In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films

Justin M. Hoffman; Joseph Strzalka; Nathan C. Flanders; Ido Hadar; Shelby A. Cuthriell; Qingteng Zhang; Richard D. Schaller; William R. Dichtel; Lin X. Chen; Mercouri G. Kanatzidis

doi:10.1002/adma.202002812

In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films

Justin M. Hoffman, Joseph Strzalka, Nathan C. Flanders, Ido Hadar, Shelby A. Cuthriell, Qingteng Zhang, Richard D. Schaller, William R. Dichtel, Lin X. Chen^*, Mercouri G. Kanatzidis

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

101 Scopus citations

Abstract

2D hybrid halide perovskites with the formula (A′)₂(A)_n_-1Pb_nI₃_n₊₁ have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor film formation during spin-coating. This elucidates the general film formation mechanism of 2D halide perovskites during one-step spin-coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D-like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.

Original language	English (US)
Article number	2002812
Journal	Advanced Materials
Volume	32
Issue number	33
DOIs	https://doi.org/10.1002/adma.202002812
State	Published - Aug 1 2020

Funding

This work was supported by the Office of Naval Research (ONR) under grant N00014‐20‐1‐2725. This project was supported in part by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program, sponsored by the Air Force Research Laboratory (AFRL), the Office of Naval Research (ONR) and the Army Research Office (ARO). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH113. Part of this work was done through Dr. Hsinhan Tsai’s user proposal (GUP‐61829) at Beamline 8‐ID‐E of the Advanced Photon Source at Argonne National Laboratory. N.C.F is partially supported by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE‐SC0001059. L.X.C. is partially support by the Solar Energy Photochemistry program of the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE‐AC02‐06CH11357.

Keywords

2D halide perovskites, film formation
kinetics
photovoltaics
spin-coating, thin films

ASJC Scopus subject areas

General Materials Science
Mechanics of Materials
Mechanical Engineering

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/adma.202002812

Cite this

Hoffman, J. M., Strzalka, J., Flanders, N. C., Hadar, I., Cuthriell, S. A., Zhang, Q., Schaller, R. D., Dichtel, W. R., Chen, L. X., & Kanatzidis, M. G. (2020). In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films. Advanced Materials, 32(33), Article 2002812. https://doi.org/10.1002/adma.202002812

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title = "In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films",

abstract = "2D hybrid halide perovskites with the formula (A′)2(A)n-1PbnI3n+1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor film formation during spin-coating. This elucidates the general film formation mechanism of 2D halide perovskites during one-step spin-coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D-like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.",

keywords = "2D halide perovskites, film formation, kinetics, photovoltaics, spin-coating, thin films",

author = "Hoffman, {Justin M.} and Joseph Strzalka and Flanders, {Nathan C.} and Ido Hadar and Cuthriell, {Shelby A.} and Qingteng Zhang and Schaller, {Richard D.} and Dichtel, {William R.} and Chen, {Lin X.} and Kanatzidis, {Mercouri G.}",

note = "Funding Information: This work was supported by the Office of Naval Research (ONR) under grant N00014‐20‐1‐2725. This project was supported in part by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program, sponsored by the Air Force Research Laboratory (AFRL), the Office of Naval Research (ONR) and the Army Research Office (ARO). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH113. Part of this work was done through Dr. Hsinhan Tsai{\textquoteright}s user proposal (GUP‐61829) at Beamline 8‐ID‐E of the Advanced Photon Source at Argonne National Laboratory. N.C.F is partially supported by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE‐SC0001059. L.X.C. is partially support by the Solar Energy Photochemistry program of the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE‐AC02‐06CH11357. Publisher Copyright: {\textcopyright} 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

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doi = "10.1002/adma.202002812",

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AU - Hoffman, Justin M.

AU - Strzalka, Joseph

AU - Flanders, Nathan C.

AU - Hadar, Ido

AU - Cuthriell, Shelby A.

AU - Zhang, Qingteng

AU - Schaller, Richard D.

AU - Dichtel, William R.

AU - Chen, Lin X.

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: This work was supported by the Office of Naval Research (ONR) under grant N00014‐20‐1‐2725. This project was supported in part by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program, sponsored by the Air Force Research Laboratory (AFRL), the Office of Naval Research (ONR) and the Army Research Office (ARO). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH113. Part of this work was done through Dr. Hsinhan Tsai’s user proposal (GUP‐61829) at Beamline 8‐ID‐E of the Advanced Photon Source at Argonne National Laboratory. N.C.F is partially supported by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE‐SC0001059. L.X.C. is partially support by the Solar Energy Photochemistry program of the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE‐AC02‐06CH11357. Publisher Copyright: © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/8/1

Y1 - 2020/8/1

N2 - 2D hybrid halide perovskites with the formula (A′)2(A)n-1PbnI3n+1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor film formation during spin-coating. This elucidates the general film formation mechanism of 2D halide perovskites during one-step spin-coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D-like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.

AB - 2D hybrid halide perovskites with the formula (A′)2(A)n-1PbnI3n+1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor film formation during spin-coating. This elucidates the general film formation mechanism of 2D halide perovskites during one-step spin-coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D-like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.

KW - 2D halide perovskites, film formation

KW - kinetics

KW - photovoltaics

KW - spin-coating, thin films

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In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

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CCDC 1999069: Experimental Crystal Structure Determination

Cite this

In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1999069: Experimental Crystal Structure Determination

Cite this