DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Multiple-stage structure transformation of organic-inorganic hybrid perovskite CH 3 NH 3 PbI 3

Abstract

© American Physical Society. By performing spatially resolved Raman and photoluminescence spectroscopy with varying excitation wavelength, density, and data acquisition parameters, we achieve a unified understanding towards the spectroscopy signatures of the organic-inorganic hybrid perovskite, transforming from the pristine state (CH 3 NH 3 PbI 3 ) to the fully degraded state (i.e., PbI 2 ) for samples with varying crystalline domain size from mesoscopic scale (approximately 100 nm) to macroscopic size (centimeters), synthesized by three different techniques. We show that the hybrid perovskite exhibits multiple stages of structure transformation occurring either spontaneously or under light illumination, with exceptionally high sensitivity to the illumination conditions (e.g., power, illumination time, and interruption pattern). We highlight four transformation stages (stages I-IV, with stage I being the pristine state) along either the spontaneous or photoinduced degradation path exhibiting distinctly different Raman spectroscopy features at each stage, and point out that previously reported Raman spectra in the literature reflect highly degraded structures of either stage III or stage IV. Additional characteristic optical features of partially degraded materials under the joint action of spontaneous and photodegradation are also given. This study offers reliable benchmark results for understanding the intrinsic material properties and structure transformation ofmore » this unique category of hybrid materials, and the findings are pertinently important to a wide range of potential applications where the hybrid material is expected to function in greatly different environment and light-matter interaction conditions.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [5];  [4];  [3];  [2];  [1]
  1. The Univ. of North Carolina at Charlotte, Charlotte, NC (United States)
  2. Sungkyunkwan Univ., Suwon (South Korea)
  3. Shaanxi Normal Univ., Xi'an (China)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1330000
Alternate Identifier(s):
OSTI ID: 1378748
Report Number(s):
NREL/JA-5900-67314
Journal ID: ISSN 2160-3308; PRXHAE
Grant/Contract Number:  
AC36-08GO28308; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. X
Additional Journal Information:
Journal Volume: 6; Journal Issue: 3; Journal ID: ISSN 2160-3308
Publisher:
American Physical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; hybrid perovskite; structure; material properties

Citation Formats

Chen, Qiong, Liu, Henan, Kim, Hui -Seon, Liu, Yucheng, Yang, Mengjin, Yue, Naili, Ren, Gang, Zhu, Kai, Liu, Shengzhong, Park, Nam -Gyu, and Zhang, Yong. Multiple-stage structure transformation of organic-inorganic hybrid perovskite CH3NH3PbI3. United States: N. p., 2016. Web. doi:10.1103/PhysRevX.6.031042.
Chen, Qiong, Liu, Henan, Kim, Hui -Seon, Liu, Yucheng, Yang, Mengjin, Yue, Naili, Ren, Gang, Zhu, Kai, Liu, Shengzhong, Park, Nam -Gyu, & Zhang, Yong. Multiple-stage structure transformation of organic-inorganic hybrid perovskite CH3NH3PbI3. United States. https://doi.org/10.1103/PhysRevX.6.031042
Chen, Qiong, Liu, Henan, Kim, Hui -Seon, Liu, Yucheng, Yang, Mengjin, Yue, Naili, Ren, Gang, Zhu, Kai, Liu, Shengzhong, Park, Nam -Gyu, and Zhang, Yong. Thu . "Multiple-stage structure transformation of organic-inorganic hybrid perovskite CH3NH3PbI3". United States. https://doi.org/10.1103/PhysRevX.6.031042. https://www.osti.gov/servlets/purl/1330000.
@article{osti_1330000,
title = {Multiple-stage structure transformation of organic-inorganic hybrid perovskite CH3NH3PbI3},
author = {Chen, Qiong and Liu, Henan and Kim, Hui -Seon and Liu, Yucheng and Yang, Mengjin and Yue, Naili and Ren, Gang and Zhu, Kai and Liu, Shengzhong and Park, Nam -Gyu and Zhang, Yong},
abstractNote = {© American Physical Society. By performing spatially resolved Raman and photoluminescence spectroscopy with varying excitation wavelength, density, and data acquisition parameters, we achieve a unified understanding towards the spectroscopy signatures of the organic-inorganic hybrid perovskite, transforming from the pristine state (CH 3 NH 3 PbI 3 ) to the fully degraded state (i.e., PbI 2 ) for samples with varying crystalline domain size from mesoscopic scale (approximately 100 nm) to macroscopic size (centimeters), synthesized by three different techniques. We show that the hybrid perovskite exhibits multiple stages of structure transformation occurring either spontaneously or under light illumination, with exceptionally high sensitivity to the illumination conditions (e.g., power, illumination time, and interruption pattern). We highlight four transformation stages (stages I-IV, with stage I being the pristine state) along either the spontaneous or photoinduced degradation path exhibiting distinctly different Raman spectroscopy features at each stage, and point out that previously reported Raman spectra in the literature reflect highly degraded structures of either stage III or stage IV. Additional characteristic optical features of partially degraded materials under the joint action of spontaneous and photodegradation are also given. This study offers reliable benchmark results for understanding the intrinsic material properties and structure transformation of this unique category of hybrid materials, and the findings are pertinently important to a wide range of potential applications where the hybrid material is expected to function in greatly different environment and light-matter interaction conditions.},
doi = {10.1103/PhysRevX.6.031042},
journal = {Physical Review. X},
number = 3,
volume = 6,
place = {United States},
year = {Thu Sep 15 00:00:00 EDT 2016},
month = {Thu Sep 15 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Synthesis of Organic-Inorganic Lead Halide Perovskite Nanoplatelets: Towards High-Performance Perovskite Solar Cells and Optoelectronic Devices
journal, May 2014

  • Ha, Son Tung; Liu, Xinfeng; Zhang, Qing
  • Advanced Optical Materials, Vol. 2, Issue 9
  • DOI: 10.1002/adom.201400106

Raman Spectroscopy of Organic–Inorganic Halide Perovskites
journal, January 2015

  • Ledinský, Martin; Löper, Philipp; Niesen, Bjoern
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 3
  • DOI: 10.1021/jz5026323

Resonance Raman and Excitation Energy Dependent Charge Transfer Mechanism in Halide-Substituted Hybrid Perovskite Solar Cells
journal, January 2015

  • Park, Byung-wook; Jain, Sagar M.; Zhang, Xiaoliang
  • ACS Nano, Vol. 9, Issue 2
  • DOI: 10.1021/nn507345e

6.5% efficient perovskite quantum-dot-sensitized solar cell
journal, January 2011

  • Im, Jeong-Hyeok; Lee, Chang-Ryul; Lee, Jin-Wook
  • Nanoscale, Vol. 3, Issue 10, p. 4088-4093
  • DOI: 10.1039/c1nr10867k

Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy
journal, December 1987

  • Poglitsch, A.; Weber, D.
  • The Journal of Chemical Physics, Vol. 87, Issue 11, p. 6373-6378
  • DOI: 10.1063/1.453467

Effects of heavy nitrogen doping in III–V semiconductors– How well does the conventional wisdom holdfor the dilute nitrogen“III–V-N alloys”?
journal, November 2003

  • Zhang, Yong; Fluegel, B.; Hanna, M. C.
  • physica status solidi (b), Vol. 240, Issue 2
  • DOI: 10.1002/pssb.200303329

Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers
journal, January 2014

  • Xiao, Zhengguo; Bi, Cheng; Shao, Yuchuan
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE01138D

Solid-State Mesostructured Perovskite CH 3 NH 3 PbI 3 Solar Cells: Charge Transport, Recombination, and Diffusion Length
journal, January 2014

  • Zhao, Yixin; Nardes, Alexandre M.; Zhu, Kai
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 3
  • DOI: 10.1021/jz500003v

Raman Spectrum of Strontium Titanate
journal, March 1968

  • Nilsen, W. G.; Skinner, J. G.
  • The Journal of Chemical Physics, Vol. 48, Issue 5
  • DOI: 10.1063/1.1669418

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

Inter-polytype conversion and layer-layer coupling in PbI2
journal, December 1975


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

Raman scattering study on anatase TiO 2 nanocrystals
journal, March 2000


Polytypism and Lattice Vibrations of PbI2
journal, February 1976


Optical Properties of Photovoltaic Organic–Inorganic Lead Halide Perovskites
journal, November 2015

  • Green, Martin A.; Jiang, Yajie; Soufiani, Arman Mahboubi
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
  • DOI: 10.1021/acs.jpclett.5b01865

Excitons versus free charges in organo-lead tri-halide perovskites
journal, April 2014

  • D’Innocenzo, Valerio; Grancini, Giulia; Alcocer, Marcelo J. P.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4586

Raman scattering in PbI2
journal, June 1977

  • Capozzi, V.; Fontana, A.; Fontana, M. P.
  • Il Nuovo Cimento B Series 11, Vol. 39, Issue 2
  • DOI: 10.1007/BF02725793

Quantum well effect in bulk PbI 2 crystals revealed by the anisotropy of photoluminescence and Raman spectra
journal, December 2008


Normal mode determination of perovskite crystal structures with octahedral rotations: theory and applications
journal, April 2013

  • Islam, Mohammad A.; Rondinelli, James M.; Spanier, Jonathan E.
  • Journal of Physics: Condensed Matter, Vol. 25, Issue 17
  • DOI: 10.1088/0953-8984/25/17/175902

Photoinduced Reversible Structural Transformations in Free-Standing CH 3 NH 3 PbI 3 Perovskite Films
journal, June 2015

  • Gottesman, Ronen; Gouda, Laxman; Kalanoor, Basanth S.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 12
  • DOI: 10.1021/acs.jpclett.5b00994

From 1D Chain to 3D Network:  Tuning Hybrid II-VI Nanostructures and Their Optical Properties
journal, June 2003

  • Huang, Xiaoying; Li, Jing; Zhang, Yong
  • Journal of the American Chemical Society, Vol. 125, Issue 23
  • DOI: 10.1021/ja0343611

Phase transitions and crystal dynamics in the cubic perovskite CH3NH3PbCl3
journal, August 1997


The reversal of the laser-beam-induced-current contrast with varying illumination density in a Cu 2 ZnSnSe 4 thin-film solar cell
journal, December 2013

  • Chen, Qiong; Zhang, Yong
  • Applied Physics Letters, Vol. 103, Issue 24
  • DOI: 10.1063/1.4844815

The Impact of the Crystallization Processes on the Structural and Optical Properties of Hybrid Perovskite Films for Photovoltaics
journal, October 2014

  • Grancini, Giulia; Marras, Sergio; Prato, Mirko
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 21
  • DOI: 10.1021/jz501877h

Far-infrared reflectivity spectra of CsPbCl3
journal, August 1972


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

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


Zero Thermal Expansion in a Nanostructured Inorganic-Organic Hybrid Crystal
journal, November 2007


Identification of the symmetry of phonon modes in CsPbCl3 in phase IV by Raman and resonance-Raman scattering
journal, December 1997

  • Calistru, Dana M.; Mihut, L.; Lefrant, S.
  • Journal of Applied Physics, Vol. 82, Issue 11
  • DOI: 10.1063/1.366307

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013

  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

Two-Inch-Sized Perovskite CH 3 NH 3 PbX 3 (X = Cl, Br, I) Crystals: Growth and Characterization
journal, August 2015


Polaronic exciton binding energy in iodide and bromide organic-inorganic lead halide perovskites
journal, December 2015

  • Soufiani, Arman Mahboubi; Huang, Fuzhi; Reece, Peter
  • Applied Physics Letters, Vol. 107, Issue 23
  • DOI: 10.1063/1.4936418

The light and shade of perovskite solar cells
journal, August 2014


An extended defect as a sensor for free carrier diffusion in a semiconductor
journal, January 2013

  • Gfroerer, T. H.; Zhang, Yong; Wanlass, M. W.
  • Applied Physics Letters, Vol. 102, Issue 1
  • DOI: 10.1063/1.4775369

High-efficiency solution-processed perovskite solar cells with millimeter-scale grains
journal, January 2015


Polytypism and the vibrational properties of Pb I 2
journal, February 1979


Raman spectrum of anatase, TiO2
journal, December 1978

  • Ohsaka, Toshiaki; Izumi, Fujio; Fujiki, Yoshinori
  • Journal of Raman Spectroscopy, Vol. 7, Issue 6
  • DOI: 10.1002/jrs.1250070606

Effects of spontaneous ordering on Raman spectra of GaInP 2
journal, July 1997

  • Cheong, Hyeonsik M.; Mascarenhas, Angelo; Ernst, Peter
  • Physical Review B, Vol. 56, Issue 4
  • DOI: 10.1103/PhysRevB.56.1882

The Raman Spectrum of the CH 3 NH 3 PbI 3 Hybrid Perovskite: Interplay of Theory and Experiment
journal, December 2013

  • Quarti, Claudio; Grancini, Giulia; Mosconi, Edoardo
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 2
  • DOI: 10.1021/jz402589q

A distinctive signature in the Raman and photoluminescence spectra of intercalated PbI 2
journal, September 2006


Raman spectrum of strontium titanate
journal, April 1961

  • Narayanan, P. S.; Vedam, K.
  • Zeitschrift f�r Physik, Vol. 163, Issue 2
  • DOI: 10.1007/bf01336873

Works referencing / citing this record:

Intrinsic Exciton-Phonon Coupling and Tuning in Zn Te Nanowires Probed by Resonant Raman Scattering
journal, January 2020