J. Semicond. > Volume 41 > Issue 5 > Article Number: 052201

Comprehensive first-principles studies on phase stability of copper-based halide perovskite derivatives AlCumXn (A = Rb and Cs; X = Cl, Br, and I)

Zhongti Sun 1, 2, , Xiwen Chen 1, 2, and Wanjian Yin 1, 2, 3, ,

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Abstract: Recently, inorganic copper-based halide perovskites and their derivatives (CHPs) with chemical formulas AlCumXn (A = Rb and Cs; X = Cl, Br and I; l, m, and n are integers.), have received increasing attention in the photoluminescence field, due to their lead-free, cost-effective, earth-abundant and low electronic dimensionality. Ascribed to flexible valence charge of Cu (Cu1+ and Cu2+) and complex competing phases, the crystal structures and phase stabilities of CHPs are complicated and ambiguous, which limits their experimental applications. Via comprehensive first-principles calculations, we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database (ICSD). Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs, i.e. Rb3Cu2Br5, Rb3Cu2I5, RbCu2Cl3, Rb2CuI3, Rb2CuBr4, RbCuBr3, Rb3Cu2Br7, Cs3Cu2Br7, Cs3Cu2Cl7 and Cs4Cu5Cl9, which have not yet been reported in experiments. This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.

Key words: first-principles calculationscopper-based halide perovskitestabilityphase diagram

Abstract: Recently, inorganic copper-based halide perovskites and their derivatives (CHPs) with chemical formulas AlCumXn (A = Rb and Cs; X = Cl, Br and I; l, m, and n are integers.), have received increasing attention in the photoluminescence field, due to their lead-free, cost-effective, earth-abundant and low electronic dimensionality. Ascribed to flexible valence charge of Cu (Cu1+ and Cu2+) and complex competing phases, the crystal structures and phase stabilities of CHPs are complicated and ambiguous, which limits their experimental applications. Via comprehensive first-principles calculations, we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database (ICSD). Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs, i.e. Rb3Cu2Br5, Rb3Cu2I5, RbCu2Cl3, Rb2CuI3, Rb2CuBr4, RbCuBr3, Rb3Cu2Br7, Cs3Cu2Br7, Cs3Cu2Cl7 and Cs4Cu5Cl9, which have not yet been reported in experiments. This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.

Key words: first-principles calculationscopper-based halide perovskitestabilityphase diagram



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Cortecchia D, Dewi H A, Yin J, et al. Lead-free MA2CuCl xBr4– x hybrid perovskites. Inorg Chem, 2016, 55(3), 1044

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Jun T, Sim K, Iimura S, et al. Lead-free highly efficient blue-emitting Cs3Cu2I5 with 0D electronic structure. Adv Mater, 2018, 30(43), 1804547

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Hull S, Berastegui P. Crystal structures and ionic conductivities of ternary derivatives of the silver and copper monohalides — II: ordered phases within the (AgX) x–(MX)1− x and (CuX)x–(MX)1− x (M = K, Rb and Cs; X = Cl, Br and I) systems. J Solid State Chem, 2004, 177(9), 3156

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Xiao Z, Du K, Meng W, et al. Chemical origin of the stability difference between copper(I)- and silver(I)-based halide double perovskites. Angew Chem Int Ed, 2017, 129, 12275

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Yang P, Liu G, Liu B, et al. All-inorganic Cs2CuX4 (X = Cl, Br, and Br/I) perovskite quantum dots with blue-green luminescence. Chem Commun, 2018, 54(82), 11638

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Helmholz L, Kruh R F. The crystal structure of cesium chlorocuprate, Cs2CuCl4, and the spectrum of the chlorocuprate ion. J Am Chem Soc, 1952, 74(5), 1176

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Aguado F, Rodríguez F, Valiente R, et al. Three-dimensional magnetic ordering in the Rb2CuCl4 layer perovskite—structural correlations. J Phys Condens Matter, 2004, 16(12), 1927

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Lim A R, Kim S H. Study of the structural phase transitions in RbCuCl3 and CsCuCl3 single crystals with the electric-magnetic-type interactions using a 87Rb and 133Cs nuclear magnetic resonance spectrometer. J Appl Phys, 2007, 101, 083519

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Kousaka Y, Koyama T, Miyagawa M, et al. Crystal growth of chiral magnetic material in CsCuCl3. J Phys Conf Ser, 2014, 502, 012019

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Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54, 11169

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Blöchl P E. Projector augmented-wave method. Phys Rev B, 1994, 50, 17953

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Perdew J P, Burke K, Ernzerh of M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77, 3865

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Persson C, Zhao Y J, Lany S, et al. n-type doping of CuInSe2 and CuGaSe2. Phys Rev B, 2005, 72(3), 035211

[26]

Zhao X G, Yang D, Sun Y, et al. Cu–In halide perovskite solar absorbers. J Am Chem Soc, 2017, 139(19), 6718

[1]

Sun Y, Giebink N C, Kanno H, et al. Management of singlet and triplet excitons for efficient white organic light-emitting devices. Nature, 2006, 440(7086), 908

[2]

Luo J, Wang X, Li S, et al. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature, 2018, 563(7732), 541

[3]

Tan Z K, Moghaddam R S, Lai M L, et al. Bright light-emitting diodes based on organometal halide perovskite. Nat Nanotechnol, 2014, 9(9), 687

[4]

Yin W J, Shi T, Yan Y. Unique properties of halide perovskites as possible origins of the superior solar cell performance. Adv Mater, 2014, 26(27), 4653

[5]

Cho H, Jeong S H, Park M H, et al. Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes. Science, 2015, 350(6265), 1222

[6]

Li J, Bade S G R, Shan X, et al. Single-layer light-emitting diodes using organometal halide perovskite/poly(ethylene oxide) composite thin films. Adv Mater, 2015, 27(35), 5196

[7]

Saidaminov M I, Almutlaq J, Sarmah S, et al. Pure Cs4PbBr6: highly luminescent zero-dimensional perovskite solids. ACS Energy Lett, 2016, 1(4), 840

[8]

Cha J H, Han J H, Yin W, et al. Photoresponse of CsPbBr3 and Cs4PbBr6 perovskite single crystals. J Phys Chem Lett, 2017, 8(3), 565

[9]

De Bastiani M, Dursun I, Zhang Y, et al. Inside perovskites: quantum luminescence from bulk Cs4PbBr6 single crystals. Chem Mater, 2017, 29(17), 7108

[10]

Cortecchia D, Dewi H A, Yin J, et al. Lead-free MA2CuCl xBr4– x hybrid perovskites. Inorg Chem, 2016, 55(3), 1044

[11]

Yang H, Zhang Y, Pan J, et al. Room-temperature engineering of all-inorganic perovskite nanocrsytals with different dimensionalities. Chem Mater, 2017, 29(21), 8978

[12]

Yang J, Zhang P, Wei S H. Band structure engineering of Cs2AgBiBr6 perovskite through order–disordered transition: a first-principle study. J Phys Chem Lett, 2017, 9(1), 31

[13]

Elseman A M, Shalan A E, Sajid S, et al. Copper-substituted lead perovskite materials constructed with different halides for working (CH3NH3)2CuX4-based perovskite solar cells from experimental and theoretical view. ACS Appl Mater Interfaces, 2018, 10(14), 11699

[14]

Jun T, Sim K, Iimura S, et al. Lead-free highly efficient blue-emitting Cs3Cu2I5 with 0D electronic structure. Adv Mater, 2018, 30(43), 1804547

[15]

Hull S, Berastegui P. Crystal structures and ionic conductivities of ternary derivatives of the silver and copper monohalides — II: ordered phases within the (AgX) x–(MX)1− x and (CuX)x–(MX)1− x (M = K, Rb and Cs; X = Cl, Br and I) systems. J Solid State Chem, 2004, 177(9), 3156

[16]

Xiao Z, Du K, Meng W, et al. Chemical origin of the stability difference between copper(I)- and silver(I)-based halide double perovskites. Angew Chem Int Ed, 2017, 129, 12275

[17]

Yang P, Liu G, Liu B, et al. All-inorganic Cs2CuX4 (X = Cl, Br, and Br/I) perovskite quantum dots with blue-green luminescence. Chem Commun, 2018, 54(82), 11638

[18]

Helmholz L, Kruh R F. The crystal structure of cesium chlorocuprate, Cs2CuCl4, and the spectrum of the chlorocuprate ion. J Am Chem Soc, 1952, 74(5), 1176

[19]

Aguado F, Rodríguez F, Valiente R, et al. Three-dimensional magnetic ordering in the Rb2CuCl4 layer perovskite—structural correlations. J Phys Condens Matter, 2004, 16(12), 1927

[20]

Lim A R, Kim S H. Study of the structural phase transitions in RbCuCl3 and CsCuCl3 single crystals with the electric-magnetic-type interactions using a 87Rb and 133Cs nuclear magnetic resonance spectrometer. J Appl Phys, 2007, 101, 083519

[21]

Kousaka Y, Koyama T, Miyagawa M, et al. Crystal growth of chiral magnetic material in CsCuCl3. J Phys Conf Ser, 2014, 502, 012019

[22]

Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54, 11169

[23]

Blöchl P E. Projector augmented-wave method. Phys Rev B, 1994, 50, 17953

[24]

Perdew J P, Burke K, Ernzerh of M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77, 3865

[25]

Persson C, Zhao Y J, Lany S, et al. n-type doping of CuInSe2 and CuGaSe2. Phys Rev B, 2005, 72(3), 035211

[26]

Zhao X G, Yang D, Sun Y, et al. Cu–In halide perovskite solar absorbers. J Am Chem Soc, 2017, 139(19), 6718

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Z T Sun, X W Chen, W J Yin, Comprehensive first-principles studies on phase stability of copper-based halide perovskite derivatives AlCumXn (A = Rb and Cs; X = Cl, Br, and I)[J]. J. Semicond., 2020, 41(5): 052201. doi: 10.1088/1674-4926/41/5/052201.

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History

Manuscript received: 21 February 2020 Manuscript revised: 03 March 2020 Online: Accepted Manuscript: 21 April 2020 Uncorrected proof: 23 April 2020 Published: 13 May 2020

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