Phase Intergrowth and Structural Defects in Organic Metal Halide Ruddlesden–Popper Thin Films
Abstract
Organic metal halide Ruddlesden–Popper phases combine the excellent optoelectronic properties of three-dimensional, bulk hybrid perovskites with superior material stability in ambient conditions. However, the thin film structure of these layered perovskites is still poorly understood, as phase purity is typically determined solely by specular X-ray diffraction. The thin film structure of these Ruddlesden–Popper phases was examined by increasingly local characterization techniques. It is difficult to assess the phase purity by purely bulk optical and diffraction measurements. From the comparison of grazing-incidence wide angle X-ray scattering (GIWAXS) patterns of cast films to expected scattering from single-crystal structures, significant in-plane disorder was observed. Spatially localized photoluminescence measurements show that films do not phase separate on the micrometer-scale. Selected area electron diffraction measurements show the intergrowth of different phases within the same thin film, consistent with previous observations seen in epitaxially-grown Ruddlesden–Popper complex oxides. Despite the presence of phase impurities that would typically be detrimental for device performance, fits to photothermal deflection spectroscopy measurements show relatively low Urbach energies of 33 meV for (C4H9NH3)2(CH3NH3)2Pb3I10 and 32 meV for (C4H9NH3)2(CH3NH3)3Pb4I13, indicating that the electronic properties are insensitive to the phase impurities.
- Authors:
-
[1];
[1];
[1];
[1]
- Univ. of California, Santa Barbara, CA (United States)
- Mitsubishi Chemical Corporation (Japan). Electronics Materials and New Energy Lab.; Univ. of California, Santa Barbara, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Santa Barbara, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1594808
- Grant/Contract Number:
- SC0012541; HDTRA1-15-1-0023; AC02-76SF00515; DMR-1720256; DMR-1454260
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 23; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Venkatesan, Naveen R., Kennard, Rhys M., DeCrescent, Ryan A., Nakayama, Hidenori, Dahlman, Clayton J., Perry, Erin E., Schuller, Jon A., and Chabinyc, Michael L. Phase Intergrowth and Structural Defects in Organic Metal Halide Ruddlesden–Popper Thin Films. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b03832.
Venkatesan, Naveen R., Kennard, Rhys M., DeCrescent, Ryan A., Nakayama, Hidenori, Dahlman, Clayton J., Perry, Erin E., Schuller, Jon A., & Chabinyc, Michael L. Phase Intergrowth and Structural Defects in Organic Metal Halide Ruddlesden–Popper Thin Films. United States. https://doi.org/10.1021/acs.chemmater.8b03832
Venkatesan, Naveen R., Kennard, Rhys M., DeCrescent, Ryan A., Nakayama, Hidenori, Dahlman, Clayton J., Perry, Erin E., Schuller, Jon A., and Chabinyc, Michael L. Tue .
"Phase Intergrowth and Structural Defects in Organic Metal Halide Ruddlesden–Popper Thin Films". United States. https://doi.org/10.1021/acs.chemmater.8b03832. https://www.osti.gov/servlets/purl/1594808.
@article{osti_1594808,
title = {Phase Intergrowth and Structural Defects in Organic Metal Halide Ruddlesden–Popper Thin Films},
author = {Venkatesan, Naveen R. and Kennard, Rhys M. and DeCrescent, Ryan A. and Nakayama, Hidenori and Dahlman, Clayton J. and Perry, Erin E. and Schuller, Jon A. and Chabinyc, Michael L.},
abstractNote = {Organic metal halide Ruddlesden–Popper phases combine the excellent optoelectronic properties of three-dimensional, bulk hybrid perovskites with superior material stability in ambient conditions. However, the thin film structure of these layered perovskites is still poorly understood, as phase purity is typically determined solely by specular X-ray diffraction. The thin film structure of these Ruddlesden–Popper phases was examined by increasingly local characterization techniques. It is difficult to assess the phase purity by purely bulk optical and diffraction measurements. From the comparison of grazing-incidence wide angle X-ray scattering (GIWAXS) patterns of cast films to expected scattering from single-crystal structures, significant in-plane disorder was observed. Spatially localized photoluminescence measurements show that films do not phase separate on the micrometer-scale. Selected area electron diffraction measurements show the intergrowth of different phases within the same thin film, consistent with previous observations seen in epitaxially-grown Ruddlesden–Popper complex oxides. Despite the presence of phase impurities that would typically be detrimental for device performance, fits to photothermal deflection spectroscopy measurements show relatively low Urbach energies of 33 meV for (C4H9NH3)2(CH3NH3)2Pb3I10 and 32 meV for (C4H9NH3)2(CH3NH3)3Pb4I13, indicating that the electronic properties are insensitive to the phase impurities.},
doi = {10.1021/acs.chemmater.8b03832},
journal = {Chemistry of Materials},
number = 23,
volume = 30,
place = {United States},
year = {Tue Nov 27 00:00:00 EST 2018},
month = {Tue Nov 27 00:00:00 EST 2018}
}
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Works referenced in this record:
Organic-inorganic electronics
journal, January 2001
- Mitzi, D. B.; Chondroudis, K.; Kagan, C. R.
- IBM Journal of Research and Development, Vol. 45, Issue 1
Hybrid Organic-Inorganic Perovskites (HOIPs): Opportunities and Challenges
journal, July 2015
- Berry, Joseph; Buonassisi, Tonio; Egger, David A.
- Advanced Materials, Vol. 27, Issue 35
Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
journal, October 1999
- Kagan, C. R.; Mitzi, D. B.; Dimitrakopoulos, C. D.
- Science, Vol. 286, Issue 5441, p. 945-947
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016
- Saparov, Bayrammurad; Mitzi, David B.
- Chemical Reviews, Vol. 116, Issue 7
Some new organic-inorganic hybrid semiconductors based on metal halide units: structural, optical and related properties
journal, November 1999
- Papavassiliou, G. C.; Mousdis, G. A.; Koutselas, I. B.
- Advanced Materials for Optics and Electronics, Vol. 9, Issue 6
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
Metal halide perovskites for energy applications
journal, May 2016
- Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.
- Nature Energy, Vol. 1, Issue 6
High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
journal, December 2013
- Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
- Advanced Materials, Vol. 26, Issue 10
Charge Carrier Lifetimes Exceeding 15 μs in Methylammonium Lead Iodide Single Crystals
journal, February 2016
- Bi, Yu; Hutter, Eline M.; Fang, Yanjun
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
The Rashba effect and indirect electron–hole recombination in hybrid organic–inorganic perovskites
journal, January 2017
- Yu, Zhi-Gang
- Physical Chemistry Chemical Physics, Vol. 19, Issue 23
Rashba Band Splitting in Organohalide Lead Perovskites: Bulk and Surface Effects
journal, May 2017
- Mosconi, Edoardo; Etienne, Thibaud; De Angelis, Filippo
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 10
Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH 3 NH 3 PbI 3
journal, November 2015
- Zheng, Fan; Tan, Liang Z.; Liu, Shi
- Nano Letters, Vol. 15, Issue 12
Long-Lived Photoinduced Polarons in Organohalide Perovskites
journal, June 2017
- Ivanovska, Tanja; Dionigi, Chiara; Mosconi, Edoardo
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 13
Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons
journal, November 2015
- Zhu, X. -Y.; Podzorov, V.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
journal, June 2017
- Yang, Woon Seok; Park, Byung-Wook; Jung, Eui Hyuk
- Science, Vol. 356, Issue 6345
Photovoltaic materials: Present efficiencies and future challenges
journal, April 2016
- Polman, A.; Knight, M.; Garnett, E. C.
- Science, Vol. 352, Issue 6283
Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites
journal, January 2017
- Xiao, Zhengguo; Kerner, Ross A.; Zhao, Lianfeng
- Nature Photonics, Vol. 11, Issue 2
Perovskite energy funnels for efficient light-emitting diodes
journal, June 2016
- Yuan, Mingjian; Quan, Li Na; Comin, Riccardo
- Nature Nanotechnology, Vol. 11, Issue 10
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
Structural origins of broadband emission from layered Pb–Br hybrid perovskites
journal, January 2017
- Smith, Matthew D.; Jaffe, Adam; Dohner, Emma R.
- Chemical Science, Vol. 8, Issue 6
Mechanism for Broadband White-Light Emission from Two-Dimensional (110) Hybrid Perovskites
journal, May 2016
- Hu, Te; Smith, Matthew D.; Dohner, Emma R.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 12
White-Light Emission from Layered Halide Perovskites
journal, February 2018
- Smith, Matthew D.; Karunadasa, Hemamala I.
- Accounts of Chemical Research, Vol. 51, Issue 3
The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers
journal, May 2015
- Aristidou, Nicholas; Sanchez-Molina, Irene; Chotchuangchutchaval, Thana
- Angewandte Chemie International Edition, Vol. 54, Issue 28
Redox Chemistry Dominates the Degradation and Decomposition of Metal Halide Perovskite Optoelectronic Devices
journal, August 2016
- Zhao, Lianfeng; Kerner, Ross A.; Xiao, Zhengguo
- ACS Energy Letters, Vol. 1, Issue 3
Stability of Metal Halide Perovskite Solar Cells
journal, September 2015
- Leijtens, Tomas; Eperon, Giles E.; Noel, Nakita K.
- Advanced Energy Materials, Vol. 5, Issue 20
New compounds of the K 2 NIF 4 type
journal, August 1957
- Ruddlesden, S. N.; Popper, P.
- Acta Crystallographica, Vol. 10, Issue 8
The compound Sr 3 Ti 2 O 7 and its structure
journal, January 1958
- Ruddlesden, S. N.; Popper, P.
- Acta Crystallographica, Vol. 11, Issue 1
Epitaxial growth of the first five members of the Srn+1TinO3n+1 Ruddlesden–Popper homologous series
journal, May 2001
- Haeni, J. H.; Theis, C. D.; Schlom, D. G.
- Applied Physics Letters, Vol. 78, Issue 21
Layered Ruddlesden−Popper Manganese Oxides: Synthesis and Cation Ordering
journal, February 1997
- Battle, P. D.; Green, M. A.; Laskey, N. S.
- Chemistry of Materials, Vol. 9, Issue 2
2D Ruddlesden-Popper Perovskites for Optoelectronics
journal, October 2017
- Chen, Yani; Sun, Yong; Peng, Jiajun
- Advanced Materials, Vol. 30, Issue 2
Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions
journal, August 2015
- Akkerman, Quinten A.; D’Innocenzo, Valerio; Accornero, Sara
- Journal of the American Chemical Society, Vol. 137, Issue 32
Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015
- Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
- Nano Letters, Vol. 15, Issue 6
Colloidal Halide Perovskite Nanoplatelets: An Exciting New Class of Semiconductor Nanomaterials
journal, May 2017
- Weidman, Mark C.; Goodman, Aaron J.; Tisdale, William A.
- Chemistry of Materials, Vol. 29, Issue 12
High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
journal, July 2016
- Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe
- Nature, Vol. 536, Issue 7616
Highly Oriented Low-Dimensional Tin Halide Perovskites with Enhanced Stability and Photovoltaic Performance
journal, May 2017
- Liao, Yuqin; Liu, Hefei; Zhou, Wenjia
- Journal of the American Chemical Society, Vol. 139, Issue 19
Charge-Carrier Dynamics and Crystalline Texture of Layered Ruddlesden–Popper Hybrid Lead Iodide Perovskite Thin Films
journal, January 2018
- Venkatesan, Naveen R.; Labram, John G.; Chabinyc, Michael L.
- ACS Energy Letters, Vol. 3, Issue 2
Charge transport in a two-dimensional hybrid metal halide thiocyanate compound
journal, January 2017
- Labram, John G.; Venkatesan, Naveen R.; Takacs, Christopher J.
- Journal of Materials Chemistry C, Vol. 5, Issue 24
Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites
journal, March 2017
- Blancon, J. -C.; Tsai, H.; Nie, W.
- Science, Vol. 355, Issue 6331
High-efficiency solution-processed perovskite solar cells with millimeter-scale grains
journal, January 2015
- Nie, W.; Tsai, H.; Asadpour, R.
- Science, Vol. 347, Issue 6221, p. 522-525
Enhanced Efficiency of Hot-Cast Large-Area Planar Perovskite Solar Cells/Modules Having Controlled Chloride Incorporation
journal, December 2016
- Liao, Hsueh-Chung; Guo, Peijun; Hsu, Che-Pu
- Advanced Energy Materials, Vol. 7, Issue 8
Strain and composition distributions in wurtzite InGaN/GaN layers extracted from x-ray reciprocal space mapping
journal, May 2002
- Pereira, S.; Correia, M. R.; Pereira, E.
- Applied Physics Letters, Vol. 80, Issue 21
Structural Characterization of BiFeO 3 Thin Films by Reciprocal Space Mapping
journal, September 2006
- Saito, Keisuke; Ulyanenkov, Alexander; Grossmann, Volkmar
- Japanese Journal of Applied Physics, Vol. 45, Issue 9B
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
Tailoring Organic Cation of 2D Air-Stable Organometal Halide Perovskites for Highly Efficient Planar Solar Cells
journal, May 2017
- Chen, Yani; Sun, Yong; Peng, Jiajun
- Advanced Energy Materials, Vol. 7, Issue 18
Phase Transition Control for High Performance Ruddlesden-Popper Perovskite Solar Cells
journal, April 2018
- Zhang, Xu; Munir, Rahim; Xu, Zhuo
- Advanced Materials, Vol. 30, Issue 21
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
On the True Composition of Mixed-Cation Perovskite Films
journal, September 2018
- Pareja-Rivera, Carina; Solís-Cambero, Ana L.; Sánchez-Torres, Mireille
- ACS Energy Letters, Vol. 3, Issue 10
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
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
Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide
journal, October 2016
- Whitfield, P. S.; Herron, N.; Guise, W. E.
- Scientific Reports, Vol. 6, Issue 1
Pb-Sn-Cu Ternary Organometallic Halide Perovskite Solar Cells
journal, March 2018
- Li, Meng; Wang, Zhao-Kui; Zhuo, Ming-Peng
- Advanced Materials, Vol. 30, Issue 20
High-Performance Photodetectors Based on Organometal Halide Perovskite Nanonets
journal, February 2017
- Wang, Wenhui; Ma, Yurong; Qi, Limin
- Advanced Functional Materials, Vol. 27, Issue 12
Ruddlesden-Popper Planar Faults and Nanotwins in Heteroepitaxial Nonstoichiometric Barium Titanate Thin Films
journal, December 2000
- Suzuki, Toshimasa; Nishi, Yuji; Fujimoto, Masayuki
- Journal of the American Ceramic Society, Vol. 83, Issue 12
Defect structure in homoepitaxial non-stoichiometric strontium titanate thin films
journal, March 2000
- Suzuki, Toshimasa; Nishi, Yuji; Fujimoto, Masayuki
- Philosophical Magazine A, Vol. 80, Issue 3
Sensitive photothermal deflection technique for measuring absorption in optically thin media
journal, January 1980
- Boccara, A. C.; Jackson, Warren; Amer, Nabil M.
- Optics Letters, Vol. 5, Issue 9
Temperature dependence of the Urbach edge in GaAs
journal, November 1995
- Johnson, S. R.; Tiedje, T.
- Journal of Applied Physics, Vol. 78, Issue 9
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
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
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
Works referencing / citing this record:
Bright magnetic dipole radiation from two-dimensional lead-halide perovskites
journal, February 2020
- DeCrescent, Ryan A.; Venkatesan, Naveen R.; Dahlman, Clayton J.
- Science Advances, Vol. 6, Issue 6
Enhanced yield-mobility products in hybrid halide Ruddlesden–Popper compounds with aromatic ammonium spacers
journal, January 2019
- Venkatesan, Naveen R.; Mahdi, Ali; Barraza, Brian
- Dalton Transactions, Vol. 48, Issue 37
Two‐Dimensional Halide Perovskites in Solar Cells: 2D or not 2D?
journal, March 2019
- Ortiz‐Cervantes, Carmen; Carmona‐Monroy, Paulina; Solis‐Ibarra, Diego
- ChemSusChem, Vol. 12, Issue 8
Bright magnetic dipole radiation from two-dimensional lead-halide perovskites
preprint, January 2019
- DeCrescent, Ryan A.; Venkatesan, Naveen R.; Dahlman, Clayton J.
- arXiv