skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3

Abstract

Understanding the formation chemistry of metal halide perovskites is key to optimizing processing conditions and realizing enhanced optoelectronic properties. Here, we reveal the structure of the crystalline precursor in the formation of methylammonium lead iodide (MAPbI 3) from the single-step deposition of lead chloride and three equivalents of methylammonium iodide (PbCl 2 + 3MAI) (MA = CH 3NH 3). The as-spun film consists of crystalline MA 2PbI 3Cl, which is composed of one-dimensional chains of lead halide octahedra, coexisting with disordered MACl. We show that the transformation of precursor into perovskite is not favored in the presence of MACl, and thus the gradual evaporation of MACl acts as a self-regulating mechanism to slow the conversion. We propose the stable precursor phase enables dense film coverage and the slow transformation may lead to improved crystal quality. As a result, this enhanced chemical understanding is paramount for the rational control of film deposition and the fabrication of superior optoelectronic devices.

Authors:
ORCiD logo; ; ; ; ; ; ORCiD logo;
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1465603
Alternate Identifier(s):
OSTI ID: 1461197
Grant/Contract Number:  
[AC02-76SF00515; DGE-1147470]
Resource Type:
Published Article
Journal Name:
Nature Communications
Additional Journal Information:
[Journal Name: Nature Communications Journal Volume: 9 Journal Issue: 1]; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Stone, Kevin H., Gold-Parker, Aryeh, Pool, Vanessa L., Unger, Eva L., Bowring, Andrea R., McGehee, Michael D., Toney, Michael F., and Tassone, Christopher J. Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3. United Kingdom: N. p., 2018. Web. doi:10.1038/s41467-018-05937-4.
Stone, Kevin H., Gold-Parker, Aryeh, Pool, Vanessa L., Unger, Eva L., Bowring, Andrea R., McGehee, Michael D., Toney, Michael F., & Tassone, Christopher J. Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3. United Kingdom. doi:10.1038/s41467-018-05937-4.
Stone, Kevin H., Gold-Parker, Aryeh, Pool, Vanessa L., Unger, Eva L., Bowring, Andrea R., McGehee, Michael D., Toney, Michael F., and Tassone, Christopher J. Mon . "Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3". United Kingdom. doi:10.1038/s41467-018-05937-4.
@article{osti_1465603,
title = {Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3},
author = {Stone, Kevin H. and Gold-Parker, Aryeh and Pool, Vanessa L. and Unger, Eva L. and Bowring, Andrea R. and McGehee, Michael D. and Toney, Michael F. and Tassone, Christopher J.},
abstractNote = {Understanding the formation chemistry of metal halide perovskites is key to optimizing processing conditions and realizing enhanced optoelectronic properties. Here, we reveal the structure of the crystalline precursor in the formation of methylammonium lead iodide (MAPbI3) from the single-step deposition of lead chloride and three equivalents of methylammonium iodide (PbCl2 + 3MAI) (MA = CH3NH3). The as-spun film consists of crystalline MA2PbI3Cl, which is composed of one-dimensional chains of lead halide octahedra, coexisting with disordered MACl. We show that the transformation of precursor into perovskite is not favored in the presence of MACl, and thus the gradual evaporation of MACl acts as a self-regulating mechanism to slow the conversion. We propose the stable precursor phase enables dense film coverage and the slow transformation may lead to improved crystal quality. As a result, this enhanced chemical understanding is paramount for the rational control of film deposition and the fabrication of superior optoelectronic devices.},
doi = {10.1038/s41467-018-05937-4},
journal = {Nature Communications},
number = [1],
volume = [9],
place = {United Kingdom},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1038/s41467-018-05937-4

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Planar Heterojunction Perovskite Solar Cells via Vapor-Assisted Solution Process
journal, December 2013

  • Chen, Qi; Zhou, Huanping; Hong, Ziruo
  • Journal of the American Chemical Society, Vol. 136, Issue 2, p. 622-625
  • DOI: 10.1021/ja411509g

Nika : software for two-dimensional data reduction
journal, March 2012


Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases
journal, November 2016

  • Munir, Rahim; Sheikh, Arif D.; Abdelsamie, Maged
  • Advanced Materials, Vol. 29, Issue 2
  • DOI: 10.1002/adma.201604113

Photo-induced halide redistribution in organic–inorganic perovskite films
journal, May 2016

  • deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11683

Crystallization of Methyl Ammonium Lead Halide Perovskites: Implications for Photovoltaic Applications
journal, September 2014

  • Tidhar, Yaron; Edri, Eran; Weissman, Haim
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja505556s

Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013

  • Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
  • Nature, Vol. 499, Issue 7458, p. 316-319
  • DOI: 10.1038/nature12340

Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
journal, June 2017


Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009

  • Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
  • Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
  • DOI: 10.1021/ja809598r

Crystallization Kinetics of Organic–Inorganic Trihalide Perovskites and the Role of the Lead Anion in Crystal Growth
journal, February 2015

  • Moore, David T.; Sai, Hiroaki; Tan, Kwan W.
  • Journal of the American Chemical Society, Vol. 137, Issue 6
  • DOI: 10.1021/ja512117e

Analysis of the kinetics of phase transformations
journal, January 1992

  • Mittemeijer, E. J.
  • Journal of Materials Science, Vol. 27, Issue 15
  • DOI: 10.1007/BF01105093

Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation
journal, January 2015

  • Azpiroz, Jon M.; Mosconi, Edoardo; Bisquert, Juan
  • Energy & Environmental Science, Vol. 8, Issue 7
  • DOI: 10.1039/C5EE01265A

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


Perovskite energy funnels for efficient light-emitting diodes
journal, June 2016

  • Yuan, Mingjian; Quan, Li Na; Comin, Riccardo
  • Nature Nanotechnology, Vol. 11, Issue 10
  • DOI: 10.1038/nnano.2016.110

Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors
journal, April 2015

  • Zhu, Haiming; Fu, Yongping; Meng, Fei
  • Nature Materials, Vol. 14, Issue 6
  • DOI: 10.1038/nmat4271

Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide
journal, July 2015

  • Ahn, Namyoung; Son, Dae-Yong; Jang, In-Hyuk
  • Journal of the American Chemical Society, Vol. 137, Issue 27
  • DOI: 10.1021/jacs.5b04930

Structural and chemical evolution of methylammonium lead halide perovskites during thermal processing from solution
journal, January 2016

  • Nenon, David P.; Christians, Jeffrey A.; Wheeler, Lance M.
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C6EE01047D

Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013

  • Stranks, S. D.; Eperon, G. E.; Grancini, G.
  • Science, Vol. 342, Issue 6156, p. 341-344
  • DOI: 10.1126/science.1243982

Controllable Grain Morphology of Perovskite Absorber Film by Molecular Self-Assembly toward Efficient Solar Cell Exceeding 17%
journal, August 2015

  • Li, Wenzhe; Fan, Jiandong; Li, Jiangwei
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b06444

A combined single crystal neutron/X-ray diffraction and solid-state nuclear magnetic resonance study of the hybrid perovskites CH 3 NH 3 PbX 3 (X = I, Br and Cl)
journal, January 2015

  • Baikie, Tom; Barrow, Nathan S.; Fang, Yanan
  • Journal of Materials Chemistry A, Vol. 3, Issue 17
  • DOI: 10.1039/C5TA01125F

Relationships between Lead Halide Perovskite Thin-Film Fabrication, Morphology, and Performance in Solar Cells
journal, November 2015

  • Sharenko, Alexander; Toney, Michael F.
  • Journal of the American Chemical Society, Vol. 138, Issue 2
  • DOI: 10.1021/jacs.5b10723

Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013

  • Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J.
  • Nature, Vol. 501, Issue 7467, p. 395-398
  • DOI: 10.1038/nature12509

Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
journal, July 2014

  • Jeon, Nam Joong; Noh, Jun Hong; Kim, Young Chan
  • Nature Materials, Vol. 13, Issue 9, p. 897-903
  • DOI: 10.1038/nmat4014

Solvent engineering towards controlled grain growth in perovskite planar heterojunction solar cells
journal, January 2015

  • Rong, Yaoguang; Tang, Zhongjia; Zhao, Yufeng
  • Nanoscale, Vol. 7, Issue 24
  • DOI: 10.1039/C5NR02866C

Roadmap and roadblocks for the band gap tunability of metal halide perovskites
journal, January 2017

  • Unger, E. L.; Kegelmann, L.; Suchan, K.
  • Journal of Materials Chemistry A, Vol. 5, Issue 23
  • DOI: 10.1039/C7TA00404D

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012


Retarding the crystallization of PbI 2 for highly reproducible planar-structured perovskite solar cells via sequential deposition
journal, January 2014

  • Wu, Yongzhen; Islam, Ashraful; Yang, Xudong
  • Energy Environ. Sci., Vol. 7, Issue 9
  • DOI: 10.1039/C4EE01624F

Perovskite-based solar cells: impact of morphology and device architecture on device performance
journal, January 2015

  • Salim, Teddy; Sun, Shuangyong; Abe, Yuichiro
  • Journal of Materials Chemistry A, Vol. 3, Issue 17
  • DOI: 10.1039/C4TA05226A

Additive Enhanced Crystallization of Solution-Processed Perovskite for Highly Efficient Planar-Heterojunction Solar Cells
journal, March 2014

  • Liang, Po-Wei; Liao, Chien-Yi; Chueh, Chu-Chen
  • Advanced Materials, Vol. 26, Issue 22, p. 3748-3754
  • DOI: 10.1002/adma.201400231

Chlorine in PbCl 2 -Derived Hybrid-Perovskite Solar Absorbers
journal, October 2015


MAPbI3-xClx Mixed Halide Perovskite for Hybrid Solar Cells: The Role of Chloride as Dopant on the Transport and Structural Properties
journal, November 2013

  • Colella, Silvia; Mosconi, Edoardo; Fedeli, Paolo
  • Chemistry of Materials, Vol. 25, Issue 22, p. 4613-4618
  • DOI: 10.1021/cm402919x

Monitoring the Formation of a CH 3 NH 3 PbI 3- x Cl x Perovskite during Thermal Annealing Using X-Ray Scattering
journal, May 2016

  • Barrows, Alexander T.; Lilliu, Samuele; Pearson, Andrew J.
  • Advanced Functional Materials, Vol. 26, Issue 27
  • DOI: 10.1002/adfm.201601309

THE CRYSTAL STRUCTURE OF LEAD(II) IODIDE-DIMETHYLSULPHOXIDE(1/2), PbI 2 (dmso) 2
journal, June 1980

  • Miyamae, Hiroshi; Numahata, Yoshinaho; Nagata, Miharu
  • Chemistry Letters, Vol. 9, Issue 6
  • DOI: 10.1246/cl.1980.663

Chloride in Lead Chloride-Derived Organo-Metal Halides for Perovskite-Absorber Solar Cells
journal, December 2014

  • Unger, Eva L.; Bowring, Andrea R.; Tassone, Christopher J.
  • Chemistry of Materials, Vol. 26, Issue 24
  • DOI: 10.1021/cm503828b

Thermal Behavior of Methylammonium Lead-Trihalide Perovskite Photovoltaic Light Harvesters
journal, October 2014

  • Dualeh, Amalie; Gao, Peng; Seok, Sang Il
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm502468k

Controlling Nucleation and Growth of Metal Halide Perovskite Thin Films for High-Efficiency Perovskite Solar Cells
journal, February 2017


Thermally Induced Structural Evolution and Performance of Mesoporous Block Copolymer-Directed Alumina Perovskite Solar Cells
journal, April 2014

  • Tan, Kwan Wee; Moore, David T.; Saliba, Michael
  • ACS Nano, Vol. 8, Issue 5
  • DOI: 10.1021/nn500526t