Research Progress on the Stability of CsPbX3 Nanocrystals

doi:10.15541/jim20190572

Abstract

Abstract:

All inorganic perovskite nanocrystals with narrow-emission, high quantum efficiency and high carrier mobility have been widely applied in the fields of light emitting diodes and solar cells. However, present surface ligands of the perovskite nanocrystals are in a dynamic bonding state, which easily fall off during separation and purification processes, resulting in the deterioration of quantum efficiency and stability. Besides, the ionic characteristic of halide perovskites makes it extremely sensitive to polar solvents. These disadvantages severely restrict the practical application of perovskite nanocrystals in optoelectronic devices. In this review, based on the surface state of perovskite nanocrystals, the effects of passivation strategies with Lewis acid, Lewis base and surface coating on optical properties, and stability of CsPbX₃ perovskite nanocrystals are analyzed in detail combined with the domestic and abroad research work. Further optimization and improvement of the stability of CsPbX₃ are prospected.

Key words: all inorganic perovskite nanocrystals, surface state, surface passivation, quantum yield, stability

CLC Number:

TQ174

YANG Dandan, LI Xiaoming, MENG Cuifang, CHEN Jiaxin, ZENG Haibo. Research Progress on the Stability of CsPbX₃ Nanocrystals[J]. Journal of Inorganic Materials, 2020, 35(10): 1088-1098.

Figures/Tables 9

Fig. 1 Schematic diagram of passivation strategies for different ligands on the surface of CsPbX3 nanocrystals

Fig. 2 (a) Schematic diagram of instability mechanism of CsPbX3 nanocrystals, (b) agglomeration and (c) decomposing product of CsPbX3 nanocrystals, and schematic diagram of (d) phase transition (non-perovskite phase) and (e) phase transition (perovskite phase)

Fig. 3 (a) Passivation strategy based on hard Lewis acid ligands (left), images under 365 nm UV light (middle), and photoluminescence decay curves (right) of nanocrystals with high and low defect densities[25]; (b) Schematic diagram of DETAI3 surface passivation strategy (left), absorption curves (middle) and long-term phase stability (right) of CsPbI3?xDETAI3 thin films[29]

Table 1 Surface passivation strategies of Lewis acid ligands

Ligands	Treating agent	QY/%	Stability	Ref.
OA/OAm	DDDMAB	~100	21 d	[9]
OA/OAm	TOAB	95	-	[25]
OA/OAm	DDAB	96	-	[26,30]
OA/OAm	NH₄BF₄	(95±2)	-	[27]
OA/OAm	NH₄SCN	(99±2)	-	[28]
OA/OAm	Trimethylsilyl iodine	85	105 d	[31]
OA/OAm	Oxalic acid	89	-	[32]

Fig. 4 (a) Schematic diagram of Lewis base surface passivation strategy for CsPbX3 nanocrystals; (b) Theoretical calculation of the binding energy of mono- and dicarboxylic acids on the surface of CsPbI3 nanocrystals[34]; (c) Schematic diagram of OPA and OAm-CsPbX3 surface passivation strategies and photos after multiple purifications[35]; (d) Surface passivation strategy with zwitterionic ligands (sulfobetaines, phosphocholines and γ-amino acids)[36]

Fig. 5 (a) Passivation strategies with different ligands (OAm, OA and DBSA) on the surface of CsPbBr3 nanocrystals and (b) the corresponding exciton recombination processes[37]; (c) Schematic diagram of PbBrx-rich surface of OAm-CsPbBr3 nanocrystals (left) and Br-rich surface of OAm/OA-CsPbBr3 nanocrystals (right)[11]; (d) Photographs showing the resistance of different samples against water treatment of OAm/OA-CsPbBr3 nanocrystals (above) and OAm-CsPbBr3 nanocrystals (below)[11]

Table 2 Surface passivation strategies of Lewis base ligands

Ligands	QY/%	Stability	Ref.
OAm	~100 %	-	[11]
OA	70	-	[33]
IDA/OAm	95	40 d	[34]
OPA/TOPO	>90	-	[35]
Zwitterion	>90	28 d	[36]
DBSA	95	5 m	[37]
TMPPA/OAm	90	28 d	[38]
OA/TOPO	90	-	[39]
TDPA/OAm	68	-	[40]
DA	94.3	70 d	[41]

Table 3 Characteristics, advantages and disadvantages of different passivation strategies

Strategies		Characteristics	Advantages	Disadvantages	Ref.
Lewis acid ligands	Quaternary ammonium salt	Large steric hindrance	High QY^*	Instable	[9,25-26,30]
Lewis base ligands	Carboxylic acids	Hard base, weak acid	Simple synthesis	Instable, low QY	[32-33]
	Phosphoric acid	Soft alkali, moderately strong acid	High QY, stable	TOPO assisted dissolution	[35]
	Zwitterionic ligands	Surfactant	High QY, stable	Complex process	[36]
	Sulfonic acid	Soft alkali, strong acid	High QY, stable	High temperature	[37]
	Neutral ligands	Lone pair electrons	High QY, stable	Room temperature	[11]

Fig. 6 (a) Schematic diagram of CPB-DBAE@SiO2 preparation process[51]; (b) Transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) images of CsPbBr3@SiO2 nanocrystals and photographs of water stability[60]; (c) Schematic representation (left), HRTEM image (middle), and plot of emission intensity under continuous pulsed laser irradiation (right) of CsPbBr3/CdS nanocrystals[67]

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Research Progress on the Stability of CsPbX₃ Nanocrystals

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