二甲基胺阳离子掺杂甲胺铅溴钙钛矿材料的固体NMR研究

doi:10.11938/cjmr20222994

摘要/Abstract

摘要：

本文利用氘核磁共振（²H NMR）技术对阳离子掺杂铅溴钙钛矿MA_0.6DMA_0.4PbBr₃中内嵌阳离子的运动状态进行了较为深入的研究．通过对二甲基胺（DMA）和甲胺（MA）阳离子的选择性氘代，我们实现了对上述材料中不同内嵌阳离子的选择性NMR观测．研究结果显示，在低温下，该材料中的DMA与MA阳离子都接近于双重旋转模型；随着温度升高，DMA与MA阳离子的运动自由度增加，其运动逐步转变为快速各向同性运动．且在相同温度时，DMA阳离子比MA阳离子运动更快，表明该材料中阳离子运动状态不一致．在对阳离子运动研究的基础上，我们对该材料相结构转变的分子机制进行了探讨．

关键词: 固体氘核磁共振, 分子运动, 选择性观测, 阳离子掺杂钙钛矿, 二甲基胺阳离子

Abstract:

In this paper, ²H nuclear magnetic resonance (NMR) was performed to study the motions of the embedded cations in the cation-doped lead bromide perovskite (MA_0.6DMA_0.4PbBr₃). By selectively deuterating dimethylamine (DMA) and methylammonium (MA) cations, we achieved selective NMR observations of the different embedded cations in the materials. The results show that at low temperatures, both the DMA and MA cations in the material have molecular motions close to the double rotation model. As the temperature increases, the motion freedom of the DMA and MA cations increases, and the motions gradually transform into fast isotropic motions. It was observed that the DMA cations have higher mobility than the MA cations in the same materials at the same temperature, indicating that there is a significant inhomogeneity in the states of cations in the material. Based on the study of the cation motions, the molecular mechanism of the phase transition of the material was discussed.

Key words: solid-state ²H NMR, molecular motion, selectively probing, cation-doped perovskite, dimethylamine cation

中图分类号:

O482.53

马开阳,乔文成,王雪璐,姚叶锋. 二甲基胺阳离子掺杂甲胺铅溴钙钛矿材料的固体NMR研究[J]. 波谱学杂志, 2023, 40(1): 10-21.

MA Kaiyang,QIAO Wencheng,WANG Xuelu,YAO Yefeng. A Solid-state NMR Study of Dimethylamine Cation-doped MAPbBr₃ Perovskite Materials[J]. Chinese Journal of Magnetic Resonance, 2023, 40(1): 10-21.

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参考文献 25

[1]	CHEN X L, LV W, SU Q C, et al. Conversion of lignocellulose studied by nuclear magnetic resonance[J]. Chinese J Magn Reson, 2021, 38(2): 277-290.
	陈晓丽, 吕微, 苏秋成, 等. 核磁共振技术在生物质转化中的应用[J]. 波谱学杂志, 2021, 38(2): 277-290.
[2]	WALTER M G, WARREN E L, MCKONE J R, et al. Solar water splitting cells[J]. Chem Rev, 2010, 110(11): 6446-6473. doi: 10.1021/cr1002326 pmid: 21062097
[3]	GOH H H, LI C, ZHANG D, et al. Application of choosing by advantages to determine the optimal site for solar power plants[J]. Sci Rep, 2022, 12(1): 1-16. doi: 10.1038/s41598-021-99269-x
[4]	NOZIK A J, MILLER J. Introduction to solar photon conversion[J]. Chem Rev, 2010, 110(11): 6443-6445. doi: 10.1021/cr1003419 pmid: 21062096
[5]	MARTINHO F. Challenges for the future of tandem photovoltaics on the path to terawatt levels: a technology review[J]. Energy Environ Sci, 2021, 14(7): 3840-3871. doi: 10.1039/D1EE00540E
[6]	JEONG J, KIM M, SEO J, et al. Pseudo-halide anion engineering for α-FAPbI₃ perovskite solar cells[J]. Nature, 2021, 592(7854): 381-385. doi: 10.1038/s41586-021-03406-5
[7]	LIU D T, LUO D Y, IQBAL A N, et al. Strain analysis and engineering in halide perovskite photovoltaics[J]. Nat Mater, 2021, 20(10): 1337-1346. doi: 10.1038/s41563-021-01097-x pmid: 34531574
[8]	SELIG O, SADHANALA A, MÜLLER C, et al. Organic cation rotation and immobilization in pure and mixed methylammonium lead-halide perovskites[J]. J Am Chem Soc, 2017, 139(11): 4068-4074. doi: 10.1021/jacs.6b12239 pmid: 28240902
[9]	LI Z, KLEIN T R, KIM D H, et al. Scalable fabrication of perovskite solar cells[J]. Nat Rev Mater, 2018, 3(4): 1-20. doi: 10.1038/s41578-018-0013-z
[10]	STRANKS S D, SNAITH H J. Metal-halide perovskites for photovoltaic and light-emitting devices[J]. Nat Nanotech, 2015, 10(5): 391-402. doi: 10.1038/nnano.2015.90
[11]	SPANOPOULOS I, KE W, STOUMPOS C C, et al. Unraveling the chemical nature of the 3D “hollow” hybrid halide perovskites[J]. J Am Chem Soc, 2018, 140(17): 5728-5742. doi: 10.1021/jacs.8b01034
[12]	STODDARD R J, RAJAGOPAL A, PALMER R L, et al. Enhancing defect tolerance and phase stability of high-bandgap perovskites via guanidinium alloying[J]. ACS Energy Lett, 2018, 3(6): 1261-1268. doi: 10.1021/acsenergylett.8b00576
[13]	JARIWALA S, KUMAR R E, EPERON G E, et al. Dimethylammonium addition to halide perovskite precursor increases vertical and lateral heterogeneity[J]. ACS Energy Lett, 2021, 7(1): 204-210. doi: 10.1021/acsenergylett.1c02302
[14]	SHI Z F, ZHANG Y, CUI C, et al. Symmetrization of the crystal lattice of MAPbI₃ boosts the performance and stability of metal-perovskite photodiodes[J]. Adv Mater, 2017, 29(30): 1701656. doi: 10.1002/adma.201701656
[15]	RAY A, MARTÍN-GARCÍA B, MOLITERNI A, et al. Mixed dimethylammonium/methylammonium lead halide perovskite crystals for improved structural stability and enhanced photodetection[J]. Adv Mater, 2022, 34(7): 2106160. doi: 10.1002/adma.202106160
[16]	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
[17]	SIMENAS M, BALCIUNAS S, WILSON J N, et al. Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites[J]. Nat Commun, 2020, 11(1): 1-9. doi: 10.1038/s41467-019-13993-7
[18]	SIMENAS M, BALČIU̅NAS S, SVIRSKAS S, et al. Phase diagram and cation dynamics of mixed MA_1-xFA_xPbBr₃ hybrid perovskites[J]. Chem Mater, 2021, 33(15): 5926-5934. doi: 10.1021/acs.chemmater.1c00885
[19]	ANELLI C, CHIEROTTI M R, BORDIGNON S, et al. Investigation of dimethylammonium solubility in MAPbBr₃ hybrid perovskite: synthesis, crystal structure, and optical properties[J]. Inorg Chem, 2018, 58(1): 944-949. doi: 10.1021/acs.inorgchem.8b03072
[20]	LI L Q, LIU X, ZHANG H J, et al. Enhanced X-ray sensitivity of MAPbBr₃ detector by tailoring the interface-states density[J]. ACS Appl Mater Interfaces, 2019, 11(7): 7522-7528. doi: 10.1021/acsami.8b18598
[21]	KUBICKI D J, STRANKS S D, GREY C P, et al. NMR spectroscopy probes microstructure, dynamics and doping of metal halide perovskites[J]. Nat Rev Chem, 2021, 5(9): 624-645. doi: 10.1038/s41570-021-00309-x
[22]	QIAO W C, LIANG J, DONG W, et al. Illumination-induced changes in methylammonium lead bromine perovskites. An in situ ²H NMR study[J]. J Phys Chem C, 2021, 125(18): 9908-9915. doi: 10.1021/acs.jpcc.1c01814
[23]	ZHANG W, YE H Y, GRAF R, et al. Tunable and switchable dielectric constant in an amphidynamic crystal[J]. J Am Chem Soc, 2013, 135(14): 5230-5233. doi: 10.1021/ja3110335 pmid: 23517129
[24]	TOBAR C, CORDOVA R, SOLOMON T, et al. Water dynamics in deuterated gypsum, CaSO₄⋅2D₂O, investigated by solid state deuterium NMR[J]. J Magn Reson, 2020, 310: 106640. doi: 10.1016/j.jmr.2019.106640
[25]	TSAI H, ASADPOUR R, BLANCON J C, et al. Light-induced lattice expansion leads to high-efficiency perovskite solar cells[J]. Science, 2018, 360(6384): 67-70. doi: 10.1126/science.aap8671 pmid: 29622649