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

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.

doi:10.1021/jacs.0c03899

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

Journal Article · Tue Jun 30 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c03899· OSTI ID:1660032

^[1]; Xiao, Chuanxiao ^[1]; Song, Ruyi ^[2]; ^[2]; ^[1]; Levin, Andrew ^[1]; Brunecky, Roman ^[1]; ^[1]; ^[2]; ^[2]; ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Duke Univ., Durham, NC (United States)

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)₂Pb_1-xSn_xI₄. 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.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1660032

Report Number(s):: NREL/JA-5900-76598; MainId:7272; UUID:105d88b4-dabe-498d-a583-03d054c8fdd5; MainAdminID:13795

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 30 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (65)

Synthesis, Structure, and Properties of Organic-Inorganic Perovskites and Related Materials Mitzi, David B. Progress in Inorganic Chemistry, Vol. 48 https://doi.org/10.1002/9780470166499.ch1	book	January 2007
The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [ R ‐ and S ‐1‐(4‐Chlorophenyl)ethylammonium] ₂ PbI ₄ Yang, Chen‐Kai; Chen, Wang‐Nan; Ding, Yan‐Ting Advanced Materials, Vol. 31, Issue 16 https://doi.org/10.1002/adma.201808088	journal	February 2019
Principles and Techniques of Diffuse-Reflectance Spectroscopy Kortüm, G.; Braun, W.; Herzog, G. Angewandte Chemie International Edition in English, Vol. 2, Issue 7 https://doi.org/10.1002/anie.196303331	journal	July 1963
Die Gesetze der Krystallochemie Goldschmidt, V. M. Die Naturwissenschaften, Vol. 14, Issue 21 https://doi.org/10.1007/BF01507527	journal	May 1926
Ab initio molecular simulations with numeric atom-centered orbitals Blum, Volker; Gehrke, Ralf; Hanke, Felix Computer Physics Communications, Vol. 180, Issue 11 https://doi.org/10.1016/j.cpc.2009.06.022	journal	November 2009
All-electron formalism for total energy strain derivatives and stress tensor components for numeric atom-centered orbitals Knuth, Franz; Carbogno, Christian; Atalla, Viktor Computer Physics Communications, Vol. 190 https://doi.org/10.1016/j.cpc.2015.01.003	journal	May 2015
Hybrid functionals for large periodic systems in an all-electron, numeric atom-centered basis framework Levchenko, Sergey V.; Ren, Xinguo; Wieferink, Jürgen Computer Physics Communications, Vol. 192 https://doi.org/10.1016/j.cpc.2015.02.021	journal	July 2015
Spin-Dependent Transport through Chiral Molecules Studied by Spin-Dependent Electrochemistry Mondal, Prakash Chandra; Fontanesi, Claudio; Waldeck, David H. Accounts of Chemical Research, Vol. 49, Issue 11 https://doi.org/10.1021/acs.accounts.6b00446	journal	October 2016
White-Light Emission from Layered Halide Perovskites Smith, Matthew D.; Karunadasa, Hemamala I. Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00433	journal	February 2018
Role of Organic Counterion in Lead- and Tin-Based Two-Dimensional Semiconducting Iodide Perovskites and Application in Planar Solar Cells Mao, Lingling; Tsai, Hsinhan; Nie, Wanyi Chemistry of Materials, Vol. 28, Issue 21 https://doi.org/10.1021/acs.chemmater.6b03054	journal	October 2016
Origin of Pronounced Nonlinear Band Gap Behavior in Lead–Tin Hybrid Perovskite Alloys Goyal, Anuj; McKechnie, Scott; Pashov, Dimitar Chemistry of Materials, Vol. 30, Issue 11 https://doi.org/10.1021/acs.chemmater.8b01695	journal	May 2018
Resolving Rotational Stacking Disorder and Electronic Level Alignment in a 2D Oligothiophene-Based Lead Iodide Perovskite Jana, Manoj K.; Liu, Chi; Lidin, Sven Chemistry of Materials, Vol. 31, Issue 20 https://doi.org/10.1021/acs.chemmater.9b03208	journal	September 2019
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design Saparov, Bayrammurad; Mitzi, David B. Chemical Reviews, Vol. 116, Issue 7 https://doi.org/10.1021/acs.chemrev.5b00715	journal	March 2016
Quantum and Dielectric Confinement Effects in Lower-Dimensional Hybrid Perovskite Semiconductors Katan, Claudine; Mercier, Nicolas; Even, Jacky Chemical Reviews, Vol. 119, Issue 5 https://doi.org/10.1021/acs.chemrev.8b00417	journal	January 2019
Two-Dimensional Lead(II) Halide-Based Hybrid Perovskites Templated by Acene Alkylamines: Crystal Structures, Optical Properties, and Piezoelectricity Du, Ke-zhao; Tu, Qing; Zhang, Xu Inorganic Chemistry, Vol. 56, Issue 15 https://doi.org/10.1021/acs.inorgchem.7b01094	journal	July 2017
Chiral Lead Halide Perovskite Nanowires for Second-Order Nonlinear Optics Yuan, Chunqing; Li, Xinyue; Semin, Sergey Nano Letters, Vol. 18, Issue 9 https://doi.org/10.1021/acs.nanolett.8b01616	journal	August 2018
Impact of Layer Thickness on the Charge Carrier and Spin Coherence Lifetime in Two-Dimensional Layered Perovskite Single Crystals Chen, Xihan; Lu, Haipeng; Li, Zhen ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b01315	journal	August 2018
Origin of Broad-Band Emission and Impact of Structural Dimensionality in Tin-Alloyed Ruddlesden–Popper Hybrid Lead Iodide Perovskites Li, Tianyang; Chen, Xihan; Wang, Xiaoming ACS Energy Letters, Vol. 5, Issue 2 https://doi.org/10.1021/acsenergylett.9b02490	journal	December 2019
Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar ACS Nano, Vol. 10, Issue 11 https://doi.org/10.1021/acsnano.6b05944	journal	October 2016
Chiral 2D Perovskites with a High Degree of Circularly Polarized Photoluminescence Ma, Jiaqi; Fang, Chen; Chen, Chao ACS Nano, Vol. 13, Issue 3 https://doi.org/10.1021/acsnano.9b00302	journal	March 2019
[(( R )-C ₈ H ₁₂ N) ₄ ][Bi ₂ Br ₁₀ ] and [(( S )-C ₈ H ₁₂ N) ₄ ][Bi ₂ Br ₁₀ ]: Chiral Hybrid Bismuth Bromides Templated by Chiral Organic Cations Moon, Tae Hwan; Oh, Seung-Jin; Ok, Kang Min ACS Omega, Vol. 3, Issue 12 https://doi.org/10.1021/acsomega.8b02877	journal	December 2018
Tunable Charge Transport in Soluble Organic–Inorganic Hybrid Semiconductors Takahashi, Yukari; Obara, Rena; Nakagawa, Kohei Chemistry of Materials, Vol. 19, Issue 25 https://doi.org/10.1021/cm702405c	journal	December 2007
Tuning the Band Gap in Hybrid Tin Iodide Perovskite Semiconductors Using Structural Templating Knutson, Jeremy L.; Martin, James D.; Mitzi, David B. Inorganic Chemistry, Vol. 44, Issue 13 https://doi.org/10.1021/ic050244q	journal	June 2005
Design, Structure, and Optical Properties of Organic−Inorganic Perovskites Containing an Oligothiophene Chromophore Mitzi, David B.; Chondroudis, Konstantinos; Kagan, Cherie R. Inorganic Chemistry, Vol. 38, Issue 26 https://doi.org/10.1021/ic991048k	journal	December 1999
Anomalous Band Gap Behavior in Mixed Sn and Pb Perovskites Enables Broadening of Absorption Spectrum in Solar Cells Hao, Feng; Stoumpos, Constantinos C.; Chang, Robert P. H. Journal of the American Chemical Society, Vol. 136, Issue 22 https://doi.org/10.1021/ja5033259	journal	May 2014
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051 https://doi.org/10.1021/ja809598r	journal	May 2009
White-Light Emission and Structural Distortion in New Corrugated Two-Dimensional Lead Bromide Perovskites Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C. Journal of the American Chemical Society, Vol. 139, Issue 14 https://doi.org/10.1021/jacs.7b01312	journal	March 2017
Two-Dimensional Hybrid Halide Perovskites: Principles and Promises Mao, Lingling; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G. Journal of the American Chemical Society, Vol. 141, Issue 3 https://doi.org/10.1021/jacs.8b10851	journal	November 2018
Direct-Bandgap 2D Silver–Bismuth Iodide Double Perovskite: The Structure-Directing Influence of an Oligothiophene Spacer Cation Jana, Manoj K.; Janke, Svenja M.; Dirkes, David J. Journal of the American Chemical Society, Vol. 141, Issue 19 https://doi.org/10.1021/jacs.9b02909	journal	April 2019
Bulk Photovoltaic Effect in a Pair of Chiral–Polar Layered Perovskite-Type Lead Iodides Altered by Chirality of Organic Cations Huang, Po-Jung; Taniguchi, Kouji; Miyasaka, Hitoshi Journal of the American Chemical Society, Vol. 141, Issue 37 https://doi.org/10.1021/jacs.9b06815	journal	September 2019
Chiral-Induced Spin Selectivity Effect Naaman, R.; Waldeck, David H. The Journal of Physical Chemistry Letters, Vol. 3, Issue 16 https://doi.org/10.1021/jz300793y	journal	July 2012
CH ₃ NH ₃ Sn _x Pb _{(1– x )} I ₃ Perovskite Solar Cells Covering up to 1060 nm Ogomi, Yuhei; Morita, Atsushi; Tsukamoto, Syota The Journal of Physical Chemistry Letters, Vol. 5, Issue 6 https://doi.org/10.1021/jz5002117	journal	March 2014
Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory Egger, David A.; Liu, Zhen-Fei; Neaton, Jeffrey B. Nano Letters, Vol. 15, Issue 4 https://doi.org/10.1021/nl504863r	journal	March 2015
Conducting tin halides with a layered organic-based perovskite structure Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A. Nature, Vol. 369, Issue 6480, p. 467-469 https://doi.org/10.1038/369467a0	journal	June 1994
Scalable fabrication of perovskite solar cells Li, Zhen; Klein, Talysa R.; Kim, Dong Hoe Nature Reviews Materials, Vol. 3, Issue 4 https://doi.org/10.1038/natrevmats.2018.17	journal	March 2018
Molecular engineering of organic–inorganic hybrid perovskites quantum wells Gao, Yao; Shi, Enzheng; Deng, Shibin Nature Chemistry, Vol. 11, Issue 12 https://doi.org/10.1038/s41557-019-0354-2	journal	November 2019
Spin control in reduced-dimensional chiral perovskites Long, Guankui; Jiang, Chongyun; Sabatini, Randy Nature Photonics, Vol. 12, Issue 9 https://doi.org/10.1038/s41566-018-0220-6	journal	August 2018
Dimensional tailoring of hybrid perovskites for photovoltaics Grancini, Giulia; Nazeeruddin, Mohammad Khaja Nature Reviews Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41578-018-0065-0	journal	November 2018
Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties Fu, Yongping; Zhu, Haiming; Chen, Jie Nature Reviews Materials, Vol. 4, Issue 3 https://doi.org/10.1038/s41578-019-0080-9	journal	February 2019
Synthesis and crystal structures of inorganic–organic hybrids incorporating an aromatic amine with a chiral functional group Billing, David G.; Lemmerer, Andreas CrystEngComm, Vol. 8, Issue 9 https://doi.org/10.1039/B606987H	journal	January 2006
A new class of chiral semiconductors: chiral-organic-molecule-incorporating organic–inorganic hybrid perovskites Ahn, Jihoon; Lee, Eunsong; Tan, Jeiwan Materials Horizons, Vol. 4, Issue 5 https://doi.org/10.1039/C7MH00197E	journal	January 2017
White-light emission in a chiral one-dimensional organic–inorganic hybrid perovskite Peng, Yu; Yao, Yunpeng; Li, Lina Journal of Materials Chemistry C, Vol. 6, Issue 22 https://doi.org/10.1039/C8TC01150H	journal	January 2018
Advances in two-dimensional organic–inorganic hybrid perovskites Zhang, Fei; Lu, Haipeng; Tong, Jinhui Energy & Environmental Science, Vol. 13, Issue 4 https://doi.org/10.1039/C9EE03757H	journal	January 2020
Tunable internal quantum well alignment in rationally designed oligomer-based perovskite films deposited by resonant infrared matrix-assisted pulsed laser evaporation Dunlap-Shohl, Wiley A.; Barraza, E. Tomas; Barrette, Andrew Materials Horizons, Vol. 6, Issue 8 https://doi.org/10.1039/C9MH00366E	journal	January 2019
Templating and structural engineering in organic–inorganic perovskites Mitzi, David B. Journal of the Chemical Society, Dalton Transactions, Issue 1 https://doi.org/10.1039/b007070j	journal	January 2001
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 124, Issue 21 https://doi.org/10.1063/1.2204597	journal	June 2006
Delocalization error of density-functional approximations: A distinct manifestation in hydrogen molecular chains Zheng, Xiao; Liu, Min; Johnson, Erin R. The Journal of Chemical Physics, Vol. 137, Issue 21 https://doi.org/10.1063/1.4768673	journal	December 2012
Structure dependent spin selectivity in electron transport through oligopeptides Kiran, Vankayala; Cohen, Sidney R.; Naaman, Ron The Journal of Chemical Physics, Vol. 146, Issue 9 https://doi.org/10.1063/1.4966237	journal	March 2017
Optical nonlinearities in multiple quantum wells: Generalized Elliott formula Campi, Domenico; Coriasso, Claudio Physical Review B, Vol. 51, Issue 16 https://doi.org/10.1103/PhysRevB.51.10719	journal	April 1995
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data Tkatchenko, Alexandre; Scheffler, Matthias Physical Review Letters, Vol. 102, Issue 7 https://doi.org/10.1103/PhysRevLett.102.073005	journal	February 2009
Tunable Semiconductors: Control over Carrier States and Excitations in Layered Hybrid Organic-Inorganic Perovskites Liu, Chi; Huhn, William; Du, Ke-Zhao Physical Review Letters, Vol. 121, Issue 14 https://doi.org/10.1103/PhysRevLett.121.146401	journal	October 2018
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
One-hundred-three compound band-structure benchmark of post-self-consistent spin-orbit coupling treatments in density functional theory Huhn, William P.; Blum, Volker Physical Review Materials, Vol. 1, Issue 3 https://doi.org/10.1103/PhysRevMaterials.1.033803	journal	August 2017
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
The geometry of polyhedral distortions. Predictive relationships for the phosphate group Baur, W. H. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 30, Issue 5 https://doi.org/10.1107/S0567740874004560	journal	May 1974
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites Giovanni, David; Chong, Wee Kiang; Dewi, Herlina Arianita Science Advances, Vol. 2, Issue 6 https://doi.org/10.1126/sciadv.1600477	journal	June 2016
Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies Zhai, Yaxin; Baniya, Sangita; Zhang, Chuang Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1700704	journal	July 2017
Spin-dependent charge transport through 2D chiral hybrid lead-iodide perovskites Lu, Haipeng; Wang, Jingying; Xiao, Chuanxiao Science Advances, Vol. 5, Issue 12 https://doi.org/10.1126/sciadv.aay0571	journal	December 2019
A chiral switchable photovoltaic ferroelectric 1D perovskite Hu, Yang; Florio, Fred; Chen, Zhizhong Science Advances, Vol. 6, Issue 9 https://doi.org/10.1126/sciadv.aay4213	journal	February 2020
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites Lee, M. M.; Teuscher, J.; Miyasaka, T. Science, Vol. 338, Issue 6107, p. 643-647 https://doi.org/10.1126/science.1228604	journal	October 2012
Quadratic Elongation: A Quantitative Measure of Distortion in Coordination Polyhedra Robinson, K.; Gibbs, G. V.; Ribbe, P. H. Science, Vol. 172, Issue 3983 https://doi.org/10.1126/science.172.3983.567	journal	May 1971
Spintronics and Chirality: Spin Selectivity in Electron Transport Through Chiral Molecules Naaman, Ron; Waldeck, David H. Annual Review of Physical Chemistry, Vol. 66, Issue 1 https://doi.org/10.1146/annurev-physchem-040214-121554	journal	April 2015

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

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