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Title: Crystallization kinetics of rapid spray plasma processed multiple cation perovskites in open air

Abstract

Rapid Spray Plasma Processing (RSPP) is a high throughput, scalable, and open-air route toward manufacturing perovskite solar modules. The plasma exposure is dosed such that the perovskite precursor solution is cured in milliseconds using a combination of rapid heating, reactive species, and UV photons. We implemented in situ wide angle X-ray scattering (WAXS) to characterize the crystal growth in multiple cation, mixed halide perovskite thin films—Csx(MAzFA1-z)1-xPb(Br0.17I0.83)3 for 0.05 ≤ x ≤ 0.25—fabricated in open air. The use of synchrotron radiation and high detector speeds resolved the formation and dissolution of a transient intermediate crystalline phase during the tens of milliseconds when the perovskite crystallized. Increasing the mole fraction of cesium and methylammonium resulted in a decrease in the intermediate phase and an increase in the average grain diameter. Increasing the cesium fraction suppressed phase segregation, as observed in photoluminescence. Calculations showed the refractive index decreased and the extinction coefficient increased with cesium fraction. Based on the rapid crystallization kinetics, RSPP perovskite films exhibit residual stress values >5× lower than spin coated films. Understanding the kinetics of perovskite formation enables the design of perovskite films with improved thermomechanical and operational stability.

Authors:
 [1];  [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [1]
  1. Stanford Univ., CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1605210
Alternate Identifier(s):
OSTI ID: 1577378
Grant/Contract Number:  
ECCS-1542152; AC02-76SF00515; DGE-1656518; EE0008559
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hovish, Michael Q., Rolston, Nicholas, Brüning, Karsten, Hilt, Florian, Tassone, Christopher, and Dauskardt, Reinhold H. Crystallization kinetics of rapid spray plasma processed multiple cation perovskites in open air. United States: N. p., 2019. Web. doi:10.1039/c9ta07980g.
Hovish, Michael Q., Rolston, Nicholas, Brüning, Karsten, Hilt, Florian, Tassone, Christopher, & Dauskardt, Reinhold H. Crystallization kinetics of rapid spray plasma processed multiple cation perovskites in open air. United States. doi:https://doi.org/10.1039/c9ta07980g
Hovish, Michael Q., Rolston, Nicholas, Brüning, Karsten, Hilt, Florian, Tassone, Christopher, and Dauskardt, Reinhold H. Fri . "Crystallization kinetics of rapid spray plasma processed multiple cation perovskites in open air". United States. doi:https://doi.org/10.1039/c9ta07980g. https://www.osti.gov/servlets/purl/1605210.
@article{osti_1605210,
title = {Crystallization kinetics of rapid spray plasma processed multiple cation perovskites in open air},
author = {Hovish, Michael Q. and Rolston, Nicholas and Brüning, Karsten and Hilt, Florian and Tassone, Christopher and Dauskardt, Reinhold H.},
abstractNote = {Rapid Spray Plasma Processing (RSPP) is a high throughput, scalable, and open-air route toward manufacturing perovskite solar modules. The plasma exposure is dosed such that the perovskite precursor solution is cured in milliseconds using a combination of rapid heating, reactive species, and UV photons. We implemented in situ wide angle X-ray scattering (WAXS) to characterize the crystal growth in multiple cation, mixed halide perovskite thin films—Csx(MAzFA1-z)1-xPb(Br0.17I0.83)3 for 0.05 ≤ x ≤ 0.25—fabricated in open air. The use of synchrotron radiation and high detector speeds resolved the formation and dissolution of a transient intermediate crystalline phase during the tens of milliseconds when the perovskite crystallized. Increasing the mole fraction of cesium and methylammonium resulted in a decrease in the intermediate phase and an increase in the average grain diameter. Increasing the cesium fraction suppressed phase segregation, as observed in photoluminescence. Calculations showed the refractive index decreased and the extinction coefficient increased with cesium fraction. Based on the rapid crystallization kinetics, RSPP perovskite films exhibit residual stress values >5× lower than spin coated films. Understanding the kinetics of perovskite formation enables the design of perovskite films with improved thermomechanical and operational stability.},
doi = {10.1039/c9ta07980g},
journal = {Journal of Materials Chemistry. A},
number = 1,
volume = 8,
place = {United States},
year = {2019},
month = {11}
}

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Works referenced in this record:

Effects of alloying on the optical properties of organic–inorganic lead halide perovskite thin films
journal, January 2016

  • Ndione, Paul F.; Li, Zhen; Zhu, Kai
  • Journal of Materials Chemistry C, Vol. 4, Issue 33
  • DOI: 10.1039/C6TC02135B

Drying stress and damage processes in human stratum corneum: Drying stress in human stratum corneum
journal, November 2009


Light and oxygen induced degradation limits the operational stability of methylammonium lead triiodide perovskite solar cells
journal, January 2016

  • Bryant, Daniel; Aristidou, Nicholas; Pont, Sebastian
  • Energy & Environmental Science, Vol. 9, Issue 5
  • DOI: 10.1039/C6EE00409A

Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells
journal, November 2017


Rapid route to efficient, scalable, and robust perovskite photovoltaics in air
journal, January 2018

  • Hilt, Florian; Hovish, Michael Q.; Rolston, Nicholas
  • Energy & Environmental Science, Vol. 11, Issue 8
  • DOI: 10.1039/C8EE01065J

Complex Refractive Indices of Cesium–Formamidinium-Based Mixed-Halide Perovskites with Optical Band Gaps from 1.5 to 1.8 eV
journal, February 2018


Acceleration of Chemical Degradation of Perfluorosulfonic Acid Ionomer Membrane by Mechanical Stress: Experimental Evidence
conference, January 2010

  • Yoon, Wonseok; Huang, Xinyu
  • 218th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.3484584

Conductive Transparent TiN x /TiO 2 Hybrid Films Deposited on Plastics in Air Using Atmospheric Plasma Processing
journal, January 2014

  • Dong, Siming; Watanabe, Makoto; Dauskardt, Reinhold H.
  • Advanced Functional Materials, Vol. 24, Issue 20
  • DOI: 10.1002/adfm.201303038

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics
journal, January 2015

  • Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R.
  • Chemical Science, Vol. 6, Issue 1
  • DOI: 10.1039/C4SC03141E

Mixed Mode Cracking in Layered Materials
book, January 1991


Photo-oxidative degradation of mechanically stressed polyolefins
journal, February 1996


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


Engineering Stress in Perovskite Solar Cells to Improve Stability
journal, September 2018

  • Rolston, Nicholas; Bush, Kevin A.; Printz, Adam D.
  • Advanced Energy Materials, Vol. 8, Issue 29
  • DOI: 10.1002/aenm.201802139

Thermal Stability of Mixed Cation Metal Halide Perovskites in Air
journal, January 2018

  • Tan, Wanliang; Bowring, Andrea R.; Meng, Andrew C.
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 6
  • DOI: 10.1021/acsami.7b15263

Photovoltaic mixed-cation lead mixed-halide perovskites: links between crystallinity, photo-stability and electronic properties
journal, January 2017

  • Rehman, Waqaas; McMeekin, David P.; Patel, Jay B.
  • Energy & Environmental Science, Vol. 10, Issue 1
  • DOI: 10.1039/C6EE03014A

Intrinsic Thermal Instability of Methylammonium Lead Trihalide Perovskite
journal, June 2015

  • Conings, Bert; Drijkoningen, Jeroen; Gauquelin, Nicolas
  • Advanced Energy Materials, Vol. 5, Issue 15
  • DOI: 10.1002/aenm.201500477

Stabilized Wide Bandgap MAPbBr x I 3- x Perovskite by Enhanced Grain Size and Improved Crystallinity
journal, December 2015


Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency
journal, January 2016

  • Saliba, Michael; Matsui, Taisuke; Seo, Ji-Youn
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C5EE03874J

Complex Refractive Index Spectra of CH 3 NH 3 PbI 3 Perovskite Thin Films Determined by Spectroscopic Ellipsometry and Spectrophotometry
journal, December 2014

  • Löper, Philipp; Stuckelberger, Michael; Niesen, Bjoern
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
  • DOI: 10.1021/jz502471h

A vacuum flash–assisted solution process for high-efficiency large-area perovskite solar cells
journal, June 2016


Degradation mechanism of (Al · Ga)As double‐heterostructure laser diodes
journal, January 1974

  • Yonezu, H.; Sakuma, I.; Kamejima, T.
  • Applied Physics Letters, Vol. 24, Issue 1
  • DOI: 10.1063/1.1654991

The Tension of Metallic Films Deposited by Electrolysis
journal, May 1909

  • Stoney, G. G.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 82, Issue 553
  • DOI: 10.1098/rspa.1909.0021

Scaffold-reinforced perovskite compound solar cells
journal, January 2017

  • Watson, Brian L.; Rolston, Nicholas; Printz, Adam D.
  • Energy & Environmental Science, Vol. 10, Issue 12
  • DOI: 10.1039/C7EE02185B

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


Effect of Selective Contacts on the Thermal Stability of Perovskite Solar Cells
journal, February 2017

  • Zhao, Xing; Kim, Hui-Seon; Seo, Ja-Young
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 8
  • DOI: 10.1021/acsami.6b15673

Scaling behavior of moisture-induced grain degradation in polycrystalline hybrid perovskite thin films
journal, January 2017

  • Wang, Qi; Chen, Bo; Liu, Ye
  • Energy & Environmental Science, Vol. 10, Issue 2
  • DOI: 10.1039/C6EE02941H

Atmospheric plasma deposition of transparent semiconducting ZnO films on plastics in ambient air
journal, March 2014


Thermo-mechanical behavior of organic-inorganic halide perovskites for solar cells
journal, June 2018


Determination of Thermal Expansion Coefficients and Locating the Temperature-Induced Phase Transition in Methylammonium Lead Perovskites Using X-ray Diffraction
journal, October 2015


Degradation of multijunction photovoltaic gridlines induced via thermal cycling
journal, June 2018


A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016


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

Improved stability and efficiency of perovskite solar cells with submicron flexible barrier films deposited in air
journal, January 2017

  • Rolston, Nicholas; Printz, Adam D.; Hilt, Florian
  • Journal of Materials Chemistry A, Vol. 5, Issue 44
  • DOI: 10.1039/C7TA09178H

A Closer Look into Two-Step Perovskite Conversion with X-ray Scattering
journal, March 2015

  • Schlipf, Johannes; Docampo, Pablo; Schaffer, Christoph J.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 7
  • DOI: 10.1021/acs.jpclett.5b00329

Controlling Thin-Film Stress and Wrinkling during Perovskite Film Formation
journal, May 2018


Effect of Cation Composition on the Mechanical Stability of Perovskite Solar Cells
journal, December 2017

  • Rolston, Nicholas; Printz, Adam D.; Tracy, Jared M.
  • Advanced Energy Materials, Vol. 8, Issue 9
  • DOI: 10.1002/aenm.201702116

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


Crystallization Kinetics of Lead Halide Perovskite Film Monitored by In Situ Terahertz Spectroscopy
journal, January 2017