DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Highly Distorted Chiral Two-Dimensional Tin Iodide Perovskites for Spin Polarized Charge Transport

Abstract

Incorporating chiral organic molecules into organic/inorganic hybrid 2D-layered metal-halide perovskites results in a novel family of chiral hybrid semiconductors with unique spin-dependent properties. The embedded chiral organic moieties induce a chiroptical response from the inorganic metal-halide sublattice. However, the structural interplay between the chiral organic molecules and the inorganic sublattice, as well as their synergic effect on the resulting electronic band structure need to be explored in a broader material scope. Here we present three new layered tin iodide perovskites templated by chiral (R/S-)methylbenzylammonium (R/S-MBA), i.e. (R-/S-MBA)2SnI4, and their racemic phase (rac-MBA)2SnI4. These MBA2SnI4 compounds exhibit the largest level of octahedral bond distortion compared to any other reported layered tin iodide perovskite. The incorporation of chiral MBA cations leads to circularly polarized absorption from the inorganic Sn–I sublattice, displaying chiroptical activity in the 300–500 nm wavelength range. The bandgap and chiroptical activity are modulated by alloying Sn with Pb, in the series of (MBA)2Pb1-xSnxI4. Finally, we show that vertical charge transport through oriented (R-/S-MBA)2SnI4 thin films is highly spin-dependent, arising from a chiral-induced spin selectivity (CISS) effect. We demonstrate a spin-polarization in the current-voltage characteristics as high as 94%. Our work shows the tremendous potential of these chiral hybrid semiconductorsmore » for controlling both spin and charge degrees of freedom.« less

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Duke Univ., Durham, NC (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1660032
Report Number(s):
NREL/JA-5900-76598
Journal ID: ISSN 0002-7863; MainId:7272;UUID:105d88b4-dabe-498d-a583-03d054c8fdd5;MainAdminID:13795
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 30; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chiral; emergent optoelectronic applications; perovskites; transport spin-polarization

Citation Formats

Lu, Haipeng, Xiao, Chuanxiao, Song, Ruyi, Li, Tianyang, Maughan, Annalise E., Levin, Andrew, Brunecky, Roman, Berry, Joseph J., Mitzi, David B., Blum, Volker, and Beard, Matthew C. Highly Distorted Chiral Two-Dimensional Tin Iodide Perovskites for Spin Polarized Charge Transport. United States: N. p., 2020. Web. doi:10.1021/jacs.0c03899.
Lu, Haipeng, Xiao, Chuanxiao, Song, Ruyi, Li, Tianyang, Maughan, Annalise E., Levin, Andrew, Brunecky, Roman, Berry, Joseph J., Mitzi, David B., Blum, Volker, & Beard, Matthew C. Highly Distorted Chiral Two-Dimensional Tin Iodide Perovskites for Spin Polarized Charge Transport. United States. https://doi.org/10.1021/jacs.0c03899
Lu, Haipeng, Xiao, Chuanxiao, Song, Ruyi, Li, Tianyang, Maughan, Annalise E., Levin, Andrew, Brunecky, Roman, Berry, Joseph J., Mitzi, David B., Blum, Volker, and Beard, Matthew C. Tue . "Highly Distorted Chiral Two-Dimensional Tin Iodide Perovskites for Spin Polarized Charge Transport". United States. https://doi.org/10.1021/jacs.0c03899. https://www.osti.gov/servlets/purl/1660032.
@article{osti_1660032,
title = {Highly Distorted Chiral Two-Dimensional Tin Iodide Perovskites for Spin Polarized Charge Transport},
author = {Lu, Haipeng and Xiao, Chuanxiao and Song, Ruyi and Li, Tianyang and Maughan, Annalise E. and Levin, Andrew and Brunecky, Roman and Berry, Joseph J. and Mitzi, David B. and Blum, Volker and Beard, Matthew C.},
abstractNote = {Incorporating chiral organic molecules into organic/inorganic hybrid 2D-layered metal-halide perovskites results in a novel family of chiral hybrid semiconductors with unique spin-dependent properties. The embedded chiral organic moieties induce a chiroptical response from the inorganic metal-halide sublattice. However, the structural interplay between the chiral organic molecules and the inorganic sublattice, as well as their synergic effect on the resulting electronic band structure need to be explored in a broader material scope. Here we present three new layered tin iodide perovskites templated by chiral (R/S-)methylbenzylammonium (R/S-MBA), i.e. (R-/S-MBA)2SnI4, and their racemic phase (rac-MBA)2SnI4. These MBA2SnI4 compounds exhibit the largest level of octahedral bond distortion compared to any other reported layered tin iodide perovskite. The incorporation of chiral MBA cations leads to circularly polarized absorption from the inorganic Sn–I sublattice, displaying chiroptical activity in the 300–500 nm wavelength range. The bandgap and chiroptical activity are modulated by alloying Sn with Pb, in the series of (MBA)2Pb1-xSnxI4. Finally, we show that vertical charge transport through oriented (R-/S-MBA)2SnI4 thin films is highly spin-dependent, arising from a chiral-induced spin selectivity (CISS) effect. We demonstrate a spin-polarization in the current-voltage characteristics as high as 94%. Our work shows the tremendous potential of these chiral hybrid semiconductors for controlling both spin and charge degrees of freedom.},
doi = {10.1021/jacs.0c03899},
journal = {Journal of the American Chemical Society},
number = 30,
volume = 142,
place = {United States},
year = {Tue Jun 30 00:00:00 EDT 2020},
month = {Tue Jun 30 00:00:00 EDT 2020}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 108 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009

  • Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
  • Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
  • DOI: 10.1021/ja809598r

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012


Scalable fabrication of perovskite solar cells
journal, March 2018


Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties
journal, February 2019


Conducting tin halides with a layered organic-based perovskite structure
journal, June 1994

  • Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.
  • Nature, Vol. 369, Issue 6480, p. 467-469
  • DOI: 10.1038/369467a0

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

Advances in two-dimensional organic–inorganic hybrid perovskites
journal, January 2020

  • Zhang, Fei; Lu, Haipeng; Tong, Jinhui
  • Energy & Environmental Science, Vol. 13, Issue 4
  • DOI: 10.1039/C9EE03757H

Templating and structural engineering in organic–inorganic perovskites
journal, January 2001

  • Mitzi, David B.
  • Journal of the Chemical Society, Dalton Transactions, Issue 1
  • DOI: 10.1039/b007070j

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


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


Origin of Broad-Band Emission and Impact of Structural Dimensionality in Tin-Alloyed Ruddlesden–Popper Hybrid Lead Iodide Perovskites
journal, December 2019


White-Light Emission and Structural Distortion in New Corrugated Two-Dimensional Lead Bromide Perovskites
journal, March 2017

  • Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C.
  • Journal of the American Chemical Society, Vol. 139, Issue 14
  • DOI: 10.1021/jacs.7b01312

Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors
journal, October 2016


Dimensional tailoring of hybrid perovskites for photovoltaics
journal, November 2018


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


Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites
journal, June 2016

  • Giovanni, David; Chong, Wee Kiang; Dewi, Herlina Arianita
  • Science Advances, Vol. 2, Issue 6
  • DOI: 10.1126/sciadv.1600477

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


Design, Structure, and Optical Properties of Organic−Inorganic Perovskites Containing an Oligothiophene Chromophore
journal, December 1999

  • Mitzi, David B.; Chondroudis, Konstantinos; Kagan, Cherie R.
  • Inorganic Chemistry, Vol. 38, Issue 26
  • DOI: 10.1021/ic991048k

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

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


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

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

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


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


Chiral Lead Halide Perovskite Nanowires for Second-Order Nonlinear Optics
journal, August 2018


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
  • DOI: 10.1039/C8TC01150H

The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [ R ‐ and S ‐1‐(4‐Chlorophenyl)ethylammonium] 2 PbI 4
journal, February 2019

  • Yang, Chen‐Kai; Chen, Wang‐Nan; Ding, Yan‐Ting
  • Advanced Materials, Vol. 31, Issue 16
  • DOI: 10.1002/adma.201808088

A chiral switchable photovoltaic ferroelectric 1D perovskite
journal, February 2020


Bulk Photovoltaic Effect in a Pair of Chiral–Polar Layered Perovskite-Type Lead Iodides Altered by Chirality of Organic Cations
journal, September 2019

  • Huang, Po-Jung; Taniguchi, Kouji; Miyasaka, Hitoshi
  • Journal of the American Chemical Society, Vol. 141, Issue 37
  • DOI: 10.1021/jacs.9b06815

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


The geometry of polyhedral distortions. Predictive relationships for the phosphate group
journal, May 1974

  • Baur, W. H.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 30, Issue 5
  • DOI: 10.1107/S0567740874004560

Quadratic Elongation: A Quantitative Measure of Distortion in Coordination Polyhedra
journal, May 1971


Tuning the Band Gap in Hybrid Tin Iodide Perovskite Semiconductors Using Structural Templating
journal, June 2005

  • Knutson, Jeremy L.; Martin, James D.; Mitzi, David B.
  • Inorganic Chemistry, Vol. 44, Issue 13
  • DOI: 10.1021/ic050244q

Optical nonlinearities in multiple quantum wells: Generalized Elliott formula
journal, April 1995


Anomalous Band Gap Behavior in Mixed Sn and Pb Perovskites Enables Broadening of Absorption Spectrum in Solar Cells
journal, May 2014

  • Hao, Feng; Stoumpos, Constantinos C.; Chang, Robert P. H.
  • Journal of the American Chemical Society, Vol. 136, Issue 22
  • DOI: 10.1021/ja5033259

CH 3 NH 3 Sn x Pb (1– x ) I 3 Perovskite Solar Cells Covering up to 1060 nm
journal, March 2014

  • Ogomi, Yuhei; Morita, Atsushi; Tsukamoto, Syota
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 6
  • DOI: 10.1021/jz5002117

Role of Organic Counterion in Lead- and Tin-Based Two-Dimensional Semiconducting Iodide Perovskites and Application in Planar Solar Cells
journal, October 2016


Origin of Pronounced Nonlinear Band Gap Behavior in Lead–Tin Hybrid Perovskite Alloys
journal, May 2018


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

Hybrid functionals for large periodic systems in an all-electron, numeric atom-centered basis framework
journal, July 2015

  • Levchenko, Sergey V.; Ren, Xinguo; Wieferink, Jürgen
  • Computer Physics Communications, Vol. 192
  • DOI: 10.1016/j.cpc.2015.02.021

All-electron formalism for total energy strain derivatives and stress tensor components for numeric atom-centered orbitals
journal, May 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

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


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


Tunable Charge Transport in Soluble Organic–Inorganic Hybrid Semiconductors
journal, December 2007

  • Takahashi, Yukari; Obara, Rena; Nakagawa, Kohei
  • Chemistry of Materials, Vol. 19, Issue 25
  • DOI: 10.1021/cm702405c

Spin-Dependent Transport through Chiral Molecules Studied by Spin-Dependent Electrochemistry
journal, October 2016

  • Mondal, Prakash Chandra; Fontanesi, Claudio; Waldeck, David H.
  • Accounts of Chemical Research, Vol. 49, Issue 11
  • DOI: 10.1021/acs.accounts.6b00446

Spintronics and Chirality: Spin Selectivity in Electron Transport Through Chiral Molecules
journal, April 2015


Chiral-Induced Spin Selectivity Effect
journal, July 2012

  • Naaman, R.; Waldeck, David H.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 16
  • DOI: 10.1021/jz300793y

Structure dependent spin selectivity in electron transport through oligopeptides
journal, March 2017

  • Kiran, Vankayala; Cohen, Sidney R.; Naaman, Ron
  • The Journal of Chemical Physics, Vol. 146, Issue 9
  • DOI: 10.1063/1.4966237

EXPGUI , a graphical user interface for GSAS
journal, April 2001


SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

Principles and Techniques of Diffuse-Reflectance Spectroscopy
journal, July 1963

  • Kortüm, G.; Braun, W.; Herzog, G.
  • Angewandte Chemie International Edition in English, Vol. 2, Issue 7
  • DOI: 10.1002/anie.196303331

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

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

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

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

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

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