Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability

Ioannis Spanopoulos; Ido Hadar; Weijun Ke; Qing Tu; Michelle Chen; Hsinhan Tsai; Yihui He; Gajendra Shekhawat; Vinayak P. Dravid; Michael R. Wasielewski; Aditya D. Mohite; Konstantinos Stoumpos; Mercouri G. Kanatzidis

doi:10.1021/jacs.9b01327

Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability

Ioannis Spanopoulos, Ido Hadar, Weijun Ke, Qing Tu, Michelle Chen, Hsinhan Tsai, Yihui He, Gajendra Shekhawat, Vinayak P. Dravid, Michael R. Wasielewski, Aditya D. Mohite, Konstantinos Stoumpos^*, Mercouri G. Kanatzidis

^*Corresponding author for this work

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

218 Scopus citations

Abstract

The unique hybrid nature of 2D Ruddlesden-Popper (R-P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R-P perovskites, by utilizing pentylamine (PA)₂(MA)_nâ1Pb_nI_3n+1 (n = 1-5, PA = CH₃(CH₂)₄NH₃⁺, C5) and hexylamine (HA)₂(MA)_nâ1Pb_nI_3n+1 (n = 1-4, HA = CH₃(CH₂)₅NH₃⁺, C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R-P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20-80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.

Original language	English (US)
Pages (from-to)	5518-5534
Number of pages	17
Journal	Journal of the American Chemical Society
Volume	141
Issue number	13
DOIs	https://doi.org/10.1021/jacs.9b01327
State	Published - Apr 3 2019

Funding

This work was supported by ONR Grant N00014-17-1-2231. APS measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. It was supported in part by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award DE-SC0001059 (evaluation of optical properties). This work made use of the SPID, EPIC, and NUFAB facilities of Northwestern University’s NUANCE Center, as well as the IMSERC facilities, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. This research used the 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-AC02-06CH1135. Work at Los Alamos National Laboratory was supported by the LDRD program (XWPG). The authors acknowledge the help of Dr. Kevin Yager and Dr. Ruipeng Li with GIWAXS setup. This research used the 11-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DESC0012704. This work was supported by ONR Grant N00014-17-1-2231. APS measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. It was supported in part by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy Office of Science, and Office of Basic Energy Sciences under Award DE-SC0001059 (evaluation of optical properties). This work made use of the SPID, EPIC, and NUFAB facilities of Northwestern University???s NUANCE Center, as well as the IMSERC facilities, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. This research used the 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-AC02-06CH1135. Work at Los Alamos National Laboratory was supported by the LDRD program (XWPG). The authors acknowledge the help of Dr. Kevin Yager and Dr. Ruipeng Li with GIWAXS setup. This research used the 11-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.9b01327

Cite this

Spanopoulos, I., Hadar, I., Ke, W., Tu, Q., Chen, M., Tsai, H., He, Y., Shekhawat, G., Dravid, V. P., Wasielewski, M. R., Mohite, A. D., Stoumpos, K., & Kanatzidis, M. G. (2019). Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability. Journal of the American Chemical Society, 141(13), 5518-5534. https://doi.org/10.1021/jacs.9b01327

@article{70946a0636da4799a3b41e56b36ccc3d,

title = "Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability",

abstract = "The unique hybrid nature of 2D Ruddlesden-Popper (R-P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R-P perovskites, by utilizing pentylamine (PA)2(MA)n{\^a}1PbnI3n+1 (n = 1-5, PA = CH3(CH2)4NH3+, C5) and hexylamine (HA)2(MA)n{\^a}1PbnI3n+1 (n = 1-4, HA = CH3(CH2)5NH3+, C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R-P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20-80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.",

author = "Ioannis Spanopoulos and Ido Hadar and Weijun Ke and Qing Tu and Michelle Chen and Hsinhan Tsai and Yihui He and Gajendra Shekhawat and Dravid, {Vinayak P.} and Wasielewski, {Michael R.} and Mohite, {Aditya D.} and Konstantinos Stoumpos and Kanatzidis, {Mercouri G.}",

note = "Funding Information: This work was supported by ONR Grant N00014-17-1-2231. APS measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. It was supported in part by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award DE-SC0001059 (evaluation of optical properties). This work made use of the SPID, EPIC, and NUFAB facilities of Northwestern University{\textquoteright}s NUANCE Center, as well as the IMSERC facilities, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. This research used the 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-AC02-06CH1135. Work at Los Alamos National Laboratory was supported by the LDRD program (XWPG). The authors acknowledge the help of Dr. Kevin Yager and Dr. Ruipeng Li with GIWAXS setup. This research used the 11-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DESC0012704. Funding Information: This work was supported by ONR Grant N00014-17-1-2231. APS measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. It was supported in part by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy Office of Science, and Office of Basic Energy Sciences under Award DE-SC0001059 (evaluation of optical properties). This work made use of the SPID, EPIC, and NUFAB facilities of Northwestern University???s NUANCE Center, as well as the IMSERC facilities, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. This research used the 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-AC02-06CH1135. Work at Los Alamos National Laboratory was supported by the LDRD program (XWPG). The authors acknowledge the help of Dr. Kevin Yager and Dr. Ruipeng Li with GIWAXS setup. This research used the 11-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = apr,

day = "3",

doi = "10.1021/jacs.9b01327",

language = "English (US)",

volume = "141",

pages = "5518--5534",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "13",

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Spanopoulos, I, Hadar, I, Ke, W, Tu, Q, Chen, M, Tsai, H, He, Y, Shekhawat, G , Dravid, VP , Wasielewski, MR, Mohite, AD, Stoumpos, K & Kanatzidis, MG 2019, 'Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability', Journal of the American Chemical Society, vol. 141, no. 13, pp. 5518-5534. https://doi.org/10.1021/jacs.9b01327

TY - JOUR

T1 - Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability

AU - Spanopoulos, Ioannis

AU - Hadar, Ido

AU - Ke, Weijun

AU - Tu, Qing

AU - Chen, Michelle

AU - Tsai, Hsinhan

AU - He, Yihui

AU - Shekhawat, Gajendra

AU - Dravid, Vinayak P.

AU - Wasielewski, Michael R.

AU - Mohite, Aditya D.

AU - Stoumpos, Konstantinos

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: This work was supported by ONR Grant N00014-17-1-2231. APS measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. It was supported in part by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award DE-SC0001059 (evaluation of optical properties). This work made use of the SPID, EPIC, and NUFAB facilities of Northwestern University’s NUANCE Center, as well as the IMSERC facilities, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. This research used the 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-AC02-06CH1135. Work at Los Alamos National Laboratory was supported by the LDRD program (XWPG). The authors acknowledge the help of Dr. Kevin Yager and Dr. Ruipeng Li with GIWAXS setup. This research used the 11-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DESC0012704. Funding Information: This work was supported by ONR Grant N00014-17-1-2231. APS measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. It was supported in part by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy Office of Science, and Office of Basic Energy Sciences under Award DE-SC0001059 (evaluation of optical properties). This work made use of the SPID, EPIC, and NUFAB facilities of Northwestern University???s NUANCE Center, as well as the IMSERC facilities, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. This research used the 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-AC02-06CH1135. Work at Los Alamos National Laboratory was supported by the LDRD program (XWPG). The authors acknowledge the help of Dr. Kevin Yager and Dr. Ruipeng Li with GIWAXS setup. This research used the 11-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/4/3

Y1 - 2019/4/3

N2 - The unique hybrid nature of 2D Ruddlesden-Popper (R-P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R-P perovskites, by utilizing pentylamine (PA)2(MA)nâ1PbnI3n+1 (n = 1-5, PA = CH3(CH2)4NH3+, C5) and hexylamine (HA)2(MA)nâ1PbnI3n+1 (n = 1-4, HA = CH3(CH2)5NH3+, C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R-P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20-80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.

AB - The unique hybrid nature of 2D Ruddlesden-Popper (R-P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R-P perovskites, by utilizing pentylamine (PA)2(MA)nâ1PbnI3n+1 (n = 1-5, PA = CH3(CH2)4NH3+, C5) and hexylamine (HA)2(MA)nâ1PbnI3n+1 (n = 1-4, HA = CH3(CH2)5NH3+, C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R-P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20-80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.

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Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability

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Uniaxial Expansion of the 2D Ruddlesden-Popper Perovskite Family for Improved Environmental Stability

Abstract

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ASJC Scopus subject areas

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Datasets

CCDC 1904714: Experimental Crystal Structure Determination

CCDC 1904717: Experimental Crystal Structure Determination

CCDC 1904718: Experimental Crystal Structure Determination

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