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

Title: Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide

Abstract

Here, we examine the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbI3) using time-of-flight neutron and synchrotron X-ray powder diffraction. Near 330 K the high temperature cubic phases transformed to a body-centered tetragonal phase. The variation of the order parameter Q for this transition scaled with temperature T as Q (Tc-T) , where Tc is the critical temperature and the exponent was close to , as predicted for a tricritical phase transition. We also observed coexistence of the cubic and tetragonal phases over a range of temperature in all cases, demonstrating that the phase transition was in fact first-order, although still very close to tricritical. Upon cooling further, all the tetragonal phases transformed into a low temperature orthorhombic phase around 160 K, again via a first-order phase transition. Finally, based upon these results, we discuss the impact of the structural phase transitions upon photovoltaic performance of MAPbI3 based solar cells.

Authors:
 [1];  [2];  [3];  [1];  [1];  [2];  [4]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  2. Dupont Electronics and Communication Technologies, Wilmington, DE (United States)
  3. Dupont Electronics and Communication Technologies, Wilmington, DE (United States); Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source
  4. Dupont Central Research and Development, Wilmington, DE (United States); Univ. of Delaware, Newark, DE (United States). Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1329767
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 6; Journal Issue: 21 Oct; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Whitfield, P. S., Herron, N., Guise, W. E., Page, K., Cheng, Y. Q., Milas, I., and Crawford, M. K. Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide. United States: N. p., 2016. Web. doi:10.1038/srep35685.
Whitfield, P. S., Herron, N., Guise, W. E., Page, K., Cheng, Y. Q., Milas, I., & Crawford, M. K. Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide. United States. https://doi.org/10.1038/srep35685
Whitfield, P. S., Herron, N., Guise, W. E., Page, K., Cheng, Y. Q., Milas, I., and Crawford, M. K. 2016. "Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide". United States. https://doi.org/10.1038/srep35685. https://www.osti.gov/servlets/purl/1329767.
@article{osti_1329767,
title = {Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide},
author = {Whitfield, P. S. and Herron, N. and Guise, W. E. and Page, K. and Cheng, Y. Q. and Milas, I. and Crawford, M. K.},
abstractNote = {Here, we examine the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbI3) using time-of-flight neutron and synchrotron X-ray powder diffraction. Near 330 K the high temperature cubic phases transformed to a body-centered tetragonal phase. The variation of the order parameter Q for this transition scaled with temperature T as Q (Tc-T) , where Tc is the critical temperature and the exponent was close to , as predicted for a tricritical phase transition. We also observed coexistence of the cubic and tetragonal phases over a range of temperature in all cases, demonstrating that the phase transition was in fact first-order, although still very close to tricritical. Upon cooling further, all the tetragonal phases transformed into a low temperature orthorhombic phase around 160 K, again via a first-order phase transition. Finally, based upon these results, we discuss the impact of the structural phase transitions upon photovoltaic performance of MAPbI3 based solar cells.},
doi = {10.1038/srep35685},
url = {https://www.osti.gov/biblio/1329767}, journal = {Scientific Reports},
issn = {2045-2322},
number = 21 Oct,
volume = 6,
place = {United States},
year = {Fri Oct 21 00:00:00 EDT 2016},
month = {Fri Oct 21 00:00:00 EDT 2016}
}

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

Citation Metrics:
Cited by: 393 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Projector augmented-wave method
journal, December 1994


Über die Cäsium- und Kalium-Bleihalogenide
journal, January 1893


Photovoltaic behaviour of lead methylammonium triiodide perovskite solar cells down to 80 K
journal, January 2015


High-performance photovoltaic perovskite layers fabricated through intramolecular exchange
journal, May 2015


Static and dynamic structures of CD3ND3GeCl3 studied by TOF high resolution neutron powder diffraction and solid state NMR
journal, April 2002


On the rigid-body motion of molecules in crystals
journal, January 1968


ISODISPLACE : a web-based tool for exploring structural distortions
journal, July 2006


Cation rotation in methylammonium lead halides
journal, November 1985


Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH 3 NH 3 PbI 3
journal, July 2014


Ferroelastic Fingerprints in Methylammonium Lead Iodide Perovskite
journal, January 2016


The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells
journal, May 2015


Interaction of Elastic Strain with the Structural Transition of Strontium Titanate
journal, May 1970


Electron–phonon coupling in hybrid lead halide perovskites
journal, May 2016


Solid-State Physics Perspective on Hybrid Perovskite Semiconductors
journal, April 2015


Rigid-body motion in crystals – the application of constraints on the TLS model
journal, September 1975


Domain Walls Conductivity in Hybrid Organometallic Perovskites and Their Essential Role in CH3NH3PbI3 Solar Cell High Performance
journal, June 2015


Chemical accuracy for the van der Waals density functional
journal, December 2009


Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites
journal, February 2015


Neutron scattering study of the lattice dynamical phase transitions in KMnF3
journal, December 1970


Treatment of hydrogen background in bulk and nanocrystalline neutron total scattering experiments
journal, May 2011


Phonon–Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites
journal, December 2015


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


The Landau Theory of Phase Transitions
book, August 1987


The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012

  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
  • https://doi.org/10.1016/j.nimb.2012.05.037

Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†
journal, January 1990


Dielectric study of CH3NH3PbX3 (X = Cl, Br, I)
journal, July 1992


Domain wall nanoelectronics
journal, February 2012


The expanding world of hybrid perovskites: materials properties and emerging applications
journal, March 2015


Structural and optical properties of methylammonium lead iodide across the tetragonal to cubic phase transition: implications for perovskite solar cells
journal, January 2016


Hybrid Organic-Inorganic Perovskites (HOIPs): Opportunities and Challenges
journal, July 2015


Generalized Gradient Approximation Made Simple
journal, October 1996


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


Role of intrinsic disorder in the structural phase transition of magnetoelectric EuTiO 3
journal, May 2012


Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films
journal, August 2014


Local Structural Origins of the Distinct Electronic Properties of Nb-Substituted SrTiO 3 and BaTiO 3
journal, November 2008


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


A symmetry-mode description of rigid-body rotations in crystalline solids: a case study of Mg(H 2 O) 6 RbBr 3
journal, February 2014


Electronic and ionic transport properties and other physical aspects of perovskites
journal, September 2004


Can ferroelectric polarization explain the high performance of hybrid halide perovskite solar cells?
journal, January 2016


Rotational dynamics of organic cations in the CH 3 NH 3 PbI 3 perovskite
journal, January 2015


Temperature-Dependent Charge-Carrier Dynamics in CH 3 NH 3 PbI 3 Perovskite Thin Films
journal, September 2015


Neutron-scattering study on phase transitions of CsPb Cl 3
journal, May 1974


Phase transitions in the perovskite methylammonium lead bromide, CH3ND3PbBr3
journal, November 2003


High-temperature phase transitions in SrZrO 3
journal, February 1999


Structural Study on Cubic–Tetragonal Transition of CH 3 NH 3 PbI 3
journal, July 2002


Isotopic Polymorphism in Pyridine
journal, January 2009


Kinetics of Phase Change. I General Theory
journal, December 1939


Powgen: A third-generation highresolution high-throughput powder diffraction instrument at the Spallation Neutron Source
book, December 2011


Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K
journal, January 2015


Ore lead isotope ratios in a continuously changing earth
journal, December 1975


Lattice Dynamics and Phase Transitions of Strontium Titanate
journal, May 1964


The classification of tilted octahedra in perovskites
journal, November 1972


Alkylammonium lead halides. Part 2. CH 3 NH 3 PbX 3 (X = Cl, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation
journal, March 1990


Structure of Methylammonium Lead Iodide Within Mesoporous Titanium Dioxide: Active Material in High-Performance Perovskite Solar Cells
journal, December 2013


Molecular Motion in Solid Tetrapropylammonium Bromide and Iodide
journal, November 1992


Isotopic Polymorphism in Pyridine
journal, January 2009


Parallel Nanoimprint Forming of One-Dimensional Chiral Semiconductor for Strain-Engineered Optical Properties
journal, August 2020


Phase transitions in ferroelastic and co-elastic crystals
journal, February 1992


Phase transitions in ferroelastic and co-elastic crystals
journal, December 1991


Chemical accuracy for the van der Waals density functional
preprint, January 2009


The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012

  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
  • https://doi.org/10.1016/j.nimb.2012.05.037

Solid-State Physics Perspective on Hybrid Perovskite Semiconductors
journal, April 2015


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


Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH 3 NH 3 PbI 3
journal, July 2014


Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites
journal, February 2015


Structure of Methylammonium Lead Iodide Within Mesoporous Titanium Dioxide: Active Material in High-Performance Perovskite Solar Cells
journal, December 2013


Domain Walls Conductivity in Hybrid Organometallic Perovskites and Their Essential Role in CH3NH3PbI3 Solar Cell High Performance
journal, June 2015


Kinetics of Phase Change. I General Theory
journal, December 1939


Intrinsic Mobility Limiting Mechanisms in Lanthanum-Doped Strontium Titanate
journal, May 2014


Lifshitz-Point Critical and Tricritical Behavior in Anisotropically Stressed Perovskites
journal, February 1979


Translation-rotation coupling, phase transitions, and elastic phenomena in orientationally disordered crystals
journal, July 1994


Validation of crystallographic models containing TLS or other descriptions of anisotropy
journal, July 2010


The expanding world of hybrid perovskites: materials properties and emerging applications
journal, March 2015


Works referencing / citing this record:

Self-Organized Superlattice and Phase Coexistence inside Thin Film Organometal Halide Perovskite
journal, January 2018


Exploring Anomalous Polarization Dynamics in Organometallic Halide Perovskites
journal, January 2018


Intrinsic Instability of Inorganic–Organic Hybrid Halide Perovskite Materials
journal, December 2018


Tracking Structural Phase Transitions in Lead‐Halide Perovskites by Means of Thermal Expansion
journal, April 2019


Steric Impediment of Ion Migration Contributes to Improved Operational Stability of Perovskite Solar Cells
journal, February 2020


Understanding the Instability of the Halide Perovskite CsPbI 3 through Temperature‐Dependent Structural Analysis
journal, July 2020


Machine Learning Stability and Bandgaps of Lead‐Free Perovskites for Photovoltaics
journal, November 2019


Conducting Bridge Resistive Switching Behaviors in Cubic MAPbI 3 , Orthorhombic RbPbI 3 , and Their Mixtures
journal, November 2018


Drying Dynamics of Solution‐Processed Perovskite Thin‐Film Photovoltaics: In Situ Characterization, Modeling, and Process Control
journal, August 2019


Influence of Grain Size on Phase Transitions in Halide Perovskite Films
journal, August 2019


Enhancing High Humidity Stability of Quasi‐2D Perovskite Thin Films through Mixed Cation Doping and Solvent Engineering
journal, May 2019


Stability Issue of Perovskite Solar Cells under Real‐World Operating Conditions
journal, April 2020


Halogen in materials design: Fluoroammonium lead triiodide (FNH 3 PbI 3 ) perovskite as a newly discovered dynamical bandgap semiconductor in 3D
journal, March 2018


Polar rotor scattering as atomic-level origin of low mobility and thermal conductivity of perovskite CH3NH3PbI3
journal, June 2017


Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals
journal, May 2018


Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites
journal, May 2018


Slow thermal equilibration in methylammonium lead iodide revealed by transient mid-infrared spectroscopy
journal, July 2018


Probing the structure–property–composition relationship in organic–inorganic tri-halide perovskites
journal, January 2018


A theoretical study of perovskites related to CH 3 NH 3 PbX 3 (X = F, Cl, Br, I)
journal, January 2018


Liquid water-induced growth of the 1D morphology of CH 3 NH 3 PbI 3 hybrid perovskites
journal, January 2019


Edge functionalized graphene nanoribbons with tunable band edges for carrier transport interlayers in organic–inorganic perovskite solar cells
journal, January 2020


Phase transition in the extreme: a cubic-to-triclinic symmetry change in dielectrically switchable cyanide perovskites
journal, January 2019


Additive-assisted synthesis and optoelectronic properties of (CH 3 NH 3 ) 4 Bi 6 I 22
journal, January 2020


Size and temperature dependence of photoluminescence of hybrid perovskite nanocrystals
journal, October 2019


Evaluation of the AMOEBA force field for simulating metal halide perovskites in the solid state and in solution
journal, January 2020


Thermal stability of mobility in methylammonium lead iodide
journal, November 2019


Ferroic multipolar order and disorder in cyanoelpasolite molecular perovskites
journal, May 2019

  • Coates, C. S.; Gray, H. J.; Bulled, J. M.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2149
  • https://doi.org/10.1098/rsta.2018.0219

Investigating temperature-induced structural changes of lead halide perovskites by in situ X-ray powder diffraction
journal, September 2019


An algebraic approach to cooperative rotations in networks of interconnected rigid units
journal, August 2018


Emerging Characterizing Techniques in the Fine Structure Observation of Metal Halide Perovskite Crystal
journal, May 2018


Interfacial Residual Stress Relaxation in Perovskite Solar Cells with Improved Stability
journal, October 2019


Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices
journal, January 2019


Structure-controlled optical thermoresponse in Ruddlesden-Popper layered perovskites
journal, November 2018


Microscopic calculation of the optical properties and intrinsic losses in the methylammonium lead iodide perovskite system
journal, January 2019


A new long-range sub-structure found in the tetragonal phase of CH 3 NH 3 PbI 3 single crystals
journal, May 2019


Phase Transitions of Hybrid Perovskites Simulated by Machine-Learning Force Fields Trained on the Fly with Bayesian Inference
journal, June 2019


Tracking Structural Phase Transitions in Lead‐Halide Perovskites by Means of Thermal Expansion
text, January 2019


Perovskites-Based Solar Cells: A Review of Recent Progress, Materials and Processing Methods
journal, May 2018


Efficient and Stable Inorganic Perovskite Solar Cells Manufactured by Pulsed Flash Infrared Annealing
journal, September 2018


Atomic‐Resolution Imaging of Halide Perovskites Using Electron Microscopy
journal, February 2020


Crystal reorientation in methylammonium lead iodide perovskite thin film with thermal annealing
journal, January 2019


Non-Perovskite Hybrid Material, Imidazolium Lead Iodide, with Enhanced Stability
journal, October 2018


Growth, characterization, and thin film transistor application of CH 3 NH 3 PbI 3 perovskite on polymeric gate dielectric layers
journal, January 2017


Structural fluctuations cause spin-split states in tetragonal (CH 3 NH 3 )PbI 3 as evidenced by the circular photogalvanic effect
journal, September 2018


Effect of annealing temperature on the phase transition, band gap and thermoelectric properties of Cu 2 SnSe 3
journal, January 2018


Efficient perovskite solar cells fabricated by manganese cations incorporated in hybrid perovskites
journal, January 2019


Perovskite synthesis, properties and their related biochemical and industrial application
journal, September 2019


The Relation between Rotational Dynamics of the Organic Cation and Phase Transitions in Hybrid Halide Perovskites
journal, May 2019


Unraveling the Water Degradation Mechanism of CH 3 NH 3 PbI 3
journal, July 2019


Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals
journal, May 2018


Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites
journal, May 2018


Slow thermal equilibration in methylammonium lead iodide revealed by transient mid-infrared spectroscopy
journal, July 2018


Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices
journal, January 2019


Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide
journal, November 2018


Perovskites-Based Solar Cells: A Review of Recent Progress, Materials and Processing Methods
journal, May 2018