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Title: Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

Abstract

The exploration of the synthetic space of halide perovskites hinges on an enormous number of parameters requiring time-consuming experimentation to decouple and optimize. Here, the formation of the prototype material CH NH PbI (MAPbI ) is investigated at different time and length scales using multimodal in situ measurements to monitor the evolution of crystalline phases, morphology, and photoluminescence as a function of the lead precursors. Kinetically fast formation of crystalline precursor phases already during the spin-coat deposition is observed using lead iodide (PbI ) or lead chloride (PbCl ) routes. These precursor phases most likely template final MAPbI film morphology. In particular, the emergence of the “needle-like” structure is shown to appear before film annealing. In situ photoluminescence measurements suggest nanoscale nucleation followed by rapid nuclei densification and growth. Using this multimodal in situ approach, different formation pathways can be identified either via precursor phases in the PbI and PbCl routes or direct perovskite formation from molecular building blocks as observed in the lead acetate (PbAc ) route. Correlation of in situ results with photovoltaic device performance demonstrates the power of in situ multimodal techniques, paves the way to a fast screening of synthetic parameters, and ultimately leads to controlledmore » synthetic procedures that yield high-efficiency devices. 3 3 3 3 2 2 3 2 2 2« less

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1); USDOE
OSTI Identifier:
1777950
Alternate Identifier(s):
OSTI ID: 1577877
Grant/Contract Number:  
AC02-05CH11231; DE‐AC02‐05CH11231; DE‐SC0004993; DE‐AC52‐07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 6
Country of Publication:
United States
Language:
English

Citation Formats

Song, TB, Yuan, Z, Mori, M, Motiwala, F, Segev, G, Masquelier, E, Stan, CV, Slack, JL, Tamura, N, and Sutter-Fella, CM. Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes. United States: N. p., 2020. Web. doi:10.1002/adfm.201908337.
Song, TB, Yuan, Z, Mori, M, Motiwala, F, Segev, G, Masquelier, E, Stan, CV, Slack, JL, Tamura, N, & Sutter-Fella, CM. Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes. United States. doi:https://doi.org/10.1002/adfm.201908337
Song, TB, Yuan, Z, Mori, M, Motiwala, F, Segev, G, Masquelier, E, Stan, CV, Slack, JL, Tamura, N, and Sutter-Fella, CM. Sat . "Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes". United States. doi:https://doi.org/10.1002/adfm.201908337. https://www.osti.gov/servlets/purl/1777950.
@article{osti_1777950,
title = {Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes},
author = {Song, TB and Yuan, Z and Mori, M and Motiwala, F and Segev, G and Masquelier, E and Stan, CV and Slack, JL and Tamura, N and Sutter-Fella, CM},
abstractNote = {The exploration of the synthetic space of halide perovskites hinges on an enormous number of parameters requiring time-consuming experimentation to decouple and optimize. Here, the formation of the prototype material CH NH PbI (MAPbI ) is investigated at different time and length scales using multimodal in situ measurements to monitor the evolution of crystalline phases, morphology, and photoluminescence as a function of the lead precursors. Kinetically fast formation of crystalline precursor phases already during the spin-coat deposition is observed using lead iodide (PbI ) or lead chloride (PbCl ) routes. These precursor phases most likely template final MAPbI film morphology. In particular, the emergence of the “needle-like” structure is shown to appear before film annealing. In situ photoluminescence measurements suggest nanoscale nucleation followed by rapid nuclei densification and growth. Using this multimodal in situ approach, different formation pathways can be identified either via precursor phases in the PbI and PbCl routes or direct perovskite formation from molecular building blocks as observed in the lead acetate (PbAc ) route. Correlation of in situ results with photovoltaic device performance demonstrates the power of in situ multimodal techniques, paves the way to a fast screening of synthetic parameters, and ultimately leads to controlled synthetic procedures that yield high-efficiency devices. 3 3 3 3 2 2 3 2 2 2},
doi = {10.1002/adfm.201908337},
journal = {Advanced Functional Materials},
number = 6,
volume = 30,
place = {United States},
year = {2020},
month = {2}
}

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Works referenced in this record:

Surface Ligand Management for Stable FAPbI3 Perovskite Quantum Dot Solar Cells
journal, September 2018


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


Metal-halide perovskites for photovoltaic and light-emitting devices
journal, May 2015

  • Stranks, Samuel D.; Snaith, Henry J.
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.90

Charge-Carrier Mobilities in Metal Halide Perovskites: Fundamental Mechanisms and Limits
journal, June 2017


Halide Perovskites: Poor Man's High-Performance Semiconductors
journal, May 2016

  • Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.
  • Advanced Materials, Vol. 28, Issue 28
  • DOI: 10.1002/adma.201600265

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

Low-temperature solution-processed wavelength-tunable perovskites for lasing
journal, March 2014

  • Xing, Guichuan; Mathews, Nripan; Lim, Swee Sien
  • Nature Materials, Vol. 13, Issue 5
  • DOI: 10.1038/nmat3911

Toward Large Scale Roll-to-Roll Production of Fully Printed Perovskite Solar Cells
journal, January 2015

  • Hwang, Kyeongil; Jung, Yen-Sook; Heo, Youn-Jung
  • Advanced Materials, Vol. 27, Issue 7
  • DOI: 10.1002/adma.201404598

Scalable fabrication of perovskite solar cells
journal, March 2018


Perovskite solar cells: film formation and properties
journal, January 2015

  • Song, Tze-Bin; Chen, Qi; Zhou, Huanping
  • Journal of Materials Chemistry A, Vol. 3, Issue 17
  • DOI: 10.1039/C4TA05246C

Perovskite precursor solution chemistry: from fundamentals to photovoltaic applications
journal, January 2019

  • Jung, Minsu; Ji, Sang-Geun; Kim, Gwisu
  • Chemical Society Reviews, Vol. 48, Issue 7
  • DOI: 10.1039/C8CS00656C

Making and Breaking of Lead Halide Perovskites
journal, January 2016

  • Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.
  • Accounts of Chemical Research, Vol. 49, Issue 2
  • DOI: 10.1021/acs.accounts.5b00455

Composition Engineering in Doctor-Blading of Perovskite Solar Cells
journal, May 2017

  • Tang, Shi; Deng, Yehao; Zheng, Xiaopeng
  • Advanced Energy Materials, Vol. 7, Issue 18
  • DOI: 10.1002/aenm.201700302

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

Recent progressive efforts in perovskite solar cells toward commercialization
journal, January 2018

  • Kim, Byeong Jo; Lee, Sangwook; Jung, Hyun Suk
  • Journal of Materials Chemistry A, Vol. 6, Issue 26
  • DOI: 10.1039/C8TA02159G

A Cryogenic Process for Antisolvent-Free High-Performance Perovskite Solar Cells
journal, September 2018


A Review of the Role of Solvents in Formation of High-Quality Solution-Processed Perovskite Films
journal, January 2019

  • Cao, Xiaobing; Zhi, Lili; Jia, Yi
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 8
  • DOI: 10.1021/acsami.8b16315

Morphology-photovoltaic property correlation in perovskite solar cells: One-step versus two-step deposition of CH 3 NH 3 PbI 3
journal, August 2014

  • Im, Jeong-Hyeok; Kim, Hui-Seon; Park, Nam-Gyu
  • APL Materials, Vol. 2, Issue 8
  • DOI: 10.1063/1.4891275

One-step, low-temperature deposited perovskite solar cell utilizing small molecule additive
journal, January 2015

  • Chen, Chun-Chao; Hong, Zirou; Li, Gang
  • Journal of Photonics for Energy, Vol. 5, Issue 1
  • DOI: 10.1117/1.JPE.5.057405

How to Make over 20% Efficient Perovskite Solar Cells in Regular ( n–i–p ) and Inverted ( p–i–n ) Architectures
journal, June 2018


Understanding macroscale functionality of metal halide perovskites in terms of nanoscale heterogeneities
journal, December 2018

  • Song, Tze-Bin; Sharp, Ian D.; Sutter-Fella, Carolin M.
  • Journal of Physics: Energy, Vol. 1, Issue 1
  • DOI: 10.1088/2515-7655/aaeee5

Crystallization Dynamics of Organolead Halide Perovskite by Real-Time X-ray Diffraction
journal, July 2015


Crystallization Kinetics of Organic–Inorganic Trihalide Perovskites and the Role of the Lead Anion in Crystal Growth
journal, February 2015

  • Moore, David T.; Sai, Hiroaki; Tan, Kwan W.
  • Journal of the American Chemical Society, Vol. 137, Issue 6
  • DOI: 10.1021/ja512117e

Ultrasmooth organic–inorganic perovskite thin-film formation and crystallization for efficient planar heterojunction solar cells
journal, January 2015

  • Zhang, Wei; Saliba, Michael; Moore, David T.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7142

Chloride in Lead Chloride-Derived Organo-Metal Halides for Perovskite-Absorber Solar Cells
journal, December 2014

  • Unger, Eva L.; Bowring, Andrea R.; Tassone, Christopher J.
  • Chemistry of Materials, Vol. 26, Issue 24
  • DOI: 10.1021/cm503828b

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


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

Structural and chemical evolution of methylammonium lead halide perovskites during thermal processing from solution
journal, January 2016

  • Nenon, David P.; Christians, Jeffrey A.; Wheeler, Lance M.
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C6EE01047D

Monitoring the Phase Formation of Coevaporated Lead Halide Perovskite Thin Films by in Situ X-ray Diffraction
journal, September 2014

  • Pistor, Paul; Borchert, Juliane; Fränzel, Wolfgang
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 19
  • DOI: 10.1021/jz5017312

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


In situ simultaneous photovoltaic and structural evolution of perovskite solar cells during film formation
journal, January 2018

  • Alsari, Mejd; Bikondoa, Oier; Bishop, James
  • Energy & Environmental Science, Vol. 11, Issue 2
  • DOI: 10.1039/C7EE03013D

In situ investigation of the formation and metastability of formamidinium lead tri-iodide perovskite solar cells
journal, January 2016

  • Aguiar, Jeffery A.; Wozny, Sarah; Holesinger, Terry G.
  • Energy & Environmental Science, Vol. 9, Issue 7
  • DOI: 10.1039/C6EE01079B

Monitoring Thermal Annealing of Perovskite Solar Cells with In Situ Photoluminescence
journal, December 2016

  • van Franeker, Jacobus J.; Hendriks, Koen H.; Bruijnaers, Bardo J.
  • Advanced Energy Materials, Vol. 7, Issue 7
  • DOI: 10.1002/aenm.201601822

High-Performance Inverted Planar Heterojunction Perovskite Solar Cells Based on Lead Acetate Precursor with Efficiency Exceeding 18%
journal, April 2016

  • Zhao, Lichen; Luo, Deying; Wu, Jiang
  • Advanced Functional Materials, Vol. 26, Issue 20
  • DOI: 10.1002/adfm.201601175

The Impact of Atmosphere on the Local Luminescence Properties of Metal Halide Perovskite Grains
journal, March 2018

  • Brenes, Roberto; Eames, Christopher; Bulović, Vladimir
  • Advanced Materials, Vol. 30, Issue 15
  • DOI: 10.1002/adma.201706208

Fractional deviations in precursor stoichiometry dictate the properties, performance and stability of perovskite photovoltaic devices
journal, January 2018

  • Fassl, Paul; Lami, Vincent; Bausch, Alexandra
  • Energy & Environmental Science, Vol. 11, Issue 12
  • DOI: 10.1039/C8EE01136B

Suppressed hysteresis and enhanced performance of triple cation perovskite solar cell with chlorine incorporation
journal, January 2018

  • Li, Lingfeng; Zhou, Peng; Li, Jing
  • Journal of Materials Chemistry C, Vol. 6, Issue 48
  • DOI: 10.1039/C8TC05484C

Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals
journal, September 2017


Crystal Structure of DMF-Intermediate Phases Uncovers the Link Between CH 3 NH 3 PbI 3 Morphology and Precursor Stoichiometry
journal, September 2017

  • Petrov, Andrey A.; Sokolova, Iuliia P.; Belich, Nikolai A.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 38
  • DOI: 10.1021/acs.jpcc.7b08468

Powder X-ray diffraction of oriented and intercalated lead iodide
journal, March 2001

  • Schaeffer, Richard W.; Ardelean, Monica
  • Powder Diffraction, Vol. 16, Issue 1
  • DOI: 10.1154/1.1332077

The Role of Chlorine in the Formation Process of “CH 3 NH 3 PbI 3-x Cl x ” Perovskite
journal, September 2014


Role of Chloride in the Morphological Evolution of Organo-Lead Halide Perovskite Thin Films
journal, October 2014

  • Williams, Spencer T.; Zuo, Fan; Chueh, Chu-Chen
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn5041922

Abnormal crystal growth in CH 3 NH 3 PbI 3−x Cl x using a multi-cycle solution coating process
journal, January 2015

  • Dong, Qingfeng; Yuan, Yongbo; Shao, Yuchuan
  • Energy & Environmental Science, Vol. 8, Issue 8
  • DOI: 10.1039/C5EE01179E

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


A Fast Deposition-Crystallization Procedure for Highly Efficient Lead Iodide Perovskite Thin-Film Solar Cells
journal, July 2014


Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free Charge, and Subgap States
journal, September 2014


Nonradiative Losses in Metal Halide Perovskites
journal, June 2017


High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors
journal, March 2014

  • Deschler, Felix; Price, Michael; Pathak, Sandeep
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
  • DOI: 10.1021/jz5005285

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

  • Milot, Rebecca L.; Eperon, Giles E.; Snaith, Henry J.
  • Advanced Functional Materials, Vol. 25, Issue 39
  • DOI: 10.1002/adfm.201502340

Ror2 signaling regulates Golgi structure and transport through IFT20 for tumor invasiveness
journal, January 2017


Crystal Growth and Dissolution of Methylammonium Lead Iodide Perovskite in Sequential Deposition: Correlation between Morphology Evolution and Photovoltaic Performance
journal, March 2017

  • Hsieh, Tsung-Yu; Huang, Chi-Kai; Su, Tzu-Sen
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 10
  • DOI: 10.1021/acsami.6b12303

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


Solution Synthesis Approach to Colloidal Cesium Lead Halide Perovskite Nanoplatelets with Monolayer-Level Thickness Control
journal, January 2016

  • Akkerman, Quinten A.; Motti, Silvia Genaro; Srimath Kandada, Ajay Ram
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b12124

Low-dimensional perovskite nanoplatelet synthesis using in situ photophysical monitoring to establish controlled growth
journal, January 2019

  • Do, Mai; Kim, Irene; Kolaczkowski, Matthew A.
  • Nanoscale, Vol. 11, Issue 37
  • DOI: 10.1039/C9NR04010B

Mechanistic insights into perovskite photoluminescence enhancement: light curing with oxygen can boost yield thousandfold
journal, January 2015

  • Tian, Yuxi; Peter, Maximilian; Unger, Eva
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 38
  • DOI: 10.1039/C5CP04410C

Environmental Effects on the Photophysics of Organic–Inorganic Halide Perovskites
journal, June 2015

  • Galisteo-López, Juan F.; Anaya, M.; Calvo, M. E.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 12
  • DOI: 10.1021/acs.jpclett.5b00785

The effect of illumination on the formation of metal halide perovskite films
journal, April 2017

  • Ummadisingu, Amita; Steier, Ludmilla; Seo, Ji-Youn
  • Nature, Vol. 545, Issue 7653
  • DOI: 10.1038/nature22072

Triggering the Passivation Effect of Potassium Doping in Mixed‐Cation Mixed‐Halide Perovskite by Light Illumination
journal, April 2019

  • Zheng, Fei; Chen, Weijian; Bu, Tongle
  • Advanced Energy Materials, Vol. 9, Issue 24
  • DOI: 10.1002/aenm.201901016

Effect of different lead precursors on perovskite solar cell performance and stability
journal, January 2015

  • Aldibaja, Fadi Kamal; Badia, Laura; Mas-Marzá, Elena
  • Journal of Materials Chemistry A, Vol. 3, Issue 17
  • DOI: 10.1039/C4TA06198E

Controllable Self-Induced Passivation of Hybrid Lead Iodide Perovskites toward High Performance Solar Cells
journal, June 2014

  • Chen, Qi; Zhou, Huanping; Song, Tze-Bin
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl501838y

Planar‐Structure Perovskite Solar Cells with Efficiency beyond 21%
journal, October 2017


Polyelemental, Multicomponent Perovskite Semiconductor Libraries through Combinatorial Screening
journal, May 2019