Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties

Organic-inorganic hybrid Ruddlesden-Popper perovskites (HRPPs) have gained much attention for optoelectronic applications due to their high moisture resistance, good processability under ambient conditions, and long functional lifetimes. Recent success in isolating molecularly thin hybrid perovskite...

Full description

Saved in:
Bibliographic Details
Main Authors: Kripalani, Devesh Raju, Cai, Yongqing, Lou, Jun, Zhou, Kun
Other Authors: School of Mechanical and Aerospace Engineering
Format: Article
Language:English
Published: 2022
Subjects:
Online Access:https://hdl.handle.net/10356/162053
Tags: Add Tag
No Tags, Be the first to tag this record!
Institution: Nanyang Technological University
Language: English
id sg-ntu-dr.10356-162053
record_format dspace
spelling sg-ntu-dr.10356-1620532022-10-03T02:58:14Z Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties Kripalani, Devesh Raju Cai, Yongqing Lou, Jun Zhou, Kun School of Mechanical and Aerospace Engineering Nanyang Environment and Water Research Institute Environmental Process Modelling Centre Engineering::Materials Ruddlesden-Popper Phase Density Functional Theory Organic-inorganic hybrid Ruddlesden-Popper perovskites (HRPPs) have gained much attention for optoelectronic applications due to their high moisture resistance, good processability under ambient conditions, and long functional lifetimes. Recent success in isolating molecularly thin hybrid perovskite nanosheets and their intriguing edge phenomena have raised the need for understanding the role of edges and the properties that dictate their fundamental behaviors. In this work, we perform a prototypical study on the edge effects in ultrathin hybrid perovskites by considering monolayer (BA)2PbI4 as a representative system. On the basis of first-principles simulations of nanoribbon models, we show that in addition to significant distortions of the octahedra network at the edges, strong edge stresses are also present in the material. Structural instabilities that arise from the edge stress could drive the relaxation process and dominate the morphological response of edges in practice. A clear downward shift of the bands at the narrower ribbons, as indicative of the edge effect, facilitates the separation of photoexcited carriers (electrons move toward the edge and holes move toward the interior part of the nanosheet). Moreover, the desorption energy of the organic molecule can also be much lower at the free edges, making it easier for functionalization and/or substitution events to take place. The findings reported in this work elucidate the underlying mechanisms responsible for edge states in HRPPs and will be important in guiding the rational design and development of high-performance layer-edge devices. We acknowledge the financial support received from the Nanyang Environment and Water Research Institute (Core Funding), Nanyang Technological University, Singapore. Y. Cai acknowledges the support provided by the University of Macau (SRG2019-00179-IAPME), the Science and Technology Development Fund from Macau SAR (FDCT-0163/2019/A3), the Natural Science Foundation of China (grant 22022309), and the Natural Science Foundation of Guangdong Province, China (2021A1515010024). Nanyang Technological University We acknowledge the financial support received from the Nanyang Environment and Water Research Institute (Core Funding), Nanyang Technological University, Singapore. Y. Cai acknowledges the support provided by the University of Macau (SRG2019-00179-IAPME), the Science and Technology Development Fund from Macau SAR (FDCT-0163/2019/A3), the Natural Science Foundation of China (grant 22022309), and the Natural Science Foundation of Guangdong Province, China (2021A1515010024). 2022-10-03T02:58:14Z 2022-10-03T02:58:14Z 2022 Journal Article Kripalani, D. R., Cai, Y., Lou, J. & Zhou, K. (2022). Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties. ACS Nano, 16(1), 261-270. https://dx.doi.org/10.1021/acsnano.1c06158 1936-0851 https://hdl.handle.net/10356/162053 10.1021/acsnano.1c06158 34978421 2-s2.0-85122661038 1 16 261 270 en ACS Nano © 2022 American Chemical Society. All rights reserved.
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering::Materials
Ruddlesden-Popper Phase
Density Functional Theory
spellingShingle Engineering::Materials
Ruddlesden-Popper Phase
Density Functional Theory
Kripalani, Devesh Raju
Cai, Yongqing
Lou, Jun
Zhou, Kun
Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties
description Organic-inorganic hybrid Ruddlesden-Popper perovskites (HRPPs) have gained much attention for optoelectronic applications due to their high moisture resistance, good processability under ambient conditions, and long functional lifetimes. Recent success in isolating molecularly thin hybrid perovskite nanosheets and their intriguing edge phenomena have raised the need for understanding the role of edges and the properties that dictate their fundamental behaviors. In this work, we perform a prototypical study on the edge effects in ultrathin hybrid perovskites by considering monolayer (BA)2PbI4 as a representative system. On the basis of first-principles simulations of nanoribbon models, we show that in addition to significant distortions of the octahedra network at the edges, strong edge stresses are also present in the material. Structural instabilities that arise from the edge stress could drive the relaxation process and dominate the morphological response of edges in practice. A clear downward shift of the bands at the narrower ribbons, as indicative of the edge effect, facilitates the separation of photoexcited carriers (electrons move toward the edge and holes move toward the interior part of the nanosheet). Moreover, the desorption energy of the organic molecule can also be much lower at the free edges, making it easier for functionalization and/or substitution events to take place. The findings reported in this work elucidate the underlying mechanisms responsible for edge states in HRPPs and will be important in guiding the rational design and development of high-performance layer-edge devices. We acknowledge the financial support received from the Nanyang Environment and Water Research Institute (Core Funding), Nanyang Technological University, Singapore. Y. Cai acknowledges the support provided by the University of Macau (SRG2019-00179-IAPME), the Science and Technology Development Fund from Macau SAR (FDCT-0163/2019/A3), the Natural Science Foundation of China (grant 22022309), and the Natural Science Foundation of Guangdong Province, China (2021A1515010024).
author2 School of Mechanical and Aerospace Engineering
author_facet School of Mechanical and Aerospace Engineering
Kripalani, Devesh Raju
Cai, Yongqing
Lou, Jun
Zhou, Kun
format Article
author Kripalani, Devesh Raju
Cai, Yongqing
Lou, Jun
Zhou, Kun
author_sort Kripalani, Devesh Raju
title Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties
title_short Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties
title_full Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties
title_fullStr Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties
title_full_unstemmed Strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties
title_sort strong edge stress in molecularly thin organic-inorganic hybrid ruddlesden-popper perovskites and modulations of their edge electronic properties
publishDate 2022
url https://hdl.handle.net/10356/162053
_version_ 1746219675601076224