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Title: Organic-to-inorganic structural chirality transfer in a 2D hybrid perovskite and impact on Rashba-Dresselhaus spin-orbit coupling

Abstract

Abstract Translation of chirality and asymmetry across structural motifs and length scales plays a fundamental role in nature, enabling unique functionalities in contexts ranging from biological systems to synthetic materials. Here, we introduce a structural chirality transfer across the organic–inorganic interface in two-dimensional hybrid perovskites using appropriate chiral organic cations. The preferred molecular configuration of the chiral spacer cations, R -(+)- or S -(−)-1-(1-naphthyl)ethylammonium and their asymmetric hydrogen-bonding interactions with lead bromide-based layers cause symmetry-breaking helical distortions in the inorganic layers, otherwise absent when employing a racemic mixture of organic spacers. First-principles modeling predicts a substantial bulk Rashba-Dresselhaus spin-splitting in the inorganic-derived conduction band with opposite spin textures between R - and S -hybrids due to the broken inversion symmetry and strong spin-orbit coupling. The ability to break symmetry using chirality transfer from one structural unit to another provides a synthetic design paradigm for emergent properties, including Rashba-Dresselhaus spin-polarization for hybrid perovskite spintronics and related applications.


Citation Formats

Jana, Manoj K., Song, Ruyi, Liu, Haoliang, Khanal, Dipak Raj, Janke, Svenja M., Zhao, Rundong, Liu, Chi, Valy Vardeny, Z., Blum, Volker, and Mitzi, David B. Organic-to-inorganic structural chirality transfer in a 2D hybrid perovskite and impact on Rashba-Dresselhaus spin-orbit coupling. United Kingdom: N. p., 2020. Web. https://doi.org/10.1038/s41467-020-18485-7.
Jana, Manoj K., Song, Ruyi, Liu, Haoliang, Khanal, Dipak Raj, Janke, Svenja M., Zhao, Rundong, Liu, Chi, Valy Vardeny, Z., Blum, Volker, & Mitzi, David B. Organic-to-inorganic structural chirality transfer in a 2D hybrid perovskite and impact on Rashba-Dresselhaus spin-orbit coupling. United Kingdom. https://doi.org/10.1038/s41467-020-18485-7
Jana, Manoj K., Song, Ruyi, Liu, Haoliang, Khanal, Dipak Raj, Janke, Svenja M., Zhao, Rundong, Liu, Chi, Valy Vardeny, Z., Blum, Volker, and Mitzi, David B. Thu . "Organic-to-inorganic structural chirality transfer in a 2D hybrid perovskite and impact on Rashba-Dresselhaus spin-orbit coupling". United Kingdom. https://doi.org/10.1038/s41467-020-18485-7.
@article{osti_1664450,
title = {Organic-to-inorganic structural chirality transfer in a 2D hybrid perovskite and impact on Rashba-Dresselhaus spin-orbit coupling},
author = {Jana, Manoj K. and Song, Ruyi and Liu, Haoliang and Khanal, Dipak Raj and Janke, Svenja M. and Zhao, Rundong and Liu, Chi and Valy Vardeny, Z. and Blum, Volker and Mitzi, David B.},
abstractNote = {Abstract Translation of chirality and asymmetry across structural motifs and length scales plays a fundamental role in nature, enabling unique functionalities in contexts ranging from biological systems to synthetic materials. Here, we introduce a structural chirality transfer across the organic–inorganic interface in two-dimensional hybrid perovskites using appropriate chiral organic cations. The preferred molecular configuration of the chiral spacer cations, R -(+)- or S -(−)-1-(1-naphthyl)ethylammonium and their asymmetric hydrogen-bonding interactions with lead bromide-based layers cause symmetry-breaking helical distortions in the inorganic layers, otherwise absent when employing a racemic mixture of organic spacers. First-principles modeling predicts a substantial bulk Rashba-Dresselhaus spin-splitting in the inorganic-derived conduction band with opposite spin textures between R - and S -hybrids due to the broken inversion symmetry and strong spin-orbit coupling. The ability to break symmetry using chirality transfer from one structural unit to another provides a synthetic design paradigm for emergent properties, including Rashba-Dresselhaus spin-polarization for hybrid perovskite spintronics and related applications.},
doi = {10.1038/s41467-020-18485-7},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {9}
}

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Works referenced in this record:

Rashba and Dresselhaus Effects in Hybrid Organic–Inorganic Perovskites: From Basics to Devices
journal, September 2015


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A Giant Bulk‐Type Dresselhaus Splitting with 3D Chiral Spin Texture in IrBiSe
journal, April 2020

  • Liu, Zhonghao; Thirupathaiah, Setti; Yaresko, Alexander N.
  • physica status solidi (RRL) – Rapid Research Letters, Vol. 14, Issue 4
  • DOI: 10.1002/pssr.201900684

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Chiral Molecules and the Spin Selectivity Effect
journal, April 2020


Delocalization error of density-functional approximations: A distinct manifestation in hydrogen molecular chains
journal, December 2012

  • Zheng, Xiao; Liu, Min; Johnson, Erin R.
  • The Journal of Chemical Physics, Vol. 137, Issue 21
  • DOI: 10.1063/1.4768673

Spin-dependent charge transport through 2D chiral hybrid lead-iodide perovskites
journal, December 2019


Two-Dimensional Hybrid Halide Perovskites: Principles and Promises
journal, November 2018

  • Mao, Lingling; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.
  • Journal of the American Chemical Society, Vol. 141, Issue 3
  • DOI: 10.1021/jacs.8b10851

Tuning the Luminescence of Layered Halide Perovskites
journal, January 2019


Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies
journal, July 2017


Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016


Quantum Spin Hall Effect and Topological Phase Transition in HgTe Quantum Wells
journal, December 2006

  • Bernevig, B. A.; Hughes, T. L.; Zhang, S.-C.
  • Science, Vol. 314, Issue 5806, p. 1757-1761
  • DOI: 10.1126/science.1133734

Tunable internal quantum well alignment in rationally designed oligomer-based perovskite films deposited by resonant infrared matrix-assisted pulsed laser evaporation
journal, January 2019

  • Dunlap-Shohl, Wiley A.; Barraza, E. Tomas; Barrette, Andrew
  • Materials Horizons, Vol. 6, Issue 8
  • DOI: 10.1039/C9MH00366E

Rashba Effect on the Structure of the Bi One-Bilayer Film: Fully Relativistic First-Principles Calculation
journal, March 2013

  • Kotaka, Hiroki; Ishii, Fumiyuki; Saito, Mineo
  • Japanese Journal of Applied Physics, Vol. 52, Issue 3R
  • DOI: 10.7567/JJAP.52.035204

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
  • DOI: 10.1039/C7SC01590A

Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH 3 NH 3 PbI 3
journal, November 2015


Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009


Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

Spintronics of Hybrid Organic–Inorganic Perovskites: Miraculous Basis of Integrated Optoelectronic Devices
journal, June 2019

  • Liao, Kun; Hu, Xiaoyong; Cheng, Yinke
  • Advanced Optical Materials, Vol. 7, Issue 15
  • DOI: 10.1002/adom.201900350

The Elephant in the Room of Density Functional Theory Calculations
journal, March 2017

  • Jensen, Stig Rune; Saha, Santanu; Flores-Livas, José A.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 7
  • DOI: 10.1021/acs.jpclett.7b00255

Reproducibility in density functional theory calculations of solids
journal, March 2016


Hidden spin polarization in inversion-symmetric bulk crystals
journal, April 2014

  • Zhang, Xiuwen; Liu, Qihang; Luo, Jun-Wei
  • Nature Physics, Vol. 10, Issue 5
  • DOI: 10.1038/nphys2933

Spin-Orbit Coupling Effects in Zinc Blende Structures
journal, October 1955


Spin control in reduced-dimensional chiral perovskites
journal, August 2018


Spin Selectivity in Photoinduced Charge-Transfer Mediated by Chiral Molecules
journal, April 2019


Atomistic Mechanism of Broadband Emission in Metal Halide Perovskites
journal, January 2019

  • Wang, Xiaoming; Meng, Weiwei; Liao, Weiqiang
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 3
  • DOI: 10.1021/acs.jpclett.8b03717

Molecular engineering of organic–inorganic hybrid perovskites quantum wells
journal, November 2019


Giant Rashba-type spin splitting in bulk BiTeI
journal, June 2011

  • Ishizaka, K.; Bahramy, M. S.; Murakawa, H.
  • Nature Materials, Vol. 10, Issue 7
  • DOI: 10.1038/nmat3051

Chiral 2D Perovskites with a High Degree of Circularly Polarized Photoluminescence
journal, March 2019


Current-driven dynamics of chiral ferromagnetic domain walls
journal, June 2013

  • Emori, Satoru; Bauer, Uwe; Ahn, Sung-Min
  • Nature Materials, Vol. 12, Issue 7
  • DOI: 10.1038/nmat3675

Controlling Chemical Selectivity in Electrocatalysis with Chiral CuO-Coated Electrodes
journal, January 2019

  • Ghosh, K. B.; Zhang, Wenyan; Tassinari, F.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 5
  • DOI: 10.1021/acs.jpcc.8b12027

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
  • DOI: 10.1039/C7MH00197E

ELSI: A unified software interface for Kohn–Sham electronic structure solvers
journal, January 2018

  • Yu, Victor Wen-zhe; Corsetti, Fabiano; García, Alberto
  • Computer Physics Communications, Vol. 222
  • DOI: 10.1016/j.cpc.2017.09.007

Highly Distorted Chiral Two-Dimensional Tin Iodide Perovskites for Spin Polarized Charge Transport
journal, June 2020

  • Lu, Haipeng; Xiao, Chuanxiao; Song, Ruyi
  • Journal of the American Chemical Society, Vol. 142, Issue 30
  • DOI: 10.1021/jacs.0c03899

Perspective of Chiral Colloidal Semiconductor Nanocrystals: Opportunity and Challenge
journal, August 2019

  • Gao, Xiaoqing; Han, Bing; Yang, Xuekang
  • Journal of the American Chemical Society, Vol. 141, Issue 35
  • DOI: 10.1021/jacs.9b05973

Resolving Rotational Stacking Disorder and Electronic Level Alignment in a 2D Oligothiophene-Based Lead Iodide Perovskite
journal, September 2019


Control of Crystal Symmetry Breaking with Halogen-Substituted Benzylammonium in Layered Hybrid Metal-Halide Perovskites
journal, February 2020

  • Schmitt, Tanja; Bourelle, Sean; Tye, Nathaniel
  • Journal of the American Chemical Society, Vol. 142, Issue 11
  • DOI: 10.1021/jacs.9b11809

Tunable Semiconductors: Control over Carrier States and Excitations in Layered Hybrid Organic-Inorganic Perovskites
journal, October 2018


Quantum and Dielectric Confinement Effects in Lower-Dimensional Hybrid Perovskite Semiconductors
journal, January 2019


Writing and Deleting Single Magnetic Skyrmions
journal, August 2013


Direct-Bandgap 2D Silver–Bismuth Iodide Double Perovskite: The Structure-Directing Influence of an Oligothiophene Spacer Cation
journal, April 2019

  • Jana, Manoj K.; Janke, Svenja M.; Dirkes, David J.
  • Journal of the American Chemical Society, Vol. 141, Issue 19
  • DOI: 10.1021/jacs.9b02909

Dynamical Origin of the Rashba Effect in Organohalide Lead Perovskites: A Key to Suppressed Carrier Recombination in Perovskite Solar Cells?
journal, April 2016

  • Etienne, Thibaud; Mosconi, Edoardo; De Angelis, Filippo
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
  • DOI: 10.1021/acs.jpclett.6b00564

Electronic structure of fcc Th: Spin-orbit calculation with 6 p 1 / 2 local orbital extension
journal, September 2001


Chiral-perovskite optoelectronics
journal, March 2020

  • Long, Guankui; Sabatini, Randy; Saidaminov, Makhsud I.
  • Nature Reviews Materials, Vol. 5, Issue 6
  • DOI: 10.1038/s41578-020-0181-5

Temperature dependence of inverse Rashba-Edelstein effect at metallic interface
journal, May 2015

  • Nomura, Akiyo; Tashiro, Takaharu; Nakayama, Hiroyasu
  • Applied Physics Letters, Vol. 106, Issue 21
  • DOI: 10.1063/1.4921765

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
  • DOI: 10.1039/B606987H

Ab initio molecular simulations with numeric atom-centered orbitals
journal, November 2009

  • Blum, Volker; Gehrke, Ralf; Hanke, Felix
  • Computer Physics Communications, Vol. 180, Issue 11
  • DOI: 10.1016/j.cpc.2009.06.022

Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications
journal, August 2013

  • Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 17
  • DOI: 10.1021/jz401532q

White-Light Emission from Layered Halide Perovskites
journal, February 2018


Spin-Dependent Ionization of Chiral Molecular Films
journal, February 2019

  • Abendroth, John M.; Cheung, Kevin M.; Stemer, Dominik M.
  • Journal of the American Chemical Society, Vol. 141, Issue 9
  • DOI: 10.1021/jacs.8b08421

Emergent phenomena induced by spin–orbit coupling at surfaces and interfaces
journal, November 2016

  • Soumyanarayanan, Anjan; Reyren, Nicolas; Fert, Albert
  • Nature, Vol. 539, Issue 7630
  • DOI: 10.1038/nature19820

The ELPA library: scalable parallel eigenvalue solutions for electronic structure theory and computational science
journal, May 2014


Macroscopic helical chirality and self-motion of hierarchical self-assemblies induced by enantiomeric small molecules
journal, September 2018


Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory
journal, March 2015

  • Egger, David A.; Liu, Zhen-Fei; Neaton, Jeffrey B.
  • Nano Letters, Vol. 15, Issue 4
  • DOI: 10.1021/nl504863r

Supramolecular Chirality in Self-Assembled Systems
journal, July 2015

  • Liu, Minghua; Zhang, Li; Wang, Tianyu
  • Chemical Reviews, Vol. 115, Issue 15
  • DOI: 10.1021/cr500671p

Gate Control of Spin-Orbit Interaction in an Inverted I n 0.53 G a 0.47 As/I n 0.52 A l 0.48 As Heterostructure
journal, February 1997


Transmission of chirality through space and across length scales
journal, May 2017

  • Morrow, Sarah M.; Bissette, Andrew J.; Fletcher, Stephen P.
  • Nature Nanotechnology, Vol. 12, Issue 5
  • DOI: 10.1038/nnano.2017.62

ELSI — An open infrastructure for electronic structure solvers
journal, November 2020

  • Yu, Victor Wen-zhe; Campos, Carmen; Dawson, William
  • Computer Physics Communications, Vol. 256
  • DOI: 10.1016/j.cpc.2020.107459

New perspectives for Rashba spin–orbit coupling
journal, August 2015

  • Manchon, A.; Koo, H. C.; Nitta, J.
  • Nature Materials, Vol. 14, Issue 9
  • DOI: 10.1038/nmat4360