Research progress of metal halide perovskite nanometer optoelectronic materials

Shi Wen-Qi; Tian Hong; Lu Yu-Xin; Zhu Hong; Li Fen; Wang Xiao-Xia; Liu Yan-Wen

doi:10.7498/aps.70.20201842

Abstract

Metal halide perovskites, which have aroused the enormous interest from scientists recently, are widely used in a variety of areas such as solar cells, light emitting diodes (LED) and lasers. Nanomaterials exhibit distinguished optical and electrical properties because of their quantum confinement as well as strong anisotropy. The metal halide perovskite nanomaterials have the advantages of adjustable band gap, high quantum efficiency, strong photoluminescence, quantum confinement and long carrier-lifetime. Besides, as a result of the low-cost fabrication and the sufficient raw material reserve, they have a broad prospect in photoelectric applications. But on the other hand, the poor stability of metal halide perovskites, due to the defect trap states and grain boundaries on the surface, cast a shadow towards their practical applications. The moisture, oxygen and ultraviolet of the environment will degrade their photoelectric performances significantly. In this review, we introduce the synthesis and growth mechanism of metal perovskite nanomaterial quantum dots, nanowires and nanoplatelets, and present their novel photoelectric properties and applications in various photoelectric devices. Finally we summarize the emerging challenges and discuss the next-generation photoelectric applications.

Keywords:

Authors and contacts

1.
Aerospace Information Research Institute, Chinese Academy of Sciences, Beijing 100190, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Tianjin Transportation Vocational College, Tianjin 300110, China

Corresponding author: Liu Yan-Wen, shiwenqi96@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 61771454)

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Cited By

图 1 (a) 2009年, 使用CH₃NH₃PbBr₃/TiO₂(实线)和CH₃NH₃PbI₃/TiO₂(虚线)的光电化学电池的入射光子到电流的量子效率(IPCE)作用谱^[9]; (b) 2009年, 使用CH₃NH₃PbBr₃/TiO₂(实线)和CH₃NH₃PbI₃/TiO₂(虚线)的电池在100 mW·cm^–2, AM 1.5 G辐射下的光电流-电压特性^[9]; (c) 2012年, 分别由质量百分比为1%和10%的前驱体溶液于氧化铝介孔薄膜上制备的CH₃NH₃PbBr₃量子点的反射光谱^[26]

Figure 1. (a) The quantum efficiency (IPCE) action spectrum of incident photon to current of a photochemical cell using CH₃NH₃PbBr₃/TiO₂ (solid line) and CH₃NH₃PbI₃/TiO₂ (dashed line) in 2009^[9]; (b) photocurrent-voltage characteristics of CH₃NH₃PbBr₃/TiO₂ (solid line) and CH₃NH₃PbI₃/TiO₂ (dotted line) under radiation of 100 mW·cm^–2 and AM 1.5 in 2009^[9]; (c) in 2012, the reflection spectra of CH₃NH₃PbBr₃ quantum dots on alumina mesoporous films were prepared from precursor solutions with the weight present of 1% and 10%^[26].

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图 2 钙钛矿纳米颗粒的HRTEM图像(尺寸为2 nm)和MX₆八面体阵列示意图^[28]

Figure 2. HRTEM images of perovskite nanoparticles (size 2 nm) and MX₆ octahedral array diagram^[28].

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图 3 钙钛矿纳米粒子在(a)甲苯中紫外-可见吸收光谱和(b)室温下荧光光谱　(a)环境光照射; (b)以365 nm为中心的紫外光照射^[28]

Figure 3. (a) UV-visible absorption spectra in toluene and (b) fluorescence spectrum at room temperature of perovskite nanoparticles: (a) Environmental light irradiation; (b) ultraviolet light irradiation centered at 365 nm^[28].

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图 4 (a)紫外灯激发下(λ = 365 nm)在甲苯中的胶体溶液照片; (b)在所示波长范围内的PL光谱可调性; (c)在不同的沉淀温度下合成的三个样品的光吸收光谱和各自的PL光谱^[31]

Figure 4. (a) A colloidal solution of toluene under UV lamp excitation (λ = 365 nm); (b) the spectral tunability of PL within the wavelength range shown; (c) light absorption spectra and respective PL spectra of the three samples synthesized at different precipitation temperatures^[31].

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图 5 (a) LARP技术的反应系统和过程示意图; (b)前体溶液中起始原料示意图; (c) CH₃NH₃PbBr₃胶体溶液典型光学图像^[32]

Figure 5. (a) Schematic diagram of reaction systems and processes for LARP technology; (b) schematic diagram of the starting material in the precursor solution; (c) typical optical images of CH₃NH₃PbBr₃ colloid solution^[32].

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图 6 用不同质量氯化物(a)和碘化物(b)处理后的10 nm CsPbX₃ NC透射电子显微镜(TEM)图像^[35]

Figure 6. Transmission electron microscope (TEM) images of 10 nm CsPbX₃ NC treated with different masses of chloride (a) and iodide (b)^[35].

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图 7 (a)含Pb钙钛矿纳米线在阳极氧化铝薄膜上不同反应时间的生长情况侧视SEM图像, 其中　(a₁) 0 min, (a₂) 20 min, (a₃) 40 min, (a₄) 80 min; (b)含Pb和(c)含Sn钙钛矿纳米线在阳极氧化铝薄膜上生长俯视SEM图像^[45]

Figure 7. (a) The sideview SEM images of Pb perovskite nanowires on anodic alumina film for different growth time, in which (a₁) 0 min, (a₂) 20 min, (a₃) 40 min and (a₄) 80 min; the overlook SEM images of Pb containing (b) and (c) Sn containing perovskite nanowires on the anodic alumina film^[45].

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图 8 (a) CH₃NH₃PbI₃纳米结构SEM图^[15]; (b) 三种卤化物钙钛矿纳米线的XRD图谱^[15]

Figure 8. (a) SEM diagram of CH₃NH₃PbI₃ nanostructure^[15]; (b) XRD pattern of the three halide perovskite nanowires^[15].

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图 9 单晶CsPbBr₃纳米线的结构表征　(a) 由PbI₂在8 mg/mL CsBr的乙醇溶液中于50 ℃加热12 h得到的CsPbBr₃纳米线和纳米片的SEM图像, 比例尺为10 μm; (b) CsPbBr₃(黑色)的XRD图样, 立方(红色)和正交晶(蓝色) CsPbBr₃的标准XRD图谱^[48]

Figure 9. Structural characterization of single crystal CsPbBr₃ nanowires: (a) SEM images of CsPbBr₃ nanowires and nanoplatelets with a scale of 10 μm obtained by heating PbI₂ in $8 \; {\rm{m}}{\rm{g}}/{\rm{m}}{\rm{L}} $ CsBr ethanol solution at 50 ℃ for 12 h; (b) XRD pattern of CsPbBr₃ (black), standard XRD pattern of cubic (red) and orthorhombic (blue) CsPbBr₃^[48].

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图 10 CsPbBr₃胶体合成中反应温度影响的研究　(a)在150 ℃, 形成绿色发射的8—10 nm纳米立方体; (b)在130 ℃下, 形成了侧面尺寸为20 nm, 厚度为几个单位晶胞(约3 nm)的蓝绿色发射纳米片; (c)在90 ℃下, 观察到了呈蓝色发光的纳米片以及数百纳米的层状^[61]

Figure 10. Study on the influence of reaction temperature in the synthesis of CsPbBr₃ colloid: (a) Formation of green-emitting 8–10 nm nanoplatelet at 150 ℃; (b) at 130 ℃, a blue-green emitting nanoplatelet with a side size of 20 nm and a thickness of several unit cells (about 3 nm) was formed; (c) at 90 ℃, blue-emitting nanoplatelet and layers of several hundred nanometers were observed^[61].

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图 11 CH₃NH₃PbI₃分别在(a) 石墨烯, (b)MoS₂, (c) h-BN基底上生长的光学图像; (d), (e), (f)分别为对应(a), (b), (c)的拉曼光谱图像^[64]

Figure 11. CH₃NH₃PbI₃ grows on (a) graphene, (b) MoS₂, (c) h-BN substrate; (d), (e), (f) Raman spectral images corresponding to (a), (b), and (c)^[64].

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图 12 (a) 卤化物纳米片与甲基卤化铵进行插层示意图; (b) 卤化物晶体转化为卤化物钙钛矿前后厚度对比图; (c)各种卤化物钙钛矿的光学性质^[55]

Figure 12. (a) Schematic diagram of intercalation between halide nanosheet and methyl ammonium halide; (b) comparison of the thickness of halide crystals before and after conversion to halide perovskite; (c) optical properties of various halide perovskites^[55].

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图 13 (a)几个单层的AFM图像, 厚度约为1.6 nm; (b)双层的AFM图像, 厚度约为3.4 nm^[24]

Figure 13. (a) The AFM image of several monolayers, with a thickness of about 1.6 nm; (b) AFM image of double layers with a thickness of 3.4 nm^[24].

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图 14 (a)机械剥落法制备的(C₄H₉NH₃)₂PbI₄光学图像^[70]; (b) Si/SiO₂上(C₄H₉NH₃)2 PbBr₄ 二维晶体的暗场光学图像; (c) (C₄H₉NH₃)₂PbBr₄ 的二维TEM图像晶体^[24]

Figure 14. (a) Mechanical spalling method for the preparation of (C₄H₉NH₃)₂PbI₄ optical images^[70]; (b) dark field optical image of two-dimensional (C₄H₉NH₃)₂PbBr₄ crystal on Si/SiO₂; (c) TEM image crystal of two-dimensional(C₄H₉NH₃)₂PbBr₄^[24].

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图 15 (a)钙钛矿太阳能电池结构的示意图, 其中光滑而致密的钙钛矿覆盖层完全覆盖了介孔TiO₂层(mp-TiO₂)的顶部^[79]; (b)整体设备结构: 玻璃/铟锡氧化物/NiO_x/钙钛矿/ZnO/Al^[80]

Figure 15. (a) Schematic diagram of perovskite solar cell structure, in which the smooth and dense perovskite covering layer completely covers the top of mesoporous TiO₂ layer (MP-TiO₂); (b) overall equipment structure of glass/indium tin oxide /NiO_x/ perovskite/ZnO/Al^[80].

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