C.Atomic radii in crystals.The Journal of Chemical Physics, 1964, 41(10): 3199.
[43] GAO P, GU M, LIU X L,et al. X-ray excited luminescence of cuprous iodide single crystals: on the nature of red luminescence. Applied Physics Letters, 2009, 95(22): 221904.
[44] YAZICIOGLU D, CAI Y, GUTSCH S, et al. Enhanced defect luminescence due to fast Auger process in cuprous iodide structures produced by solvent/anti-solvent crystallization. Journal of Luminescence, 2020, 220(11): 116961.
[45] YAN LEI H Q, GONG ZIYAO,et al. Ultrafast nonlinear optical absorption and carrier dynamics of CrPS₄ thin films. Chinese Optics Letters, 2024, 22(11): 111901.
[46] JIE LI J L, CHENGLONG ZHENG,et al. Broadband and tunable terahertz absorption via photogenerated carriers in undoped silicon. Science China-Physics Mechanics & Astronomy, 2022, 65(1): 214211.
[47] LU C H, XUAN H W, ZHOU Y X,et al. Saturable and reverse saturable absorption in molybdenum disulfide dispersion and film by defect engineering. Photonics Research, 2020, 8(9): 1512.
[48] BASU S, LEE B J, ZHANG Z M.Infrared radiative properties of heavily doped silicon at room temperature.Journal of Heat Transfer-Transactions of the Asme, 2010, 132(2): 023301.
[49] MARQUIER F, JOULAIN K, MULET J P,et al. Engineering infrared emission properties of silicon in the near field and the far field. Optics Communications, 2004, 237(4/5/6): 379.
[50] MACDONALD D, GEERLIGS L J.Recombination activity of interstitial iron and other transition metal point defects in p- and n-type crystalline silicon.Applied Physics Letters, 2004, 85(18): 4061.
[51] SCHRODER D K, THOMAS R N, SWARTZ J C.Free carrier absorption in silicon.IEEE Transactions on Electron Devices, 1978, 25(2): 254.