MAPbCl3钙钛矿中甲胺阳离子运动的固体2H NMR研究

doi:10.11938/cjmr20212915

摘要/Abstract

摘要：

本文利用固体²H核磁共振（²H NMR）技术探究了甲胺铅氯（MAPbCl₃）钙钛矿正交相、四方相和立方相晶体结构内甲胺阳离子（MA）的运动特征.结合²H NMR实验数据和拟合数据，本文分析和建立了不同相结构中MA阳离子的运动模型，揭示了不同相结构中MA阳离子的运动特征：正交相中MA并不处于完全静止状态，而是在围绕C-N键快速内旋转的同时局部晃动；随着温度升高，MA在钙钛矿晶格中呈现出多种不同的运动模式，MA阳离子运动在不同温度下的变化过程与该材料的相转变过程并不一致.该研究有助于加深对MAPbCl₃相结构转变分子机制的理解.

关键词: 固体²H NMR, 离子运动, NMR模拟, MAPbCl₃钙钛矿

Abstract:

In this work, the motions of methylammonium cations (MA) in different phase structures of MAPbCl₃ perovskites, including orthorhombic, tetragonal and cubic phases, were studied by solid-state ²H nuclear magnetic resonance (NMR). By a combination of experimental ²H NMR and numerical simulations, the motion models in different phase structures of MAPbCl₃ were established in this work. The NMR results disclosed the characteristics of the motions of MA in different phase structures. In the orthorhombic phase, the MA cations are not completely frozen but wobble locally while rapidly rotating around the C-N bond. As the temperature increases, MA cations show various modes of motion in the perovskite lattice. The NMR results also showed that the changes of the motions of MA in different temperatures are not accompanied by the changes of phase structures. The observations in this work will deepen our understanding of the molecular mechanism of the MAPbCl₃ phase transitions.

Key words: solid-state ²H NMR, ionic motion, NMR simulation, MAPbCl₃ perovskite

中图分类号:

O482.53

梁佳琪, 乔文成, 姚叶锋. MAPbCl₃钙钛矿中甲胺阳离子运动的固体²H NMR研究[J]. 波谱学杂志, 2022, 39(2): 144-154.

Jia-qi LIANG, Wen-cheng QIAO, Ye-feng YAO. Solid-state ²H NMR Study of the Motion of CH₃NH₃⁺ in MAPbCl₃ Perovskite[J]. Chinese Journal of Magnetic Resonance, 2022, 39(2): 144-154.

图/表 13

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

图13

参考文献 25

1	MATSUSHIMA T, BENCHEIKH F, KOMINO T, et al High performance from extraordinarily thick organic light-emitting diodes[J]. Nature, 2019, 572 (7770):502-506. doi: 10.1038/s41586-019-1435-5
2	WU W Q, WANG X D, HAN X, et al Flexible photodetector arrays based on patterned CH₃NH₃PbI_3−xCl_x perovskite film for real-time photosensing and imaging[J]. Adv Mater, 2019, 31 (3):1805913. doi: 10.1002/adma.201805913
3	XIAO M D, HUANG F Z, HUANG W C, et al A fast deposition-crystallization procedure for highly efficient lead iodide perovskite thin-film solar cells[J]. Angew Chem Int Edit, 2014, 53 (37):9898-9903. doi: 10.1002/anie.201405334
4	CHENG X H, JING L, ZHAO Y, et al Crystal orientation-dependent optoelectronic properties of MAPbCl₃ single crystals[J]. J Mater Chem C, 2018, 6 (6):1579-1586. doi: 10.1039/C7TC05156E
5	DING J, CHENG X, JING L, et al Polarization-dependent optoelectronic performances in hybrid halide perovskite MAPbX₃ (X = Br, Cl) single-crystal photodetectors[J]. ACS Appl Mater Inter, 2018, 10 (1):845-850. doi: 10.1021/acsami.7b13111
6	MACULAN G, SHEIKH A D, ABDELHADY A L, et al CH₃NH₃PbCl₃ single crystals: inverse temperature crystallization and visible-blind UV-photodetector[J]. J Phys Chem Lett, 2015, 6 (19):3781-3786. doi: 10.1021/acs.jpclett.5b01666
7	ADINOLFI V, OUELLETTE O, SAIDAMINOV M I, et al Fast and sensitive solution-processed visible-blind perovskite UV photodetectors[J]. Adv Mater, 2016, 28 (33):7264-7268. doi: 10.1002/adma.201601196
8	YANG J, LIU K, CHENG Z, et al Investigation of interface effect on the performance of CH₃NH₃PbCl₃/ZnO UV photodetectors[J]. ACS Appl Mater Inter, 2018, 10 (40):34744-34750. doi: 10.1021/acsami.8b11722
9	MOSCONI E, AMAT A, NAZEERUDDIN M K, et al First-principles modeling of mixed halide organometal perovskites for photovoltaic applications[J]. J Phys Chem C, 2013, 117 (27):13902-13913. doi: 10.1021/jp4048659
10	AMAT A, MOSCONI E, RONCA E, et al Cation-induced band-gap tuning in organohalide perovskites: interplay of spin-orbit coupling and octahedra tilting[J]. Nano Lett, 2014, 14 (6):3608-3616. doi: 10.1021/nl5012992
11	POGLITSCH A, WEBER D Dynamic disorder in methylammoniumtrihalogenoplumbates (Ⅱ) observed by millimeter-wave spectroscopy[J]. J Chem Phys, 1987, 87 (11):6373-6378. doi: 10.1063/1.453467
12	BERNARD G M, WASYLISHEN R E, RATCLIFFE C I, et al Methylammonium cation dynamics in methylammonium lead halide perovskites: a solid-state NMR perspective[J]. J Phys Chem A, 2018, 122 (6):1560-1573. doi: 10.1021/acs.jpca.7b11558
13	LIM A R, KIM S H, JOO Y L Structural dynamics of CH₃NH₃⁺ and PbBr₃⁻ in tetragonal and cubic phases of CH₃NH₃PbBr₃ hybrid perovskite by nuclear magnetic resonance[J]. Sci Rep, 2020, 10 (1):13140. doi: 10.1038/s41598-020-70128-5
14	KNOP O, WASYLISHEN R E, WHITE M A, et al Alkylammonium lead halides. Part 2. CH₃NH₃PbX₃ (X = Cl, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation[J]. Canadian J Chem, 1990, 68 (3):412-422. doi: 10.1139/v90-063
15	MAALEJ A, ABID Y, KALLEL A, et al Phase transitions and crystal dynamics in the cubic perovskite CH₃NH₃PbCl₃[J]. Solid State Commun, 1997, 103 (5):279-284. doi: 10.1016/S0038-1098(97)00199-3
16	QIAO W C, WU J, ZHANG R, et al In situ NMR investigation of the photoresponse of perovskite crystal[J]. Matter, 2020, 3 (6):2042-2054. doi: 10.1016/j.matt.2020.09.004
17	WASYLISHEN R E, KNOP O, MACDONALD J B Cation totation in methylammonium lead halides[J]. Solid State Commun, 1985, 56 (7):581-582. doi: 10.1016/0038-1098(85)90959-7
18	WELLER M T, WEBER O J, HENRY P F, et al Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K[J]. Chemical Commun, 2015, 51 (20):4180-4183. doi: 10.1039/C4CC09944C
19	FRANSSEN W M J, VAN ES S G D, DERVISOGLU R, et al Symmetry, dynamics, and defects in methylammonium lead halide perovskites[J]. J Phys Chem Lett, 2017, 8 (1):61-66. doi: 10.1021/acs.jpclett.6b02542
20	CHENG X, JING L, YUAN Y, et al Fe²⁺/Fe³⁺ doped into MAPbCl₃ single crystal: impact on crystal growth and optical and photoelectronic properties[J]. J Phys Chem C, 2019, 123 (3):1669-1676. doi: 10.1021/acs.jpcc.8b12428
21	SPIESS H W Deuteron spin alignment: a probe for studying ultraslow motions in solids and solid polymers[J]. J Chem Phys, 1980, 72 (12):6755-6762. doi: 10.1063/1.439165
22	MACHO V, BROMBACHER L, SPIESS H W The NMR-WEBLAB: an internet approach to NMR lineshape analysis[J]. Appl Magn Reson, 2001, 20 (3):405-432. doi: 10.1007/BF03162288
23	HENTSCHEL D, SILLESCU H, SPIESS H Molecular motion in solid polyethylene as studied by 2D wide line NMR spectroscopy[J]. Die Makromolekulare Chemie, 2003, 180, 241-249.
24	HENTSCHEL R, SPIESS H W Deuterium fourier transform NMR in solids and solid polymers[J]. J Magn Reson, 1979, 35 (1):157-162.
25	WANG J, ZHANG X, GRAF R, et al A small lattice change induces significant dynamic changes of CH₃NH₃⁺ caged in hybrid perovskite crystals: toward understanding the interplay between host lattices and guest molecules[J]. Inorg Chem, 2019, 58 (11):7426-7432. doi: 10.1021/acs.inorgchem.9b00497

MAPbCl₃钙钛矿中甲胺阳离子运动的固体²H NMR研究

Solid-state ²H NMR Study of the Motion of CH₃NH₃⁺ in MAPbCl₃ Perovskite

RichHTML

PDF

评审附件

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 25

相关文章 1

编辑推荐

Metrics

本文评价