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; Xiwen Chen; Wanjian Yin

doi:10.1088/1674-4926/41/5/052201

J. Semicond. > 2020, Volume 41 > Issue 5 > 052201

ARTICLES

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

Zhongti Sun^{1, 2}, Xiwen Chen^{1, 2} and Wanjian Yin^{1, 2, 3,}

+ Author Affiliations

Corresponding author: Wanjian Yin, Email: wjyin@suda.edu.cn

DOI: 10.1088/1674-4926/41/5/052201

Abstract: Recently, inorganic copper-based halide perovskites and their derivatives (CHPs) with chemical formulas A_lCu_mX_n (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 A_lCu_mX_n 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 calculations, copper-based halide perovskite, stability, phase diagram

References

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Fig. 1. (Color online) (a) The optimized structure of CHPs with 325-type, they own the isostructural model with space group of Pnma, isolated [Cu₂X₅]^3– anion unit is composed of two types of Cu⁺ sites, a trigonal site and a tetragonal site. (b) Calculated phase stability regions versus μ_Cu and μ_X (referring to the chemical potential of Cu and X from that of their elementary substance) from left to right for the X site of I, Br, and Cl element and up to down for Cs and Rb element on A site, respectively. The cyan polygon region represents thermodynamic stability growth region, which is encircled by possible competing phases using colored line (red, blue, violet, and pink). A, Cu, and X atoms are in purple, coral and brown, respectively.

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Fig. 2. (Color online) (a) The structure model of CHPs with 123-type, they all own octahedral structure with the space group of Cmcm (No. 63), composed of edge-sharing [CuX₄] tetrahedron 1D chain. (b) Calculated thermodynamic stability regions of ACu₂X₃ (A = Rb and Cs; X = Cl, Br, and I) CHPs versus μ_Cu and μ_X (deviation of actual chemical potential of Cu and X from that of their elementary substance). The above from left to right is the CHP for the X site of I, Br, and Cl element, and up to down is for Cs and Rb element on A site, respectively. The cyan polygon region represents thermodynamic stable interval, which is surrounded by competing phases using colored line (red, blue, orange, violet, and pink). A, Cu, and X atoms are in purple, coral and brown, respectively.

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Fig. 3. (Color online) (a) The structure model of CHPs with 213-type, they possess isostructural model with Pnma symmetry, which is composed of 1D [Cu–X] tetrahedron chain with isolated alkali metal cation (Rb⁺ , Cs⁺ ). (b) Calculated phase stability regions in cyan polygon of A₂CuX₃ (A = Cs and Rb; X = I, Br, and Cl) CHPs versus μ_Cu and μ_X (deviation of actual chemical potential of Cu and X from that of their elementary substance). The cyan polygon region indicates thermodynamic phase stability growth interval, which is encompassed by competing phases with colored line (red, blue, and pink). A, Cu, and X atoms are in purple, coral and brown, respectively.

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Fig. 4. (Color online) (a) The structure model of 459-type CHPs with space group of Pc, they own isolated [Cu₅X₉]^4– anion with three types of Cu⁺ ions, a tetrahedral site, a trigonal site and a 2-fold coordination site. (b) Calculated thermodynamic stability regions of 459-type CHPs against μ_Cu and μ_X (deviation of actual chemical potential of Cu and X from that of their elementary substance). The cyan polygon region reveals thermodynamic stable growth interval and each colored line corresponds to one most probable competing phase. A, Cu, and X atoms are in purple, coral and brown, respectively.

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Fig. 5. (Color online) (a) The structure model of 214-type CHPs, most of them possess octahedral space group Pnma with isolated [Cu–X] tetrahedron. But for Rb₂CuCl₄, it owns Cmca symmetry with 2D [Cu₂Cl₄]^2– layers, induced by [Cu-Cl] octahedron Jahn-Teller distortion. (b) Calculated thermodynamic stability regions of A₂CuX₄ (A = Rb and Cs; X = Cl, Br, and I) halide perovskites versus μ_Cu and μ_X (deviation of actual chemical potential of Cu and X from that of their elementary substance). The horizontal and vertical axis is from I to Cl element and from Cs to Rb element, respectively. The cyan polygon region shows thermodynamic stability growth interval, which is encircled by most probable competing phases with colored lines (red, blue, violet, and pink). A, Cu, and X atoms are in purple, coral and brown, respectively.

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Fig. 6. (Color online) (a) The structure model of 113-type CHPs, even though they possess different structures, they all have the same [CuX₆] octahedron unit via face- and corner-sharing. (b) Calculated thermodynamic stability regions of ACuX₃ (A = Rb and Cs; X = Cl, Br, and I) versus μ_Cu and μ_X (deviation of actual chemical potential of Cu and X from that of their elementary substance). The horizontal and vertical axis is from I to Cl element and from Cs to Rb element, respectively. The cyan polygon region represents thermodynamic stable growth interval, which is surrounded by most probable competing phases using colored line (red, blue, orange, violet, and pink). A, Cu, and X atoms are in purple, coral and brown, respectively.

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Fig. 7. (Color online) (a) The structure model of 327-type CHPs, they all own tetragonal space group Ccca with isolated [Cu₂X₇]^3– anion composing of elongated [Cu–X] octahedron unit. (b) Calculated thermodynamic stability regions of 327-type CHPs versus μ_Cu and μ_X (deviation of actual chemical potential of Cu and X from that of their elementary substance). The cyan polygon region represents phase stability growth condition, which is encircled by competing phases using colored line (red, blue, violet, and pink). A, Cu, and X atoms are in purple, coral and brown, respectively.

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Table 1. The Space group of existing CHPs with various types encompassing 325-, 123-, 213-, 459-, 214-, 113-, and 327-type from inorganic crystal structure database (ICSD). ‘√’ and blank grid symbol indicates the existing and non-existing phase in experiment, respectively.

Type	Space group (No.)	Rb			Cs
Type	Space group (No.)	Cl	Br	I	Cl	Br	I
325	Pnma (62)				√	√	√
123	Cmcm (63)		√	√	√	√	√
213	Pnma (62)	√	√
459	Pc (7)	√
214	Pnma (62)				√	√
214	Cmca (64)	√
113	P6122 (178)				√
	C2221 (20)					√
	Pbcn (60)	√
327	Ccca (68)	√

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Table 2. Calculated decomposition energies together with ODP in the CHPs A_lCu_mX_n (A = Rb and Cs; X = Cl, Br, and I; l, m, and n are integers).

Compound		ΔH_d (meV/atom)	Optimal decomposition pathway
325-type	Cs₃Cu₂I₅	25	Cs₃Cu₂I₅ → 2CsI + CsCu₂I₃
	Cs₃Cu₂Br₅	29	Cs₃Cu₂Br₅ → 2CsBr + CsCu₂Br₃
	Cs₃Cu₂Cl₅	33	Cs₃Cu₂Cl₅ → Cu + CsCl + Cs₂CuCl₄
	Rb₃Cu₂I₅	13	Rb₃Cu₂I₅ → 2RbI + RbCu₂I₃
	Rb₃Cu₂Br₅	5	Rb₃Cu₂Br₅ → 4/3Rb₂CuBr₃ + 1/3RbCu₂Br₃
	Rb₃Cu₂Cl₅	–2	Rb₃Cu₂Cl₅ → 7/5RbCl + 2/5Rb₄Cu₅Cl₉
123-type	CsCu₂I₃	0	CsCu₂I₃ → 4/3CuI + 1/3Cs₃Cu₂I₅
	CsCu₂Br₃	22	CsCu2Br₃ → 4/3CuBr + 1/3Cs₃Cu₂Br₅
	CsCu₂Cl₃	24	CsCu₂Cl₃ → 4/3CuCl + 1/3Cu₃Cu₂Cl₅
	RbCu₂I₃	23	RbCu₂I₃ → RbI + 2CuI
	RbCu₂Br₃	28	RbCu₂Br₃ → 3/2CuBr + 1/2Rb₂CuBr₃
	RbCu₂Cl₃	6	RbCu₂Cl₃ → 3/4CuCl + 1/4Rb₄Cu₅Cl₉
213-type	Cs₂CuI₃	–22	Cs₂CuI₃ → 1/2CsI + 1/2Cs₃Cu₂I₅
	Cs₂CuBr₃	–16	Cs₂CuBr₃ → 1/2CsBr + 1/2Cs₃Cu₂Br₅
	Cs₂CuCl₃	–19	Cs₂CuCl₃ → 1/2CsCl + 1/2Cs₃Cu₂Cl₅
	Rb₂CuI₃	6	Rb₂CuI₃ → 3/2RbI + 1/2RbCu₂I₃
	Rb₂CuBr₃	6	Rb₂CuBr₃ → 3/2RbBr + 1/2RbCu₂Br₃
	Rb₂CuCl₃	8	Rb₂CuCl₃ → 1/2Cu + RbCl + 1/2Rb₂CuCl₄
459-type	Cs₄Cu₅I₉	–20	Cs₄Cu₅I₉ → 3/4Cs₃Cu₂I₅ + 7/4CsCu₂I₃
	Cs₄Cu₅Br₉	–9	Cs₄Cu₅Br₉ → 3/4Cs₃Cu₂Br₅ + 7/4CsCu₂Br₃
	Cs₄Cu₅Cl₉	8	Cs₄Cu₅Cl₉ → 3/4Cs₃Cu₂Cl₅ + 7/4CsCu₂Cl₃
	Rb₄Cu₅I₉	–17	Rb₄Cu₅I₉ → 3/2RbI + 5/2RbCu₂I₃
	Rb₄Cu₅Br₉	–4	Rb₄Cu₅Br₉ → Rb₂CuBr₃ + 2RbCu₂Br₃
	Rb₄Cu₅Cl₉	22	Rb₄Cu₅Cl₉ → 12/5Cu + 1/5Rb₂CuCl₃ + 6/5Rb₃Cu₂Cl₇
214-type	Cs₂CuI₄	–17	Cs₂CuI₄ → 1/2CsI₃ + 1/2Cs₃Cu₂I₅
	Cs₂CuBr₄	14	Cs₂CuBr₄ → 1/2CsBr + 1/4CsBr₃ + 1/2CsCuBr₃ + 1/4Cs₃Cu₂Br₅
	Cs₂CuCl₄	34	Cs₂CuCl₄ → CsCl + CsCuCl₃
	Rb₂CuI₄	–2	Rb₂CuI₄ → RbI + 1/2RbI₃ + 1/2RbCu₂I₃
	Rb₂CuBr₄	10	Rb₂CuBr₄ → 2RbBr + CuBr₂
	Rb₂CuCl₄	–9	Rb₂CuCl₄ → 1/2RbCl + 1/2Rb₃Cu₂Cl₇
113-type	CsCuI₃	–34	CsCuI₃ → 1/2CsI₃ + 1/2CsCu₂I₃
	CsCuBr₃	19	CsCuBr₃ → 1/2CuBr₂ + 1/2Cs₂CuBr₄
	CsCuCl₃	5	CsCuCl₃ → 1/2CuCl₂ + 1/2Cs₂CuCl₄
	RbCuI₃	–42	RbCuI₃ → 1/2RbI₃ + 1/2RbCu₂I₃
	RbCuBr₃	21	RbCuBr₃ → RbBr + CuBr₂
	RbCuCl₃	–10	RbCuCl₃ → 1/3CuCl₂ + 1/3Rb₃Cu₂Cl₇
327-type	Cs₃Cu₂I₇	–31	Cs₃Cu₂I₇ → CsI₃ + 1/2Cs₃Cu₂I₅ + 1/2CsCu₂I₃
	Cs₃Cu₂Br₇	9	Cs₃Cu₂Br₇ → Cs₂CuBr₄ + CsCuBr₃
	Cs₃Cu₂Cl₇	9	Cs₃Cu₂Cl₇ → CsCuCl₃ + Cs₂CuCl₄
	Rb₃Cu₂I₇	–31	Rb₃Cu₂I₇ → RbI + RbI₃ + RbCu₂I₃
	Rb₃Cu₂Br₇	23	Rb₃Cu₂Br₇ → 3RbBr + 2CuBr₂
	Rb₃Cu₂Cl₇	15	Rb₃Cu₂Cl₇ → Rb₂CuCl₄ + RbCuCl₃

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Table 3. The relative energy per formula unit (eV/f.u.) of 214-type CHPs including Cs₂CuI₄, Rb₂CuI₄, and Rb₂CuBr₄ in the different space group encompassing Pnma and Cmca, which are all non-existing phase in the ICSD.

Space group	Cs₂CuI₄	Rb₂CuI₄	Rb₂CuBr₄
Pnma	0.00	0.00	0.00
Cmca	0.29	0.33	0.04

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Table 4. The relative energy per formula unit (eV/f.u.) of 113-type CHP including CsCuI₃, RbCuI₃, and RbCuBr₃ in the different space group containing C2221, P6₁22, Pbcn, which are non-existing phase in the ICSD.

Space group	CsCuI₃	RbCuI₃	RbCuBr₃
C2221	0.00	0.00	0.00
P6₁22	0.03	0.02	0.10
Pbcn	0.15	0.09	0.11

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Table 5. Summary for the stability region and decomposition energy of ODP in the different type CHPs A_lB_mX_n (A = Rb and Cs; B = Cu; X = Cl, Br, and I; l, m, and n are integers; named as lmn-type). For each type CHP, number 1 and 2 represent decomposition energy and stability region, respectively. ‘√’ and ‘×’ symbols indicate ‘stable’ and ‘non-stable’ phase, respectively. Yellow square shows that this type is existing phase from inorganic Crystal Structure Database (ICSD).

A	B	X	325		123		213		459		214		113		327
Cs	Cu	I	√	√	√	√	×	×	×	×	×	×	×	×	×	×
		Br	√	√	√	√	×	×	×	×	√	√	√	√	√	√
		Cl	√	√	√	√	×	×	√	√	√	√	√	√	√	√
Rb		I	√	√	√	√	√	√	×	×	×	×	×	×	×	×
		Br	√	√	√	√	√	√	×	×	√	√	√	√	√	√
		Cl	×	×	√	√	√	×	√	√	×	×	×	×	√	√
Note: 1: Decomposition energy. 2: Stability region. √: stable. × : Non-stable. : Exist.

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[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 doi: 10.1038/nature04645
[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 doi: 10.1038/s41586-018-0691-0
[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 doi: 10.1038/nnano.2014.149
[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 doi: 10.1002/adma.201306281
[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 doi: 10.1126/science.aad1818
[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 doi: 10.1002/adma.201502490
[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 doi: 10.1021/acsenergylett.6b00396
[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 doi: 10.1021/acs.jpclett.6b02763
[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 doi: 10.1021/acs.chemmater.7b02415
[10]	Cortecchia D, Dewi H A, Yin J, et al. Lead-free MA₂CuCl_xBr_{4– x} hybrid perovskites. Inorg Chem, 2016, 55(3), 1044 doi: 10.1021/acs.inorgchem.5b01896
[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 doi: 10.1021/acs.chemmater.7b04161
[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 doi: 10.1021/acs.jpclett.7b02992
[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 doi: 10.1021/acsami.8b00495
[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 doi: 10.1002/adma.201804547
[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 doi: 10.1016/j.jssc.2004.05.004
[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 doi: 10.1002/ange.201705113
[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 doi: 10.1039/C8CC07118G
[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 doi: 10.1021/ja01125a012
[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 doi: 10.1088/0953-8984/16/12/003
[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 doi: 10.1063/1.2719290
[21]	Kousaka Y, Koyama T, Miyagawa M, et al. Crystal growth of chiral magnetic material in CsCuCl₃. J Phys Conf Ser, 2014, 502, 012019 doi: 10.1088/1742-6596/502/1/012019
[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 doi: 10.1103/PhysRevB.54.11169
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[26]	Zhao X G, Yang D, Sun Y, et al. Cu–In halide perovskite solar absorbers. J Am Chem Soc, 2017, 139(19), 6718 doi: 10.1021/jacs.7b02120

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

Article Navigation > Journal of Semiconductors > 2020 > 41(5): 052201

Zhongti Sun, Xiwen Chen, Wanjian 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]. Journal of Semiconductors, 2020, 41(5): 052201. doi: 10.1088/1674-4926/41/5/052201 ****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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Zhongti Sun, Xiwen Chen, Wanjian Yin. Comprehensive first-principles studies on phase stability of copper-based halide perovskite derivatives A_lCu_mX_n (A = Rb and Cs; X = Cl, Br, and I)[J]. Journal of Semiconductors, 2020, 41(5): 052201. doi: 10.1088/1674-4926/41/5/052201 ****

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

DOI: 10.1088/1674-4926/41/5/052201

1.
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS), Soochow University, Suzhou 215006, China
2.
Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies, Soochow University, Suzhou 215006, China
3.
Key Lab of Advanced Optical Manufacturing Technologies of Jiangsu Province & Key Lab of Modern Optical Technologies of Education Ministry of China, Soochow University, Suzhou 215006, China

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Corresponding author: Email: wjyin@suda.edu.cn
Received Date: 2020-02-21
Revised Date: 2020-03-03
Published Date: 2020-05-01

Abstract

Abstract

Recently, inorganic copper-based halide perovskites and their derivatives (CHPs) with chemical formulas A_lCu_mX_n (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 A_lCu_mX_n 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.
- first-principles calculations,
- copper-based halide perovskite,
- stability,
- phase diagram

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References

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

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

DOI: 10.1088/1674-4926/41/5/052201

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

DOI: 10.1088/1674-4926/41/5/052201

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

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