Research progress of stability of luminous lead halide perovskite nanocrystals

Fan Qin-Hua; Zu Yan-Qing; Li Lu; Dai Jin-Fei; Wu Zhao-Xin

doi:10.7498/aps.69.20191767

Abstract

The lead halide perovskite nanocrystals (NCs) have become more ideal luminescent materials due to the excellent properties such as narrow emission linewidth, photoluminescence quantum yield (PLQY), adjustable spectrum and facile preparation in comparison with traditional II-VI or III-V group semiconductor NCs. Until now, the external quantum efficiency (EQE) of light-emitting diode (LED) devices using perovskite NCs as emitting layers, has reached > 20%. This optical performance is close to that of the commercially available organic LED, which shows their great potential applications in solid state lighting and panel displaying. However, when perovskite NCs suffer light, heat and polar solvent, they exhibit the poor stability owing to the intrinsic ion properties of perovskite, and highly dynamic interface between NCs and ligands as well as the abundant defects on the surface of NCs. Therefore, how to elevate their stability is a key and urgent problem. In this review, three methods to improve the stability of NCs are summarized: 1) In situ surface passivation with tight-binding or protonation-free sole ligands such as oleic acid (OA), oleamine (OAM), dodecyl benzene sulfonic acid, octylphosphonic acid, sulfobetaines, lecithin and two ligands such as 2-hexyldecanoic acid/OAM, bis-(2,2,4-trimethylpentyl)phosphinic acid/OAM as well as three ligands such as OA/OAM/Al(NO₃)₃·9H₂O, OA/OAM/tris(diethylamino)phosphine); the postsynthetic ligand exchange or passivation with 1-tetradecyl-3-methylimidazolium bromide, 2-aminoethanethiol, silver-trioctylphosphine complex and n-dodecylammonium thiocyanate; 2) the doping of Cs⁺ by FA⁺, Na⁺ and the doping of Pb²⁺ by Zn²⁺, Mn²⁺, Cd²⁺, Sr²⁺, Sb³⁺ in perovskite NCs; 3) the surface coating with inorganic oxides (SiO₂, ZrO₂, Al₂O₃, NiO_x), inorganic salts (NaNO₃, NH₄Br, PbSO₄, NaBr, RbBr, PbBr(OH)), porous materials (mesoporous silica, zeolite-Y, lead-based metal-organic frameworks), polymer materials (polystyrene, poly(styrene-ethylene-butylene-styrene, poly(laurylmethacrylate), poly(maleic anhydride-alt-1-octadecene), polyimide, poly(n-butyl methacrylate-co-2-(methacryloyloxy)ethyl-sulfobetaine)). Besides, we make some suggestions to further improve the stability of NCs as follows: 1) Developing the surface ligands with good dispersity and multi-coordination groups; 2) theoretically studying the influence of ion doping on the structure and stability; 3) realizing the stable and conductive metal oxides shell for uniform and compact encapsulation of NCs core. In a word, these conventional methods can enhance the stability of NCs to a certain extent, which fail to meet the requirements for practical application, so more efforts will be needed in the future.

Keywords:

Authors and contacts

1.
Ningbo Exciton Innovation Materials Research Institute Co., Ltd., Ningbo 315000, China
2.
Key Laboratory of Photonics Technology for Information of Shaanxi Province, School of Electronic and Information Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Corresponding author: Wu Zhao-Xin, zhaoxinwu@mail.xjtu.edu.cn

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References

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Cited By

图 1 胶体铅卤钙钛矿NCs　(a) APbX₃钙钛矿结构, 具有三维共角八面体, 左侧为立方结构(MAPbX₃, FAPbX₃; 显示了两个晶胞), 右侧为正交结构(CsPbX₃); (b)单个立方形CsPbX₃ NCs大角度环形暗场扫描透射电子显微照片, 边缘长度为15 nm; (c)高发光胶体NCs的照片, 从左至右, CsPbBr₃的发射峰为520 nm, CsPb(Cl/Br)₃的发射峰为450 nm, FAPb(Br/I)₃的发射峰为640 nm^[15]

Figure 1. Colloidal lead halide perovskite NCs: (a) The APbX₃ perovskite structure with 3D-corner-sharing octahedra. (Cubic (MAPbX₃, FAPbX₃; two unit cells shown) on the left and orthorhombic (CsPbX₃) on the right); (b) high-angle annular dark-field scanning transmission electron micrograph (HAADF-STEM) of a single, cube-shaped CsPbBr₃ NCs, with 15 nm edge length; (c) photograph of highly luminescent colloidal NCs, from left to right, CsPbBr₃ with emission peak at 520 nm, CsPb(Cl/Br)₃ emitting at 450 nm and FAPb(Br/I)₃ emitting at 640 nm)^[15].

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图 2 磺酸基团的理论钝化效应　(a) CsPbBr₃存在V_Br 的价带最大值和导带最小值的电子DOS曲线; (b)CsPbBr₃存在V_Br 的电子离域结果; (c)磺酸基团钝化CsPbBr₃中V_Br后的价带最大值和导带最小值的电子DOS曲线价带最大值和导带最小值的电子DOS曲线; (d) 磺酸基团钝化CsPbBr₃中V_Br后的电子离域结果^[34]

Figure 2. Theoretical sulfonate passivation effect: (a) Electronic DOS curves of valence band maximum (VBM) and conduction band minimum (CBM) of CsPbBr₃ with V_Br; (b) electron localization function results of CsPbBr₃ with V_Br; (c) electronic DOS curves of valence band maximum (VBM) and conduction band minimum (CBM) of CsPbBr₃ with V_Br passivated by the sulfonate group; (d) electron localization function results of CsPbBr₃ with V_Br passivated by the sulfonate group^[34].

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图 3 CsPbCl₃ NCs中Pb²⁺被Cd²⁺取代的示意图^[50]

Figure 3. Representative scheme for exchange of Pb²⁺ by Cd²⁺ in CsPbCl₃ NCs^[50].

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图 4 CsPbBr₃ NCs被嵌于SiO₂的示意图^[56]

Figure 4. The schematic diagram of synthesis CsPbBr₃ NCs into SiO₂^[56].

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图 5 水辅助使CsPbBr₃/Cs₄PbBr₆复合NCs向CsPbBr₃/CsPb₂Br₅复合NCs转化过程的示意图^[62]

Figure 5. Schematic illustration of the water-assisted transformation process from CsPbBr₃/Cs₄PbBr₆ composite NCs to CsPbBr₃/CsPb₂Br₅ composite NCs^[62].

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图 6 MAPbBr₃形貌变化的示意图^[67]

Figure 6. Schematic illustration of the morphology evolution of MAPbBr₃^[67].

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图 7 厚PMAO聚合物层包覆钙钛矿NCs的后合成处理示意图^[69]

Figure 7. Schematic illustration of postsynthetic treatment for obtaining perovskite NCs with a thick PMAO polymer coating layer^[69].

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图 8 CsPbX₃/介孔二氧化硅复合物的制备过程示意图^[73]

Figure 8. The synthesis process of CsPbX₃/mesoporous silica nanocomposite^[73].

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图 9 分别以星形P4 VP-b-PtBA-b-PS和P4 VP-b-PtBA-b-PEO为纳米反应器逐步合成PS包覆MAPbBr₃/SiO₂核/壳NCs和PEO包覆MAPbBr₃/SiO₂核/壳NCs的路线. CD表示环糊精; BMP表示2-溴–2-甲基丙酸盐; TOABr表示四辛基溴化铵^[77]

Figure 9. Stepwise representation of the synthetic route to PS-capped MAPbBr₃/SiO₂ core/shell NCs and PEO-capped MAPbBr₃/SiO₂ core/shell NCs by exploiting star-like P4 VP-b-PtBA-b-PS and P4 VP-b-PtBA-b-PEO as nanoreactors, respectively. CD, cyclodextrin; BMP, 2-bromo-2-methylpropionate; and TOABr, tetraoctylammonium bromide^[77].

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[12]	He J, Chen H, Chen H, Wang Y, Wu S, Dong Y 2017 Opt. Express 25 12915 Google Scholar
[13]	Won Y, Cho O, Kim T, Chung D, Kim T, Chung H, Jang H, Lee J, Kim D, Jang E 2019 Science 575 634
[14]	Yu D, Cao F, Gao Y, Xiong Y, Zeng H 2018 Adv. Funct. Mater. 28 1800248 Google Scholar
[15]	Akkerman Q, Raino G, Kovalenko M, Manna L 2018 Nat. Mater. 17 394 Google Scholar
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[21]	谢启飞, 王新中, 李玥, 马艳红 2018 深圳信息职业技术学院学报 16 56 Google Scholar Xie Q F, Wang X Z, Li Y, Ma Y H 2018 Journal of Shenzhen Institute of information tecnology 16 56 Google Scholar
[22]	王恩胜, 余丽萍, 廉世勋, 周文理 2019 材料导报 33 777 Google Scholar Wang E S, Yu L P, Lian S X, Zhou W L 2019 Materials Reports 33 777 Google Scholar
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