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Title: Controlling Solvate Intermediate Growth for Phase-Pure Organic Lead Iodide Ruddlesden–Popper (C4H9NH3)2(CH3NH3)n-1PbnI3n+1 Perovskite Thin Films

Abstract

The growth of Ruddlesden-Popper perovskite thin films is complicated by the existence of multiple crystallization pathways available to precursors in solution. During conventional thin film growth processes, such as spin-coating or blade-coating, solvents can evaporate too quickly to clearly resolve different reaction intermediates and products that form during crystallization. Here, we resolve multiple reaction products and intermediates that form during Ruddlesden-Popper phase growth by studying drop-cast precursor solutions in situ through the evolution of X-ray diffraction, photoluminescence, and optical micrographs over long timescales in a thin film geometry. We found that methylammonium-rich solvate intermediates play a crucial role in directing the bulk optical properties of the films, and form simultaneously with smaller regions of Ruddlesden-Popper phases during growth. The microstructure and optical properties of these sub-phases were characterized during growth and after annealing, revealing that discrepancies between thin film and single-crystal optical properties originate from solvate intermediates. These lower band-gap solvate-mediated minority phases dominate the optical emission spectrum by means of rapid energy migration, and contribute to sub-band-gap electronic states in photovoltaic devices. Processing routes to yield thin films with optical properties similar to single crystals of Ruddlesden-Popper phases were developed by tuning the precursor stoichiometry and deposition kinetics.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Westmont College, Santa Barbara, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Quantum Materials for Energy Efficient Neuromorphic Computing (Q-MEEN-C); Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1594806
Grant/Contract Number:  
SC0012541; SC0019273; AC02-76SF00515; AC0205CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 15; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Thin films; Crystallization; Precursors; Solvates; Deposition

Citation Formats

Dahlman, Clayton J., DeCrescent, Ryan A., Venkatesan, Naveen R., Kennard, Rhys M., Wu, Guang, Everest, Michael A., Schuller, Jon A., and Chabinyc, Michael L.. Controlling Solvate Intermediate Growth for Phase-Pure Organic Lead Iodide Ruddlesden–Popper (C4H9NH3)2(CH3NH3)n-1PbnI3n+1 Perovskite Thin Films. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.chemmater.9b01952.
Dahlman, Clayton J., DeCrescent, Ryan A., Venkatesan, Naveen R., Kennard, Rhys M., Wu, Guang, Everest, Michael A., Schuller, Jon A., & Chabinyc, Michael L.. Controlling Solvate Intermediate Growth for Phase-Pure Organic Lead Iodide Ruddlesden–Popper (C4H9NH3)2(CH3NH3)n-1PbnI3n+1 Perovskite Thin Films. United States. https://doi.org/10.1021/acs.chemmater.9b01952
Dahlman, Clayton J., DeCrescent, Ryan A., Venkatesan, Naveen R., Kennard, Rhys M., Wu, Guang, Everest, Michael A., Schuller, Jon A., and Chabinyc, Michael L.. Tue . "Controlling Solvate Intermediate Growth for Phase-Pure Organic Lead Iodide Ruddlesden–Popper (C4H9NH3)2(CH3NH3)n-1PbnI3n+1 Perovskite Thin Films". United States. https://doi.org/10.1021/acs.chemmater.9b01952. https://www.osti.gov/servlets/purl/1594806.
@article{osti_1594806,
title = {Controlling Solvate Intermediate Growth for Phase-Pure Organic Lead Iodide Ruddlesden–Popper (C4H9NH3)2(CH3NH3)n-1PbnI3n+1 Perovskite Thin Films},
author = {Dahlman, Clayton J. and DeCrescent, Ryan A. and Venkatesan, Naveen R. and Kennard, Rhys M. and Wu, Guang and Everest, Michael A. and Schuller, Jon A. and Chabinyc, Michael L.},
abstractNote = {The growth of Ruddlesden-Popper perovskite thin films is complicated by the existence of multiple crystallization pathways available to precursors in solution. During conventional thin film growth processes, such as spin-coating or blade-coating, solvents can evaporate too quickly to clearly resolve different reaction intermediates and products that form during crystallization. Here, we resolve multiple reaction products and intermediates that form during Ruddlesden-Popper phase growth by studying drop-cast precursor solutions in situ through the evolution of X-ray diffraction, photoluminescence, and optical micrographs over long timescales in a thin film geometry. We found that methylammonium-rich solvate intermediates play a crucial role in directing the bulk optical properties of the films, and form simultaneously with smaller regions of Ruddlesden-Popper phases during growth. The microstructure and optical properties of these sub-phases were characterized during growth and after annealing, revealing that discrepancies between thin film and single-crystal optical properties originate from solvate intermediates. These lower band-gap solvate-mediated minority phases dominate the optical emission spectrum by means of rapid energy migration, and contribute to sub-band-gap electronic states in photovoltaic devices. Processing routes to yield thin films with optical properties similar to single crystals of Ruddlesden-Popper phases were developed by tuning the precursor stoichiometry and deposition kinetics.},
doi = {10.1021/acs.chemmater.9b01952},
journal = {Chemistry of Materials},
number = 15,
volume = 31,
place = {United States},
year = {2019},
month = {7}
}

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Works referenced in this record:

Present status and future prospects of perovskite photovoltaics
journal, April 2018


Metal halide perovskites for energy applications
journal, May 2016


Hybrid organic—inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties
journal, January 2016

  • Brenner, Thomas M.; Egger, David A.; Kronik, Leeor
  • Nature Reviews Materials, Vol. 1, Issue 1
  • DOI: 10.1038/natrevmats.2015.7

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

  • Berry, Joseph; Buonassisi, Tonio; Egger, David A.
  • Advanced Materials, Vol. 27, Issue 35
  • DOI: 10.1002/adma.201502294

Perovskites: The Emergence of a New Era for Low-Cost, High-Efficiency Solar Cells
journal, October 2013

  • Snaith, Henry J.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 21, p. 3623-3630
  • DOI: 10.1021/jz4020162

Reversible Hydration of CH 3 NH 3 PbI 3 in Films, Single Crystals, and Solar Cells
journal, April 2015


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

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

Ligand-Stabilized Reduced-Dimensionality Perovskites
journal, February 2016

  • Quan, Li Na; Yuan, Mingjian; Comin, Riccardo
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b11740

High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
journal, July 2016

  • Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe
  • Nature, Vol. 536, Issue 7616
  • DOI: 10.1038/nature18306

Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors
journal, April 2016

  • Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J.
  • Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867
  • DOI: 10.1021/acs.chemmater.6b00847

2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications
journal, June 2015

  • Cao, Duyen H.; Stoumpos, Constantinos C.; Farha, Omar K.
  • Journal of the American Chemical Society, Vol. 137, Issue 24
  • DOI: 10.1021/jacs.5b03796

A Layered Hybrid Perovskite Solar-Cell Absorber with Enhanced Moisture Stability
journal, September 2014

  • Smith, Ian C.; Hoke, Eric T.; Solis-Ibarra, Diego
  • Angewandte Chemie, Vol. 126, Issue 42
  • DOI: 10.1002/ange.201406466

Scaling law for excitons in 2D perovskite quantum wells
journal, June 2018


Optical properties due to electronic transitions in two-dimensional semiconductors ( C n H 2 n + 1 NH 3 ) 2 PbI 4
journal, December 1990


Exploration of Crystallization Kinetics in Quasi Two-Dimensional Perovskite and High Performance Solar Cells
journal, December 2017

  • Zhou, Ning; Shen, Yiheng; Li, Liang
  • Journal of the American Chemical Society, Vol. 140, Issue 1
  • DOI: 10.1021/jacs.7b11157

Orientation Regulation of Phenylethylammonium Cation Based 2D Perovskite Solar Cell with Efficiency Higher Than 11%
journal, January 2018

  • Zhang, Xinqian; Wu, Gang; Fu, Weifei
  • Advanced Energy Materials, Vol. 8, Issue 14
  • DOI: 10.1002/aenm.201702498

Two-Dimensional Ruddlesden–Popper Perovskite with Nanorod-like Morphology for Solar Cells with Efficiency Exceeding 15%
journal, August 2018

  • Lai, Hongtao; Kan, Bin; Liu, Tingting
  • Journal of the American Chemical Society, Vol. 140, Issue 37
  • DOI: 10.1021/jacs.8b04604

Oriented Quasi-2D Perovskites for High Performance Optoelectronic Devices
journal, October 2018


Stable high efficiency two-dimensional perovskite solar cells via cesium doping
journal, January 2017

  • Zhang, Xu; Ren, Xiaodong; Liu, Bin
  • Energy & Environmental Science, Vol. 10, Issue 10
  • DOI: 10.1039/C7EE01145H

The Diversity of Layered Halide Perovskites
journal, July 2018


2D Ruddlesden-Popper Perovskites for Optoelectronics
journal, October 2017


Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016


Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells
journal, September 2016


Stable Light-Emitting Diodes Using Phase-Pure Ruddlesden-Popper Layered Perovskites
journal, January 2018

  • Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe
  • Advanced Materials, Vol. 30, Issue 6
  • DOI: 10.1002/adma.201704217

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

Synthetic Control over Quantum Well Width Distribution and Carrier Migration in Low-Dimensional Perovskite Photovoltaics
journal, February 2018

  • Proppe, Andrew H.; Quintero-Bermudez, Rafael; Tan, Hairen
  • Journal of the American Chemical Society, Vol. 140, Issue 8
  • DOI: 10.1021/jacs.7b12551

Phase Transition Control for High Performance Ruddlesden-Popper Perovskite Solar Cells
journal, April 2018


Preferential Orientation of Crystals Induced by Incorporation of Organic Ligands in Mixed-Dimensional Hybrid Perovskite Films
journal, January 2018


Phase Intergrowth and Structural Defects in Organic Metal Halide Ruddlesden–Popper Thin Films
journal, November 2018


Charge-Carrier Dynamics and Crystalline Texture of Layered Ruddlesden–Popper Hybrid Lead Iodide Perovskite Thin Films
journal, January 2018


Manipulating the Phase Distributions and Carrier Transfers in Hybrid Quasi‐Two‐Dimensional Perovskite Films
journal, February 2019


Unveiling the operation mechanism of layered perovskite solar cells
journal, March 2019


General Post-annealing Method Enables High-Efficiency Two-Dimensional Perovskite Solar Cells
journal, September 2018

  • Yan, Liang; Hu, Jun; Guo, Zhenkun
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 39
  • DOI: 10.1021/acsami.8b10230

Energy transfer mechanisms in layered 2D perovskites
journal, April 2018

  • Williams, Olivia F.; Guo, Zhenkun; Hu, Jun
  • The Journal of Chemical Physics, Vol. 148, Issue 13
  • DOI: 10.1063/1.5009663

Observation of Internal Photoinduced Electron and Hole Separation in Hybrid Two-Dimentional Perovskite Films
journal, January 2017

  • Liu, Junxue; Leng, Jing; Wu, Kaifeng
  • Journal of the American Chemical Society, Vol. 139, Issue 4
  • DOI: 10.1021/jacs.6b12581

Highly Efficient Ruddlesden–Popper Halide Perovskite PA 2 MA 4 Pb 5 I 16 Solar Cells
journal, July 2018


Understanding Film Formation Morphology and Orientation in High Member 2D Ruddlesden-Popper Perovskites for High-Efficiency Solar Cells
journal, September 2017

  • Soe, Chan Myae Myae; Nie, Wanyi; Stoumpos, Constantinos C.
  • Advanced Energy Materials, Vol. 8, Issue 1
  • DOI: 10.1002/aenm.201700979

Spectrally Resolved Ultrafast Exciton Transfer in Mixed Perovskite Quantum Wells
journal, January 2019

  • Proppe, Andrew H.; Elkins, Madeline H.; Voznyy, Oleksandr
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 3
  • DOI: 10.1021/acs.jpclett.9b00018

Perovskite energy funnels for efficient light-emitting diodes
journal, June 2016

  • Yuan, Mingjian; Quan, Li Na; Comin, Riccardo
  • Nature Nanotechnology, Vol. 11, Issue 10
  • DOI: 10.1038/nnano.2016.110

Unveiling Structurally Engineered Carrier Dynamics in Hybrid Quasi-Two-Dimensional Perovskite Thin Films toward Controllable Emission
journal, September 2017

  • Shang, Qiuyu; Wang, Yunuan; Zhong, Yangguang
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 18
  • DOI: 10.1021/acs.jpclett.7b01857

Binary Solvent Engineering for High-Performance Two-Dimensional Perovskite Solar Cells
journal, January 2019


Favorable growth of well-crystallized layered hybrid perovskite by combination of thermal and solvent assistance
journal, May 2019


Reduced-Dimensional Perovskite Enabled by Organic Diamine for Efficient Photovoltaics
journal, April 2019


Synthetic control over orientational degeneracy of spacer cations enhances solar cell efficiency in two-dimensional perovskites
journal, March 2019


Improving the Stability and Monodispersity of Layered Cesium Lead Iodide Perovskite Thin Films by Tuning Crystallization Dynamics
journal, June 2019


2D Intermediate Suppression for Efficient Ruddlesden–Popper (RP) Phase Lead-Free Perovskite Solar Cells
journal, June 2019


Phase-Pure Hybrid Layered Lead Iodide Perovskite Films Based on a Two-Step Melt-Processing Approach
journal, May 2019


Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites
journal, March 2017


Single-crystalline layered metal-halide perovskite nanowires for ultrasensitive photodetectors
journal, July 2018


Aligned and Graded Type-II Ruddlesden-Popper Perovskite Films for Efficient Solar Cells
journal, May 2018

  • Qing, Jian; Liu, Xiao-Ke; Li, Mingjie
  • Advanced Energy Materials, Vol. 8, Issue 21
  • DOI: 10.1002/aenm.201800185

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

Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide
journal, July 2015

  • Ahn, Namyoung; Son, Dae-Yong; Jang, In-Hyuk
  • Journal of the American Chemical Society, Vol. 137, Issue 27
  • DOI: 10.1021/jacs.5b04930

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


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

Controlled Growth of Monocrystalline Organo-Lead Halide Perovskite and Its Application in Photonic Devices
journal, July 2017

  • Mao, Wenxin; Zheng, Jialu; Zhang, Yupeng
  • Angewandte Chemie International Edition, Vol. 56, Issue 41
  • DOI: 10.1002/anie.201703786

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

Fabrication of high quality perovskite films by modulating the Pb–O bonds in Lewis acid–base adducts
journal, January 2017

  • Cao, X. B.; Li, C. L.; Zhi, L. L.
  • Journal of Materials Chemistry A, Vol. 5, Issue 18
  • DOI: 10.1039/C7TA00539C

Influence of Solvent Coordination on Hybrid Organic–Inorganic Perovskite Formation
journal, November 2017


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


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


Rapid Crystallization for Efficient 2D Ruddlesden–Popper (2DRP) Perovskite Solar Cells
journal, December 2018

  • Qiu, Jian; Zheng, Yiting; Xia, Yingdong
  • Advanced Functional Materials, Vol. 29, Issue 47
  • DOI: 10.1002/adfm.201806831

Efficient green light-emitting diodes based on quasi-two-dimensional composition and phase engineered perovskite with surface passivation
journal, February 2018


Understanding the Formation of Vertical Orientation in Two-dimensional Metal Halide Perovskite Thin Films
journal, January 2019


Shedding Light on the Moisture Stability of 3D/2D Hybrid Perovskite Heterojunction Thin Films
journal, January 2019

  • Schlipf, Johannes; Hu, Yinghong; Pratap, Shambhavi
  • ACS Applied Energy Materials, Vol. 2, Issue 2
  • DOI: 10.1021/acsaem.9b00005

Extrinsic and Dynamic Edge States of Two-Dimensional Lead Halide Perovskites
journal, February 2019


Systematic study on the impact of water on the performance and stability of perovskite solar cells
journal, January 2016


Crystalline Intermediates and Their Transformation Kinetics during the Formation of Methylammonium Lead Halide Perovskite Thin Films
journal, December 2016


Absorption of Water into Organic Solvents Used for Electrochemistry under Conventional Operating Conditions
journal, February 2011

  • Hui, Yanlan; Webster, Richard D.
  • Analytical Chemistry, Vol. 83, Issue 3
  • DOI: 10.1021/ac102734a

Mechanism of the transition from fractal to dendritic growth of surface aggregates
journal, June 1994

  • Brune, Harald; Romainczyk, Christoph; Röder, Holger
  • Nature, Vol. 369, Issue 6480
  • DOI: 10.1038/369469a0

Hybrid Halide Perovskite Solar Cell Precursors: Colloidal Chemistry and Coordination Engineering behind Device Processing for High Efficiency
journal, March 2015

  • Yan, Keyou; Long, Mingzhu; Zhang, Tiankai
  • Journal of the American Chemical Society, Vol. 137, Issue 13
  • DOI: 10.1021/jacs.5b00321

Programmable and coherent crystallization of semiconductors
journal, March 2017

  • Yu, Liyang; Niazi, Muhammad R.; Ngongang Ndjawa, Guy O.
  • Science Advances, Vol. 3, Issue 3
  • DOI: 10.1126/sciadv.1602462

Shape-Evolution Control of hybrid perovskite CH3NH3PbI3 crystals via solvothermal synthesis
journal, February 2017


Controllable Perovskite Crystallization at a Gas–Solid Interface for Hole Conductor-Free Solar Cells with Steady Power Conversion Efficiency over 10%
journal, November 2014

  • Hao, Feng; Stoumpos, Constantinos C.; Liu, Zhao
  • Journal of the American Chemical Society, Vol. 136, Issue 46
  • DOI: 10.1021/ja509245x

Charge-Carrier Dynamics in 2D Hybrid Metal–Halide Perovskites
journal, October 2016


Structure-Tuned Lead Halide Perovskite Nanocrystals
journal, November 2015

  • Hassan, Yasser; Song, Yin; Pensack, Ryan D.
  • Advanced Materials, Vol. 28, Issue 3
  • DOI: 10.1002/adma.201503461

Toward a Unified Theory of Urbach's Rule and Exponential Absorption Edges
journal, January 1972


Temperature Dependence of the Urbach Energy in Lead Iodide Perovskites
journal, February 2019

  • Ledinsky, Martin; Schönfeldová, Tereza; Holovský, Jakub
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 6
  • DOI: 10.1021/acs.jpclett.9b00138

Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance
journal, March 2014

  • De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 6
  • DOI: 10.1021/jz500279b

Stable High-Performance Perovskite Solar Cells via Grain Boundary Passivation
journal, March 2018


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