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

Title: Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation

Abstract

Understanding crystallization processes and their pathways in metal-halide perovskites is of crucial importance as this strongly affects the film microstructure, its stability, and device performance. While many approaches are developed to control perovskite formation, the mechanisms of film formation are still poorly known. Using time-resolved in situ grazing incidence wideangle X-ray scattering, the film formation of perovskites is investigated with average stoichiometry Cs0.15FA0.85PbI3, where FA is formamidinium, using the popular antisolvent dropping and gas jet treatments and this is contrasted with untreated films. i) The crystallization pathways during spin coating, ii) the subsequent postdeposition thermal annealing, and iii) crystallization during blade coating are studied. The findings reveal that the formation of a nonperovskite FAPbI3 phase during spin coating is initially dominant regardless of the processing and that the processing treatment (e.g., antisolvent dropping, gas jet) has a significant impact on the as-cast film structure and affects the phase evolution during subsequent thermal treatment. It is shown that blade coating can be used to overcome the nonperovskite phase formation via solvothermal direct crystallization of perovskite phase. This work shows how real-time investigation of perovskite formation can help to establish processing–microstructure–functionality relationships.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. Paderborn (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1646798
Alternate Identifier(s):
OSTI ID: 1638560
Grant/Contract Number:  
AC02‐76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 38; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Abdelsamie, Maged, Xu, Junwei, Bruening, Karsten, Tassone, Christopher J., Steinrück, Hans‐Georg, and Toney, Michael F.. Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation. United States: N. p., 2020. Web. https://doi.org/10.1002/adfm.202001752.
Abdelsamie, Maged, Xu, Junwei, Bruening, Karsten, Tassone, Christopher J., Steinrück, Hans‐Georg, & Toney, Michael F.. Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation. United States. https://doi.org/10.1002/adfm.202001752
Abdelsamie, Maged, Xu, Junwei, Bruening, Karsten, Tassone, Christopher J., Steinrück, Hans‐Georg, and Toney, Michael F.. Wed . "Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation". United States. https://doi.org/10.1002/adfm.202001752. https://www.osti.gov/servlets/purl/1646798.
@article{osti_1646798,
title = {Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation},
author = {Abdelsamie, Maged and Xu, Junwei and Bruening, Karsten and Tassone, Christopher J. and Steinrück, Hans‐Georg and Toney, Michael F.},
abstractNote = {Understanding crystallization processes and their pathways in metal-halide perovskites is of crucial importance as this strongly affects the film microstructure, its stability, and device performance. While many approaches are developed to control perovskite formation, the mechanisms of film formation are still poorly known. Using time-resolved in situ grazing incidence wideangle X-ray scattering, the film formation of perovskites is investigated with average stoichiometry Cs0.15FA0.85PbI3, where FA is formamidinium, using the popular antisolvent dropping and gas jet treatments and this is contrasted with untreated films. i) The crystallization pathways during spin coating, ii) the subsequent postdeposition thermal annealing, and iii) crystallization during blade coating are studied. The findings reveal that the formation of a nonperovskite FAPbI3 phase during spin coating is initially dominant regardless of the processing and that the processing treatment (e.g., antisolvent dropping, gas jet) has a significant impact on the as-cast film structure and affects the phase evolution during subsequent thermal treatment. It is shown that blade coating can be used to overcome the nonperovskite phase formation via solvothermal direct crystallization of perovskite phase. This work shows how real-time investigation of perovskite formation can help to establish processing–microstructure–functionality relationships.},
doi = {10.1002/adfm.202001752},
journal = {Advanced Functional Materials},
number = 38,
volume = 30,
place = {United States},
year = {2020},
month = {7}
}

Works referenced in this record:

The Role of Intrinsic Defects in Methylammonium Lead Iodide Perovskite
journal, March 2014

  • Kim, Jongseob; Lee, Sung-Hoon; Lee, Jung Hoon
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
  • DOI: 10.1021/jz500370k

Induced Crystallization of Perovskites by a Perylene Underlayer for High-Performance Solar Cells
journal, May 2016


Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys
journal, December 2015


In Situ Real-Time Study of the Dynamic Formation and Conversion Processes of Metal Halide Perovskite Films
journal, January 2018


Progress on Perovskite Materials and Solar Cells with Mixed Cations and Halide Anions
journal, July 2017

  • Ono, Luis K.; Juarez-Perez, Emilio J.; Qi, Yabing
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 36
  • DOI: 10.1021/acsami.7b06001

Chemical stability and instability of inorganic halide perovskites
journal, January 2019

  • Zhou, Yuanyuan; Zhao, Yixin
  • Energy & Environmental Science, Vol. 12, Issue 5
  • DOI: 10.1039/C8EE03559H

Interfacial Control Toward Efficient and Low-Voltage Perovskite Light-Emitting Diodes
journal, February 2015


23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability
journal, February 2017

  • Bush, Kevin A.; Palmstrom, Axel F.; Yu, Zhengshan J.
  • Nature Energy, Vol. 2, Issue 4
  • DOI: 10.1038/nenergy.2017.9

The emergence of perovskite solar cells
journal, July 2014

  • Green, Martin A.; Ho-Baillie, Anita; Snaith, Henry J.
  • Nature Photonics, Vol. 8, Issue 7, p. 506-514
  • DOI: 10.1038/nphoton.2014.134

Manipulating the Mixed‐Perovskite Crystallization Pathway Unveiled by In Situ GIWAXS
journal, April 2019


Scalable slot-die coating of high performance perovskite solar cells
journal, January 2018

  • Whitaker, James B.; Kim, Dong Hoe; Larson, Bryon W.
  • Sustainable Energy & Fuels, Vol. 2, Issue 11
  • DOI: 10.1039/C8SE00368H

Fully Air-Bladed High-Efficiency Perovskite Photovoltaics
journal, February 2019


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


Temperature- and Component-Dependent Degradation of Perovskite Photovoltaic Materials under Concentrated Sunlight
journal, January 2015

  • Misra, Ravi K.; Aharon, Sigalit; Li, Baili
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 3
  • DOI: 10.1021/jz502642b

Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite
journal, October 2017

  • Chia, Hao-Chung; Sheu, Hwo-Shuenn; Hsiao, Yu-Yun
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 42
  • DOI: 10.1021/acsami.7b12378

Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3
journal, August 2018


VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites
journal, January 2017


Exploring the formation of formamidinium-based hybrid perovskites by antisolvent methods: in situ GIWAXS measurements during spin coating
journal, January 2019

  • Szostak, Rodrigo; Marchezi, Paulo Ernesto; Marques, Adriano dos Santos
  • Sustainable Energy & Fuels, Vol. 3, Issue 9
  • DOI: 10.1039/C9SE00306A

Heterogeneity at multiple length scales in halide perovskite semiconductors
journal, July 2019

  • Tennyson, Elizabeth M.; Doherty, Tiarnan A. S.; Stranks, Samuel D.
  • Nature Reviews Materials, Vol. 4, Issue 9
  • DOI: 10.1038/s41578-019-0125-0

Compositional Engineering for Efficient Wide Band Gap Perovskites with Improved Stability to Photoinduced Phase Segregation
journal, January 2018


Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells
journal, July 2015

  • Bi, Cheng; Wang, Qi; Shao, Yuchuan
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8747

Scalable Fabrication of Perovskite Solar Cells to Meet Climate Targets
journal, November 2018


Nanoscale mapping of chemical composition in organic-inorganic hybrid perovskite films
journal, October 2019

  • Szostak, R.; Silva, J. C.; Turren-Cruz, S. -H.
  • Science Advances, Vol. 5, Issue 10
  • DOI: 10.1126/sciadv.aaw6619

Formamidinium and Cesium Hybridization for Photo- and Moisture-Stable Perovskite Solar Cell
journal, September 2015

  • Lee, Jin-Wook; Kim, Deok-Hwan; Kim, Hui-Seon
  • Advanced Energy Materials, Vol. 5, Issue 20
  • DOI: 10.1002/aenm.201501310

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

Entropic stabilization of mixed A-cation ABX 3 metal halide perovskites for high performance perovskite solar cells
journal, January 2016

  • Yi, Chenyi; Luo, Jingshan; Meloni, Simone
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE03255E

Blade-Coated Hybrid Perovskite Solar Cells with Efficiency > 17%: An In Situ Investigation
journal, March 2018


Efficient blue light-emitting diodes based on quantum-confined bromide perovskite nanostructures
journal, August 2019


Multi-cation Synergy Suppresses Phase Segregation in Mixed-Halide Perovskites
journal, July 2019


Photovoltaic solar cell technologies: analysing the state of the art
journal, March 2019

  • Nayak, Pabitra K.; Mahesh, Suhas; Snaith, Henry J.
  • Nature Reviews Materials, Vol. 4, Issue 4
  • DOI: 10.1038/s41578-019-0097-0

The fast azimuthal integration Python library: pyFAI
journal, March 2015

  • Ashiotis, Giannis; Deschildre, Aurore; Nawaz, Zubair
  • Journal of Applied Crystallography, Vol. 48, Issue 2
  • DOI: 10.1107/S1600576715004306

Rational molecular passivation for high-performance perovskite light-emitting diodes
journal, March 2019


A Universal Deposition Protocol for Planar Heterojunction Solar Cells with High Efficiency Based on Hybrid Lead Halide Perovskite Families
journal, October 2016

  • Conings, Bert; Babayigit, Aslihan; Klug, Matthew T.
  • Advanced Materials, Vol. 28, Issue 48
  • DOI: 10.1002/adma.201603747

Soft-cover deposition of scaling-up uniform perovskite thin films for high cost-performance solar cells
journal, January 2016

  • Ye, Fei; Chen, Han; Xie, Fengxian
  • Energy & Environmental Science, Vol. 9, Issue 7
  • DOI: 10.1039/C6EE01411A

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

Thermal engineering of FAPbI3 perovskite material via radiative thermal annealing and in situ XRD
journal, January 2017

  • Pool, Vanessa L.; Dou, Benjia; Van Campen, Douglas G.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14075

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

Insights into operational stability and processing of halide perovskite active layers
journal, January 2019

  • Schelhas, Laura T.; Li, Zhen; Christians, Jeffrey A.
  • Energy & Environmental Science, Vol. 12, Issue 4
  • DOI: 10.1039/C8EE03051K

Anharmonicity and Disorder in the Black Phases of Cesium Lead Iodide Used for Stable Inorganic Perovskite Solar Cells
journal, March 2018


Die Gesetze der Krystallochemie
journal, May 1926


Solid-state principles applied to organic–inorganic perovskites: new tricks for an old dog
journal, January 2014

  • Kieslich, Gregor; Sun, Shijing; Cheetham, Anthony K.
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/C4SC02211D

Electronic Properties of {111} Twin Boundaries in a Mixed-Ion Lead Halide Perovskite Solar Absorber
journal, October 2018


Mixing Behavior in Small Molecule:Fullerene Organic Photovoltaics
journal, March 2017


Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites
journal, June 2016

  • Nagabhushana, G. P.; Shivaramaiah, Radha; Navrotsky, Alexandra
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 28
  • DOI: 10.1073/pnas.1607850113

Scalable Ambient Fabrication of High-Performance CsPbI2Br Solar Cells
journal, October 2019


All-optical control of lead halide perovskite microlasers
journal, April 2019


Antisolvent processing of lead halide perovskite thin films studied by in situ X-ray diffraction
journal, January 2018

  • Bruening, Karsten; Tassone, Christopher J.
  • Journal of Materials Chemistry A, Vol. 6, Issue 39
  • DOI: 10.1039/C8TA06025H

High-Performance Single-Crystalline Perovskite Thin-Film Photodetector
journal, January 2018

  • Yang, Zhenqian; Deng, Yuhao; Zhang, Xiaowei
  • Advanced Materials, Vol. 30, Issue 8
  • DOI: 10.1002/adma.201704333

From scalable solution fabrication of perovskite films towards commercialization of solar cells
journal, January 2019

  • Huang, Fei; Li, Mengjie; Siffalovic, Peter
  • Energy & Environmental Science, Vol. 12, Issue 2
  • DOI: 10.1039/C8EE03025A

Compositional and orientational control in metal halide perovskites of reduced dimensionality
journal, September 2018

  • Quintero-Bermudez, Rafael; Gold-Parker, Aryeh; Proppe, Andrew H.
  • Nature Materials, Vol. 17, Issue 10
  • DOI: 10.1038/s41563-018-0154-x

The Many Faces of Mixed Ion Perovskites: Unraveling and Understanding the Crystallization Process
journal, November 2017


Thermodynamics and the Intrinsic Stability of Lead Halide Perovskites CH 3 NH 3 PbX 3
journal, June 2018


From Nano- to Micrometer Scale: The Role of Antisolvent Treatment on High Performance Perovskite Solar Cells
journal, April 2017


Degradation observations of encapsulated planar CH 3 NH 3 PbI 3 perovskite solar cells at high temperatures and humidity
journal, January 2015

  • Han, Yu; Meyer, Steffen; Dkhissi, Yasmina
  • Journal of Materials Chemistry A, Vol. 3, Issue 15
  • DOI: 10.1039/C5TA00358J

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

  • Quarti, Claudio; Mosconi, Edoardo; Ball, James M.
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE02925B

Structural Origins of Light-Induced Phase Segregation in Organic-Inorganic Halide Perovskite Photovoltaic Materials
journal, January 2020


Introduction: Perovskites
journal, March 2019


Cubic Perovskite Structure of Black Formamidinium Lead Iodide, α-[HC(NH 2 ) 2 ]PbI 3 , at 298 K
journal, July 2015

  • Weller, Mark T.; Weber, Oliver J.; Frost, Jarvist M.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 16
  • DOI: 10.1021/acs.jpclett.5b01432