Ligand Coverage and Exciton Delocalization Control Chiral Imprinting in Perovskite Nanoplatelets
Abstract
Chiral perovskites have generated significant recent interest, yet little is known about how their chiro-optical properties arise. In this study, chiral methylammonium lead halide perovskite nanoplatelets (NPLs) with varied halide and ligand compositions are prepared using direct synthetic methods. Circular dichroism (CD) and 1H NMR studies find a non-linear relationship between the chiroptical properties and the ratio of chiral phenylethylammonium (PEA) to achiral octylamine (OA) ligands on the NPL surface. We use density functional theory (DFT) computations and a chiral imprinted particle-in-a-box model to rationalize the experimentally observed CD spectra and find that the saturation point of the induced chirality depends on the size of the perovskite exciton relative to the size of the ligands. Temperature-dependent CD and 1H NMR studies, combined with DFT analysis, show that both the CD intensity and sign depend strongly on the structure and orientation of the ligands. Furthermore, this work reveals the complex nature of chiral imprinting in perovskite nanostructures and establishes a simple physical model for ligand-induced chiral imprinting to guide the further development of chiral materials.
- Authors:
-
[1];
[1];
[1]
- Univ. of Pittsburgh, PA (United States)
- Duke Univ., Durham, NC (United States)
- Publication Date:
- Research Org.:
- Univ. of Pittsburgh, PA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1905454
- Grant/Contract Number:
- FG02-07ER46430; SC0010662
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 126; Journal Issue: 37; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; chirality; perovskite; chiral exciton; excitons; ligands; nanoparticles
Citation Formats
Georgieva, Zheni N., Zhang, Zhendian, Zhang, Peng, Bloom, Brian P., Beratan, David N., and Waldeck, David H. Ligand Coverage and Exciton Delocalization Control Chiral Imprinting in Perovskite Nanoplatelets. United States: N. p., 2022.
Web. doi:10.1021/acs.jpcc.2c04192.
Georgieva, Zheni N., Zhang, Zhendian, Zhang, Peng, Bloom, Brian P., Beratan, David N., & Waldeck, David H. Ligand Coverage and Exciton Delocalization Control Chiral Imprinting in Perovskite Nanoplatelets. United States. https://doi.org/10.1021/acs.jpcc.2c04192
Georgieva, Zheni N., Zhang, Zhendian, Zhang, Peng, Bloom, Brian P., Beratan, David N., and Waldeck, David H. Tue .
"Ligand Coverage and Exciton Delocalization Control Chiral Imprinting in Perovskite Nanoplatelets". United States. https://doi.org/10.1021/acs.jpcc.2c04192. https://www.osti.gov/servlets/purl/1905454.
@article{osti_1905454,
title = {Ligand Coverage and Exciton Delocalization Control Chiral Imprinting in Perovskite Nanoplatelets},
author = {Georgieva, Zheni N. and Zhang, Zhendian and Zhang, Peng and Bloom, Brian P. and Beratan, David N. and Waldeck, David H.},
abstractNote = {Chiral perovskites have generated significant recent interest, yet little is known about how their chiro-optical properties arise. In this study, chiral methylammonium lead halide perovskite nanoplatelets (NPLs) with varied halide and ligand compositions are prepared using direct synthetic methods. Circular dichroism (CD) and 1H NMR studies find a non-linear relationship between the chiroptical properties and the ratio of chiral phenylethylammonium (PEA) to achiral octylamine (OA) ligands on the NPL surface. We use density functional theory (DFT) computations and a chiral imprinted particle-in-a-box model to rationalize the experimentally observed CD spectra and find that the saturation point of the induced chirality depends on the size of the perovskite exciton relative to the size of the ligands. Temperature-dependent CD and 1H NMR studies, combined with DFT analysis, show that both the CD intensity and sign depend strongly on the structure and orientation of the ligands. Furthermore, this work reveals the complex nature of chiral imprinting in perovskite nanostructures and establishes a simple physical model for ligand-induced chiral imprinting to guide the further development of chiral materials.},
doi = {10.1021/acs.jpcc.2c04192},
journal = {Journal of Physical Chemistry. C},
number = 37,
volume = 126,
place = {United States},
year = {Tue Aug 23 00:00:00 EDT 2022},
month = {Tue Aug 23 00:00:00 EDT 2022}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition
journal, July 2016
- Weidman, Mark C.; Seitz, Michael; Stranks, Samuel D.
- ACS Nano, Vol. 10, Issue 8
Colloidal Organohalide Perovskite Nanoplatelets Exhibiting Quantum Confinement
journal, May 2015
- Tyagi, Pooja; Arveson, Sarah M.; Tisdale, William A.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 10
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013
- Stranks, S. D.; Eperon, G. E.; Grancini, G.
- Science, Vol. 342, Issue 6156, p. 341-344
Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015
- Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan
- Science, Vol. 347, Issue 6225
Photoluminescence Lifetimes Exceeding 8 μs and Quantum Yields Exceeding 30% in Hybrid Perovskite Thin Films by Ligand Passivation
journal, July 2016
- deQuilettes, Dane W.; Koch, Susanne; Burke, Sven
- ACS Energy Letters, Vol. 1, Issue 2
Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013
- Xing, G.; Mathews, N.; Sun, S.
- Science, Vol. 342, Issue 6156, p. 344-347
Recent advances in perovskite solar cells: efficiency, stability and lead-free perovskite
journal, January 2017
- Yang, Shida; Fu, Weifei; Zhang, Zhongqiang
- Journal of Materials Chemistry A, Vol. 5, Issue 23
Engineering Color-Stable Blue Light-Emitting Diodes with Lead Halide Perovskite Nanocrystals
journal, May 2019
- Ochsenbein, Stefan T.; Krieg, Franziska; Shynkarenko, Yevhen
- ACS Applied Materials & Interfaces, Vol. 11, Issue 24
Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent
journal, October 2018
- Lin, Kebin; Xing, Jun; Quan, Li Na
- Nature, Vol. 562, Issue 7726
Vapor Growth and Tunable Lasing of Band Gap Engineered Cesium Lead Halide Perovskite Micro/Nanorods with Triangular Cross Section
journal, December 2016
- Zhou, Hong; Yuan, Shuangping; Wang, Xiaoxia
- ACS Nano, Vol. 11, Issue 2
Near-infrared random lasing realized in a perovskite CH 3 NH 3 PbI 3 thin film
journal, January 2016
- Shi, Zhi-Feng; Sun, Xu-Guang; Wu, Di
- Journal of Materials Chemistry C, Vol. 4, Issue 36
Single-Mode Lasers Based on Cesium Lead Halide Perovskite Submicron Spheres
journal, September 2017
- Tang, Bing; Dong, Hongxing; Sun, Liaoxin
- ACS Nano, Vol. 11, Issue 11
Perovskite nanomaterials as optical and electrochemical sensors
journal, January 2020
- George K., Jesna; Halali, Vishaka V.; C. G., Sanjayan
- Inorganic Chemistry Frontiers, Vol. 7, Issue 14
Plasmonic–perovskite solar cells, light emitters, and sensors
journal, January 2022
- Ai, Bin; Fan, Ziwei; Wong, Zi Jing
- Microsystems & Nanoengineering, Vol. 8, Issue 1
Synthesis and crystal structures of inorganic–organic hybrids incorporating an aromatic amine with a chiral functional group
journal, January 2006
- Billing, David G.; Lemmerer, Andreas
- CrystEngComm, Vol. 8, Issue 9
A new class of chiral semiconductors: chiral-organic-molecule-incorporating organic–inorganic hybrid perovskites
journal, January 2017
- Ahn, Jihoon; Lee, Eunsong; Tan, Jeiwan
- Materials Horizons, Vol. 4, Issue 5
Exploration of Chiral Organic–Inorganic Hybrid Semiconducting Lead Halides
journal, May 2019
- Peng, Yu; Yao, Yunpeng; Li, Lina
- Chemistry – An Asian Journal, Vol. 14, Issue 13
Circularly polarized light detection using chiral hybrid perovskite
journal, April 2019
- Chen, Chao; Gao, Liang; Gao, Wanru
- Nature Communications, Vol. 10, Issue 1
White-light emission in a chiral one-dimensional organic–inorganic hybrid perovskite
journal, January 2018
- Peng, Yu; Yao, Yunpeng; Li, Lina
- Journal of Materials Chemistry C, Vol. 6, Issue 22
Chiral Lead Halide Perovskite Nanowires for Second-Order Nonlinear Optics
journal, August 2018
- Yuan, Chunqing; Li, Xinyue; Semin, Sergey
- Nano Letters, Vol. 18, Issue 9
Chiral 2D Perovskites with a High Degree of Circularly Polarized Photoluminescence
journal, March 2019
- Ma, Jiaqi; Fang, Chen; Chen, Chao
- ACS Nano, Vol. 13, Issue 3
Endowing Perovskite Nanocrystals with Circularly Polarized Luminescence
journal, January 2018
- Shi, Yonghong; Duan, Pengfei; Huo, Shengwei
- Advanced Materials, Vol. 30, Issue 12
Imprinting Chirality onto the Electronic States of Colloidal Perovskite Nanoplatelets
journal, April 2018
- Georgieva, Zheni N.; Bloom, Brian P.; Ghosh, Supriya
- Advanced Materials, Vol. 30, Issue 23
Spin control in reduced-dimensional chiral perovskites
journal, August 2018
- Long, Guankui; Jiang, Chongyun; Sabatini, Randy
- Nature Photonics, Vol. 12, Issue 9
Two-Photon Absorption-Based Upconverted Circularly Polarized Luminescence Generated in Chiral Perovskite Nanocrystals
journal, May 2019
- Chen, Wenjie; Zhang, Shuai; Zhou, Minghao
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 12
Strategies to Achieve High Circularly Polarized Luminescence from Colloidal Organic–Inorganic Hybrid Perovskite Nanocrystals
journal, July 2020
- Kim, Young-Hoon; Zhai, Yaxin; Gaulding, E. Ashley
- ACS Nano, Vol. 14, Issue 7
Circularly Polarized Emission from Organic–Inorganic Hybrid Perovskites via Chiral Fano Resonances
journal, July 2021
- Seo, In Cheol; Lim, Yeonsoo; An, Soo-Chan
- ACS Nano, Vol. 15, Issue 8
Chiral 1D perovskite microwire arrays for circularly polarized light detection
journal, March 2022
- Zhao, Yingjie; Li, Xinyi; Feng, Jiangang
- Giant, Vol. 9
Using post-synthetic ligand modification to imprint chirality onto the electronic states of cesium lead bromide (CsPbBr 3 ) perovskite nanoparticles
journal, January 2021
- Debnath, Gouranga H.; Georgieva, Zheni N.; Bloom, Brian P.
- Nanoscale, Vol. 13, Issue 36
Chirality Control of Electron Transfer in Quantum Dot Assemblies
journal, June 2017
- Bloom, Brian P.; Graff, Brittney M.; Ghosh, Supriya
- Journal of the American Chemical Society, Vol. 139, Issue 26
Contribution of a Solute's Chiral Solvent Imprint to Optical Rotation
journal, August 2007
- Mukhopadhyay, Parag; Zuber, Gérard; Wipf, Peter
- Angewandte Chemie International Edition, Vol. 46, Issue 34
The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates
journal, January 2006
- Goldsmith, Michael-Rock; George, Christopher B.; Zuber, Gérard
- Phys. Chem. Chem. Phys., Vol. 8, Issue 1
Optical Rotation of Noncovalent Aggregates
journal, December 2003
- Goldsmith, Michael-Rock; Jayasuriya, Nilu; Beratan, David N.
- Journal of the American Chemical Society, Vol. 125, Issue 51
Optical Signatures of Molecular Dissymmetry: Combining Theory with Experiments To Address Stereochemical Puzzles
journal, June 2009
- Mukhopadhyay, Parag; Wipf, Peter; Beratan, David N.
- Accounts of Chemical Research, Vol. 42, Issue 6
A Unified Strategy for the Chemically Intuitive Interpretation of Molecular Optical Response Properties
journal, November 2020
- de Wergifosse, Marc; Grimme, Stefan
- Journal of Chemical Theory and Computation, Vol. 16, Issue 12
Atomic Contributions to the Optical Rotation Angle as a Quantitative Probe of Molecular Chirality
journal, December 1998
- Kondru, Rama K.; Wipf, Peter; Beratan, David N.
- Science, Vol. 282, Issue 5397
Chiral highly luminescent CdS quantum dots
journal, January 2007
- Moloney, Mícheál P.; Gun'ko, Yurii K.; Kelly, John M.
- Chemical Communications, Vol. 0, Issue 38, p. 3900-3902
Intrinsic Chirality of CdSe/ZnS Quantum Dots and Quantum Rods
journal, April 2015
- Mukhina, Maria V.; Maslov, Vladimir G.; Baranov, Alexander V.
- Nano Letters, Vol. 15, Issue 5
Optical Activity and Chiral Memory of Thiol-Capped CdTe Nanocrystals
journal, July 2009
- Nakashima, Takuya; Kobayashi, Yuki; Kawai, Tsuyoshi
- Journal of the American Chemical Society, Vol. 131, Issue 30
Chiral Shells and Achiral Cores in CdS Quantum Dots
journal, August 2008
- Elliott, Simon D.; Moloney, Mícheál P.; Gun’ko, Yurii K.
- Nano Letters, Vol. 8, Issue 8
Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand
journal, February 2016
- Choi, Jung Kyu; Haynie, Benjamin E.; Tohgha, Urice
- ACS Nano, Vol. 10, Issue 3
Alternative chiral thiols for preparation of chiral CdS quantum dots covered immediately by achiral thiols
journal, January 2011
- Zhou, Rong; Wei, Ke-Yi; Zhao, Jin-Song
- Chemical Communications, Vol. 47, Issue 22
Biomimetic Hierarchical Assembly of Helical Supraparticles from Chiral Nanoparticles
journal, February 2016
- Zhou, Yunlong; Marson, Ryan L.; van Anders, Greg
- ACS Nano, Vol. 10, Issue 3
Excitonic Circular Dichroism of Chiral Quantum Rods
journal, June 2017
- Gao, Xiaoqing; Zhang, Xiuwen; Deng, Ke
- Journal of the American Chemical Society, Vol. 139, Issue 25
Ligand-induced chirality and optical activity in semiconductor nanocrystals: theory and applications
journal, November 2020
- Kuznetsova, Vera; Gromova, Yulia; Martinez-Carmona, Marina
- Nanophotonics, Vol. 10, Issue 2
Probing the Interaction of Quantum Dots with Chiral Capping Molecules Using Circular Dichroism Spectroscopy
journal, November 2016
- Ben-Moshe, Assaf; Teitelboim, Ayelet; Oron, Dan
- Nano Letters, Vol. 16, Issue 12
Ligand Induced Circular Dichroism and Circularly Polarized Luminescence in CdSe Quantum Dots
journal, November 2013
- Tohgha, Urice; Deol, Kirandeep K.; Porter, Ashlin G.
- ACS Nano, Vol. 7, Issue 12
Distinct Excitonic Circular Dichroism between Wurtzite and Zincblende CdSe Nanoplatelets
journal, October 2018
- Gao, Xiaoqing; Zhang, Xiuwen; Zhao, Luyang
- Nano Letters, Vol. 18, Issue 11
CdSe Quantum Dots Functionalized with Chiral, Thiol-Free Carboxylic Acids: Unraveling Structural Requirements for Ligand-Induced Chirality
journal, October 2017
- Varga, Krisztina; Tannir, Shambhavi; Haynie, Benjamin E.
- ACS Nano, Vol. 11, Issue 10
Effect of Chiral Ligand Concentration and Binding Mode on Chiroptical Activity of CdSe/CdS Quantum Dots
journal, November 2019
- Kuznetsova, Vera A.; Mates-Torres, Eric; Prochukhan, Nadezda
- ACS Nano, Vol. 13, Issue 11
Alkyl–Aryl Cation Mixing in Chiral 2D Perovskites
journal, October 2021
- Yan, Liang; Jana, Manoj K.; Sercel, Peter C.
- Journal of the American Chemical Society, Vol. 143, Issue 43
Density Functional Study of Cubic, Tetragonal, and Orthorhombic CsPbBr 3 Perovskite
journal, March 2020
- Ghaithan, Hamid M.; Alahmed, Zeyad A.; Qaid, Saif M. H.
- ACS Omega, Vol. 5, Issue 13
A comprehensive theoretical study of halide perovskites ABX3
journal, October 2016
- Qian, Jingyu; Xu, Bin; Tian, Wenjing
- Organic Electronics, Vol. 37
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004
- Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
- Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
- Weigend, Florian; Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
Atomic-scale view of stability and degradation of single-crystal MAPbBr3 surfaces
journal, January 2019
- Choi, Joong Il Jake; Khan, Muhammad Ejaz; Hawash, Zafer
- Journal of Materials Chemistry A, Vol. 7, Issue 36
Modeling of Lead Halide Perovskites for Photovoltaic Applications
journal, November 2014
- Jishi, Radi A.; Ta, Oliver B.; Sharif, Adel A.
- The Journal of Physical Chemistry C, Vol. 118, Issue 49
Temperature-Dependent Optical Band Gap in CsPbBr 3 , MAPbBr 3 , and FAPbBr 3 Single Crystals
journal, March 2020
- Mannino, Giovanni; Deretzis, Ioannis; Smecca, Emanuele
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 7
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Effective mass of heavy, light, and spin split-off band electron and hole g-factor in cubic perovskite materials
journal, December 2020
- Ompong, David; Inkoom, Godfred; Singh, Jai
- Journal of Applied Physics, Vol. 128, Issue 23
Pressures Tuning the Band Gap of Organic–Inorganic Trihalide Perovskites (MAPbBr3): A First-Principles Study
journal, September 2018
- Tan, Mengping; Wang, Sanjun; Rao, Fengfei
- Journal of Electronic Materials, Vol. 47, Issue 12
Ligand-engineered bandgap stability in mixed-halide perovskite LEDs
journal, March 2021
- Hassan, Yasser; Park, Jong Hyun; Crawford, Michael L.
- Nature, Vol. 591, Issue 7848
On the Mechanism of Alkylammonium Ligands Binding to the Surface of CsPbBr3 Nanocrystals
journal, June 2021
- Stelmakh, Andriy; Aebli, Marcel; Baumketner, Andrij
- Chemistry of Materials, Vol. 33, Issue 15
Stable Ligand Coordination at the Surface of Colloidal CsPbBr 3 Nanocrystals
journal, June 2019
- Quarta, Danila; Imran, Muhammad; Capodilupo, Agostina-Lina
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 13
Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots
journal, November 2019
- Balan, Arunima D.; Olshansky, Jacob H.; Horowitz, Yonatan
- ACS Nano, Vol. 13, Issue 12
Ligand-Mediated Interactions between Nanoscale Surfaces Depend Sensitively and Nonlinearly on Temperature, Facet Dimensions, and Ligand Coverage
journal, January 2016
- Widmer-Cooper, Asaph; Geissler, Phillip L.
- ACS Nano, Vol. 10, Issue 2
Giant Fine Structure Splitting of the Bright Exciton in a Bulk MAPbBr3 Single Crystal
journal, September 2019
- Baranowski, Michał; Galkowski, Krzysztof; Surrente, Alessandro
- Nano Letters, Vol. 19, Issue 10
Origin of the Enhanced Photoluminescence Quantum Yield in MAPbBr 3 Perovskite with Reduced Crystal Size
journal, May 2018
- Droseros, Nikolaos; Longo, Giulia; Brauer, Jan C.
- ACS Energy Letters, Vol. 3, Issue 6