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

Journal Article · · Physical Review. X
 [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)

© 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.

Research Organization:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
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)
Grant/Contract Number:
AC36-08GO28308; AC02-05CH11231
OSTI ID:
1330000
Alternate ID(s):
OSTI ID: 1378748
Report Number(s):
NREL/JA-5900-67314; PRXHAE
Journal Information:
Physical Review. X, Vol. 6, Issue 3; ISSN 2160-3308
Publisher:
American Physical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

References (42)

Synthesis of Organic-Inorganic Lead Halide Perovskite Nanoplatelets: Towards High-Performance Perovskite Solar Cells and Optoelectronic Devices journal May 2014
Raman Spectroscopy of Organic–Inorganic Halide Perovskites journal January 2015
Resonance Raman and Excitation Energy Dependent Charge Transfer Mechanism in Halide-Substituted Hybrid Perovskite Solar Cells journal January 2015
6.5% efficient perovskite quantum-dot-sensitized solar cell journal January 2011
Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy journal December 1987
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
Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers journal January 2014
Solid-State Mesostructured Perovskite CH 3 NH 3 PbI 3 Solar Cells: Charge Transport, Recombination, and Diffusion Length journal January 2014
Raman Spectrum of Strontium Titanate journal March 1968
Sequential deposition as a route to high-performance perovskite-sensitized solar cells journal July 2013
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
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
Excitons versus free charges in organo-lead tri-halide perovskites journal April 2014
Raman scattering in PbI2 journal June 1977
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
Photoinduced Reversible Structural Transformations in Free-Standing CH 3 NH 3 PbI 3 Perovskite Films journal June 2015
From 1D Chain to 3D Network:  Tuning Hybrid II-VI Nanostructures and Their Optical Properties journal June 2003
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
The Impact of the Crystallization Processes on the Structural and Optical Properties of Hybrid Perovskite Films for Photovoltaics journal October 2014
Far-infrared reflectivity spectra of CsPbCl3 journal August 1972
Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells journal July 2014
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites journal October 2012
Global electronic structure of semiconductor alloys through direct large-scale computations for III-V alloys Ga x In 1 x P journal April 2011
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
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties journal July 2013
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
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
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
Effects of spontaneous ordering on Raman spectra of GaInP 2 journal July 1997
The Raman Spectrum of the CH 3 NH 3 PbI 3 Hybrid Perovskite: Interplay of Theory and Experiment journal December 2013
A distinctive signature in the Raman and photoluminescence spectra of intercalated PbI 2 journal September 2006
Raman spectrum of strontium titanate journal April 1961

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