Lead-Free Halide Double Perovskites Nanomaterials: Fundamentals, Recent Advances and Perspectives

Ferreira, Igor F. L.; Magalhães, Letícia F.; Carvalho, Thaís A. S.; Schiavon, Marco A.

doi:10.21577/0103-5053.20240092

Igor F. L. Ferreira

a graduate with a Bachelor’s degree in Chemistry from the Federal University of São João del-Rei, is currently a Quality Manager at a tin smelting factory. As a member of the Material Chemistry Research Group (GPQM), he focused on lead-free semiconductors, particularly the synthesis and characterization of rudorfite (Ag₂BiI₅), and conducting a comprehensive literature review on double perovskites, under the guidance of Prof Dr Marco Antonio Schiavon.

Grupo de Pesquisa em Química de Materiais (GPQM), Departamento de Ciências Naturais (DCNat), Universidade Federal de São João del-Rei (UFSJ), Campus Dom Bosco, Praça Dom Helvécio, 74, 36301-160 São João del-Rei-MG, Brazil

https://orcid.org/0000-0003-1264-4287

Letícia F. Magalhães

is graduated in Chemistry Bachelor’s degree from the Federal University of São João del-Rei (2016-2019). Master by the Graduate Program in Physics and Chemistry of Materials at the Federal University of São João Del-Rei (2020-2022), with the project: study of photophysical processes resulting from the interaction between CsPbBr₃ nanocrystals and the Rhodamine 6G dye. PhD student at the Graduate Program in Physics and Chemistry of Materials at the Federal University of São João Del-Rei (2022) and member of the Research Group in Materials Chemistry (GPQM) under the guidance of Prof Dr Marco Antonio Schiavon.

Grupo de Pesquisa em Química de Materiais (GPQM), Departamento de Ciências Naturais (DCNat), Universidade Federal de São João del-Rei (UFSJ), Campus Dom Bosco, Praça Dom Helvécio, 74, 36301-160 São João del-Rei-MG, Brazil

https://orcid.org/0000-0002-4496-5424

Thaís A. S. Carvalho

is graduated in Chemical Engineering from the Federal University of São João Del-Rei (Brazil). Currently, she is a PhD student in Physics and Chemistry of Materials at the Federal University of São João Del-Rei and member of the Research Group in Materials Chemistry (GPQM). Her research interest focuses on synthesis and characterization of inorganic nanocrystals of lead-free perovskites, based on cesium and halides under the guidance of Prof Dr Marco Antonio Schiavon.

Grupo de Pesquisa em Química de Materiais (GPQM), Departamento de Ciências Naturais (DCNat), Universidade Federal de São João del-Rei (UFSJ), Campus Dom Bosco, Praça Dom Helvécio, 74, 36301-160 São João del-Rei-MG, Brazil

https://orcid.org/0000-0002-5958-1757

Marco A. Schiavon ^** e-mail: schiavon@ufsj.edu.br

is a chemist and obtained his PhD in 2002 at State University of Campinas (Brazil). Currently, he is a full professor of Inorganic Chemistry at Natural Sciences Department at the Federal University of São João del-Rei (Brazil). He is a research fellow of the National Council of Technological and Scientific Development-CNPq (Brazil). His research interest focuses on synthesis of semiconductor nanocrystals such as colloidal quantum dots and perovskite nanocrystals for energy conversion and understanding photoinduced processes employing optical spectroscopy techniques.

Grupo de Pesquisa em Química de Materiais (GPQM), Departamento de Ciências Naturais (DCNat), Universidade Federal de São João del-Rei (UFSJ), Campus Dom Bosco, Praça Dom Helvécio, 74, 36301-160 São João del-Rei-MG, Brazil

https://orcid.org/0000-0002-1553-5388

* e-mail: schiavon@ufsj.edu.br

Editor handled this article: Ítalo O. Mazali (Guest)

Prof M. A. Schiavon is grateful and honored to have had Prof Oswaldo L. Alves as coauthor of many of his works in recent years.

Perovskite	Tolerance factor	Octahedral factor
Cs₂CuInCl₆	1	0.43
Rb₂CuInCl₆	0.96	0.43
K₂CuInCl₆	0.93	0.43
Cs₂NaInCl₆	0.96	0.5
Cs₂AgInBr₆	0.93	0.49
Cs₂AgInCl₆	0.94	0.54
Rb₂AgInCl₆	0.89	0.54
K₂AgInCl₆	0.87	0.54
Cs₂KInCl₆	0.84	0.67
Cs₂LiYCl₆	0.97	0.45
Cs₂LiCeCl₆	0.96	0.48
Cs₂NaTbCl₆	0.94	0.54
Cs₂NaCeCl₆	0.92	0.56
Cs₂NaEuCl₆	0.89	0.6
Cs₂NaSbCl₆	0.96	0.49
Cs₂AgSbCl₆	0.94	0.53
Cs₂AgSbBr₆	0.93	0.48
Cs₂KSbCl₆	0.87	0.66
Cs₂NaBiCl₆	0.92	0.56
Cs₂AgBiCl₆	0.9	0.6
Cs₂AgBiCl₆	0.9	0.6
Cs₂AgBiBr₆	0.89	0.55
Cs₂KBiCl₆	0.73	0.83

Perovskite	Inserted elements	Synthesis method	Morphology	Max PLQY / %	Applications	Reference
Cs₂AgInCl₆	Na⁺, Bi³⁺	hot injection	nanocrystals	22	^a	96
Cs₂NaInCl₆	Bi³⁺, Mn²⁺	hydrothermal	single crystal	56	^a	82
Cs₂NaInCl₆	Ag⁺	hot injection	nanocrystals	31.1	^a	97
Cs₂AgBiBr₆	Yb³⁺, Eu³⁺	hydrothermal, antisolvent	bulk powder, thin film	–	^a	98
Cs₂AgInCl₆	Na⁺, Bi³⁺	hydrothermal	single crystal	–	scintillator for X-ray imaging	99
Cs₂NaInCl₆	K⁺, Sb³⁺	solution (HCl)	single crystal, bulk powder	82	^a	100
Cs₂KInCl₆	Na⁺, Sb³⁺	solution (HCl)	bulk powder	93	^a	100
Cs₂AgBiBr₆	Cu⁺	hydrothermal	single crystal	–	potential application in near-infrared photodetectors	94
Cs₂AgInCl₆	Cu⁺	hot injection, solution (HCl)	nanocrystals, bulk powder	–	potential application in solar cells and other optoelectronic devices	77
Cs₂LiBiCl6	Mn²⁺	solid state	bulk powder	–	^a	101
Cs2NaBiCl₆	Mn²⁺	solid state	bulk powder	–	^a	101
Cs₂AgInCl₆	Cu⁺	hot injection	nanocrystals	–	potential application in solar cells and other optoelectronic devices	102
Cs2AgBiBr₆	H⁺	solution, spin coating	thin film	–	solar cell	46
Cs₂AgBiCl₆	Al³⁺	hot injection	nanocrystals	17.2	LED	95
Cs₂AgBiBr₆	Sb⁺	hydrothermal	bulk powder	–	composite to enhance photocatalytic oxidation of toluene	56
Cs₂NaInCl₆	Sb³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺	hot injection	nanocrystals	80.1	anti-counterfeiting devices, optical and LED thermometry	53
Cs₂NaYCl₆	Sb³⁺, Eu³⁺, Tb³⁺	hydrothermal	single crystal	58.3	LED	103
Cs₂AgInCl₆	K⁺, La³⁺	hydrothermal	bulk powder	19.9	LED	104
Cs₂NaBiCl₆	Mn²⁺	solution (HCl)	bulk powder	–	^a	105
Cs₂AgInCl₆	Sb³⁺, Yb³⁺	solution (HCl)	bulk powder	50	LED	91
Cs₂AgInCl₆	Fe³⁺	hydrothermal	single crystal	–	potential application in solar cells and other optoelectronic devices	106
Cs₂SnCl₆	Mn²⁺	hot injection	nanocrystals	–	^a	107
Rb₂ZrCl₆	Cs⁺, Te⁴⁺, Sn⁴⁺	hydrothermal	bulk powder	69.7	LED	108
Cs₂HfCl₆	Sb³⁺, Pr³⁺, Eu³⁺, Tb³⁺, Ho³⁺	hot injection	nanocrystals	40.7	scintillator for X-ray and LED imaging	109
Cs₂SnCl₆	Te⁴⁺, Bi³⁺	solution (HCl)	bulk powder	38.6	LED	110
Cs₂SnCl₆	Bi³⁺	hot injection	nanocrystals	35.2	^a	111
Cs₂ZrCl₆	Te⁴⁺, Er³⁺, Nd³⁺, Yb³⁺	co-precipitation	bulk powder	6.1	^a	112
Rb₂HfCl₆	Cs⁺, Bi³⁺	solution (HCl)	bulk powder	66	^a	93
Cs₂SnCl₆	Gd³⁺	hydrothermal (solvothermal)	bulk powder	–	^a	113
Cs₂SnCl₆	La³⁺	hydrothermal (solvothermal)	bulk powder	55	^a	114

Perovskite	Synthesis method	Morphology	Film deposition method	Bandgap / eV	PCE / %	Reference
Cs₂AgBiBr₆	solution process	film	spin-coating	direct 2.21	2.43	43
Cs₂AgBiBr₆	solution process	film	vapor deposition	indirect 2.02	1.37	139
Cs₂AgBiBr₆	precipitation in solution - HBr	crystalline powder	low pressure assisted method	direct 2.05	1.44	140
Cs₂AgBiBr₆	precipitation in solution - HBr	crystalline powder	anti-solvent drip	direct –	2.23	132
Cs₂AgBiBr₆	precipitation in solution - HBr	crystalline powder	spin-coating	direct 2.20	1.26	134
Cs₂AgBiBr₆	modified solution process	crystalline powder	spin-coating	indirect 2.02	0.82	141
Cs₂AgBiBr₆	precipitation in solution - HBr	crystalline powder	solution processing	1.99	2.51	142
Cs₂AgBiBr₆	precipitation in solution - HBr	crystalline powder	vacuum sublimation	2.01	1.41	142
Cs₂AgBiBr₆	solution process	film	two-step heating process	2.02	2.84	136
Cs₂AgBiBr₆	hot-injection	nanocrystal	layer-by-layer deposition process	indirect 2.28	0.46	143
Cs₂AgBiBr₆:Sn	–	film	spin coating	–	2.74	144
Cs₂AgBiBr₆:H	solution process	film	spin coating	1.64	6.37	44
Cs₂AgBi_0.6Sb_0.4Br₆	hot-injection	nanocrystal	spin-coating	indirect 2.22 - DCB 2.26 - toluene	0.09	145
Cs₂NaBiI₆	hydrothermal (solvent processing)	crystalline powder	spin-coating	1.66	0.42	76
Cs₂TiBr₆	vapor-based method	film	vapor-based method	1.8	3.3	146
Cs₂SnI₆	modified solution process	crystalline powder	spin-coating	direct 1.48	0.86	147
Cs₃Fe₂Cl₉	solution process	nanocrystal	simple chemical process/drop-casting	direct 2.73	0.6	148
Cs₃Bi₂I₉	solution process	nanocrystal	spin-coating	2.2	1.09	149

Perovskite	Synthesis method	Morphology	Bandgap / eV	Application	Total electron consumption	Reference
Cs₂AgBiBr₆	hot-injection	nanocrystal	indirect 2.52	CO₂ reduction	105 μmol g^–1	18
Cs₂AgBiBr₆	precursor injection at room temperature, followed by heating	nanoplates	indirect 2.06	CO₂ reduction	255.4 μmol g^–1	153
Cs₂AgBiI₆	antisolvent recrystallization	nanocrystal	indirect 1.82	CO₂ reduction	37.8 μmol g^–1	153
Cs₂AgBiBr₆-Cu-RGO	mechanochemically	nanoplates	indirect 2.0	CO₂ reduction	122 μmol g^–1	152
Cs₂AgBiBr₆-MXene	hot-injection	nanocrystal	–	CO₂ reduction	50.6 μmol g^–1	151
Cs₂NaBiCl₆	milling	microspheres	–	CO₂ reduction	–	154
Cs₂AgBiBr₆	hot-injection	nanocrystal	indirect 2.52	NO removal	–	155
Cs₂AgBiBr₆/RGO	aqueous solution	powder	–	H₂ generation	489 μmol g^–1	58
Cs₂SnI₆/Pt	one-pot hydrothermal	powder	1.22	H₂ generation	430 μmol g^–1	85
Cs₂AgSbCl₆	hot-injection	nanocrystal	2.63	organic synthesis catalysis	–	156
Cs₂AgSbCl₆	precipitation in solution - HCl	crystals	2.46	organic dye degradation	–	157
Cs₂AgSbCl₆	anti-solvent recrystallization	crystals	2.56	organic dye degradation	95.7%	157
Cs₂AgBiBr₆	precipitation in solution - HBr	powder	2.08	organic dye degradation	–	158
Cs₂AgInCl₆	precipitation in solution - HCl	crystals	3.33	degradation of organic pollutants	98.5%	159
Bi₂WO₆/Cs₂AgBiBr₆	hydrothermal, ball milling and thermal evaporation	nanocomposite	2.89/1.98	degradation of organic pollutants	97.4%	160

Perovskite	Synthesis method	Morphology	Bandgap / eV	PLQY / %	Reference
Cs₂TiBr₆:Bi	hydrothermal/autoclave	powder	3.0	78.9	162
Cs₂AgInCl₆:Bi³⁺	hot-injection	nanocrystal	4.71	31.4	163
Cs₂AgInCl₆:Bi³⁺, Eu³⁺	hot-injection	powder	3.1	80.1	164
Cs2(Ag_0.6Na_0.4)InCl₆	hydrothermal/autoclave	powder	3.27	86	165
Cs₂NaInCl₆:Sb³⁺	hot-injection	nano polycrystal	3.947	75	166
Cs₂NaBiCl₆: Eu³⁺	hydrothermal	crystal	–	0.8	167
Ba₂CaWO₆:Mn⁴⁺	solid state reaction	crystal	–	–	168
Cs₂NaYCl₆:Sb³⁺, Eu³⁺	hydrothermal/autoclave	single crystal	–	58.33	127

Perovskite	Synthesis method	Morphology	Bandgap	Application	Reference
Cs₂AgInCl₆	hydrothermal	single crystal	direct 3.2 eV	UV detectors	171
Cs₂AgBiBr₆	one-step spin-coating	thin film	–	photodetectors	172
Cs₂AgInBr₆/SnO₂	home-made low-pressure assisted method	film	–	stable UV and deep blue detector	173
Cs₂PdBr₆	precipitation with HBr	single crystal	1.6 eV	photodetectors	174
Cs₂SnI₆	hot-injection	nanocrystal	1.67 eV	photodetectors	175
Cs₂TeI₆	non-solution process	thin film	indirect 1.62 eV	gas sensor for NO₂	176
Cs₂AgInBr₆	inverse temperature crystallization	single crystal	indirect 2.1 eV	X-ray detectors	177
Cs₂NaTbCl₆	hydrothermal	crystals	–	X-ray detectors	178
Cs₂TeI₆	electrospray deposition	film	–	X-ray detectors	179
Cs₂NaScCl₆:Tb	hydrothermal	single crystal	–	radiation-storage battery	180

[1] * e-mail: schiavon@ufsj.edu.br

Brasil

Brasil

Lead-Free Halide Double Perovskites Nanomaterials: Fundamentals, Recent Advances and Perspectives