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Title: Dimensional reduction of the small-bandgap double perovskite Cs2AgTlBr6

Abstract

Quantum confinement effects in lower-dimensional derivatives of the ABX 3 (A = monocation, X = halide) single perovskites afford striking optical and electronic changes, enabling applications ranging from solar absorbers to phosphors and light-emitting diodes. Halide double perovskites form a larger materials family, known since the late 1800s, but lower-dimensional derivatives remain rare and prior work has revealed a minimal effect of quantum confinement on their optical properties. Here, we synthesize three new lower-dimensional derivatives of the 3D double perovskite Cs 2AgTlBr 6: 2D derivatives with mono- ( 1-Tl) and bi-layer thick ( 2-Tl) inorganic sheets and a quasi-1D derivative ( 1'-Tl). Single-crystal ellipsometry studies of these materials show the first clear demonstration that dimensional reduction can significantly alter the optical properties of 2D halide double perovskites. This large quantum confinement effect is attributed to the substantial electronic delocalization of the parent 3D Ag–Tl perovskite. Calculations track the evolution of the electronic bands with dimensional reduction and the accompanying structural distortions and show a direct-to-indirect bandgap transition as the 3D perovskite lattice is thinned to a monolayer in 1-Tl. This bandgap transition at the monolayer limit is also evident in the calculations for 1-In, an isostructural, isoelectronic analogue to 1-Tlmore » in which In 3+ replaces Tl 3+, underscoring the orbital basis for the direct/indirect nature of the bandgap. Thus, in complement to the massive compositional diversity of halide double perovskites, dimensional reduction may be used as a systematic route for harnessing electronic confinement effects and obtaining new electronic structures.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Department of Chemistry;Stanford University;Stanford;USA
  2. Institute of Physics;University of Bayreuth;95440 Bayreuth;Germany
  3. Department of Chemistry;Stanford University;Stanford;USA;Stanford Institute for Materials and Energy Sciences
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF); German Research Foundation (DFG)
OSTI Identifier:
1633366
Alternate Identifier(s):
OSTI ID: 1656548
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515; ECCS-1542152; DGE-114747; SFB840
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 29; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Connor, Bridget A., Biega, Raisa-Ioana, Leppert, Linn, and Karunadasa, Hemamala I. Dimensional reduction of the small-bandgap double perovskite Cs2AgTlBr6. United Kingdom: N. p., 2020. Web. doi:10.1039/d0sc01580f.
Connor, Bridget A., Biega, Raisa-Ioana, Leppert, Linn, & Karunadasa, Hemamala I. Dimensional reduction of the small-bandgap double perovskite Cs2AgTlBr6. United Kingdom. doi:10.1039/d0sc01580f.
Connor, Bridget A., Biega, Raisa-Ioana, Leppert, Linn, and Karunadasa, Hemamala I. Wed . "Dimensional reduction of the small-bandgap double perovskite Cs2AgTlBr6". United Kingdom. doi:10.1039/d0sc01580f.
@article{osti_1633366,
title = {Dimensional reduction of the small-bandgap double perovskite Cs2AgTlBr6},
author = {Connor, Bridget A. and Biega, Raisa-Ioana and Leppert, Linn and Karunadasa, Hemamala I.},
abstractNote = {Quantum confinement effects in lower-dimensional derivatives of the ABX3 (A = monocation, X = halide) single perovskites afford striking optical and electronic changes, enabling applications ranging from solar absorbers to phosphors and light-emitting diodes. Halide double perovskites form a larger materials family, known since the late 1800s, but lower-dimensional derivatives remain rare and prior work has revealed a minimal effect of quantum confinement on their optical properties. Here, we synthesize three new lower-dimensional derivatives of the 3D double perovskite Cs2AgTlBr6: 2D derivatives with mono- (1-Tl) and bi-layer thick (2-Tl) inorganic sheets and a quasi-1D derivative (1'-Tl). Single-crystal ellipsometry studies of these materials show the first clear demonstration that dimensional reduction can significantly alter the optical properties of 2D halide double perovskites. This large quantum confinement effect is attributed to the substantial electronic delocalization of the parent 3D Ag–Tl perovskite. Calculations track the evolution of the electronic bands with dimensional reduction and the accompanying structural distortions and show a direct-to-indirect bandgap transition as the 3D perovskite lattice is thinned to a monolayer in 1-Tl. This bandgap transition at the monolayer limit is also evident in the calculations for 1-In, an isostructural, isoelectronic analogue to 1-Tl in which In3+ replaces Tl3+, underscoring the orbital basis for the direct/indirect nature of the bandgap. Thus, in complement to the massive compositional diversity of halide double perovskites, dimensional reduction may be used as a systematic route for harnessing electronic confinement effects and obtaining new electronic structures.},
doi = {10.1039/d0sc01580f},
journal = {Chemical Science},
issn = {2041-6520},
number = 29,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/d0sc01580f

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Works referenced in this record:

Exciton state in two-dimensional perovskite semiconductor (C10H21NH3)2PbI4
journal, March 1989


Optical properties of Cs2NaBiCl6
journal, June 1978


Anomalous electro-absorption in the low-temperature phase of (C10H21NH3)2PbI4
journal, March 1991


Nontemplate Synthesis of CH 3 NH 3 PbBr 3 Perovskite Nanoparticles
journal, January 2014

  • Schmidt, Luciana C.; Pertegás, Antonio; González-Carrero, Soranyel
  • Journal of the American Chemical Society, Vol. 136, Issue 3
  • DOI: 10.1021/ja4109209

Preparation and characterization of layered lead halide compounds
journal, March 1991

  • Calabrese, J.; Jones, N. L.; Harlow, R. L.
  • Journal of the American Chemical Society, Vol. 113, Issue 6, p. 2328-2330
  • DOI: 10.1021/ja00006a076

On minerals of the cryolite group recently found in Colorado
journal, October 1883


Organic-Based Layered Perovskites of Mixed-Valent Gold(I)/Gold(III) Iodides
journal, June 2003

  • Castro-Castro, Laura M.; Guloy, Arnold M.
  • Angewandte Chemie International Edition, Vol. 42, Issue 24
  • DOI: 10.1002/anie.200350929

Reduced Band Gap Hybrid Perovskites Resulting from Combined Hydrogen and Halogen Bonding at the Organic−Inorganic Interface
journal, February 2007

  • Sourisseau, Sebastien; Louvain, Nicolas; Bi, Wenhua
  • Chemistry of Materials, Vol. 19, Issue 3
  • DOI: 10.1021/cm062380e

Luminescence of Cs2ZrCl6 and Cs2HfCl6
journal, December 1984


Emerging Photoluminescence in Monolayer MoS2
journal, April 2010

  • Splendiani, Andrea; Sun, Liang; Zhang, Yuanbo
  • Nano Letters, Vol. 10, Issue 4, p. 1271-1275
  • DOI: 10.1021/nl903868w

Dimensional Reduction:  A Practical Formalism for Manipulating Solid Structures
journal, April 2001

  • Tulsky, Eric G.; Long, Jeffrey R.
  • Chemistry of Materials, Vol. 13, Issue 4
  • DOI: 10.1021/cm0007858

843. Stereochemistry of metals of the B sub-groups. Part I. Ions with filled d-electron shells
journal, January 1958


Two-dimensional lead-free iodide-based hybrid double perovskites: crystal growth, thin-film preparation and photocurrent responses
journal, January 2019

  • Bi, Le-Yu; Hu, Yue-Qiao; Li, Mu-Qing
  • Journal of Materials Chemistry A, Vol. 7, Issue 34
  • DOI: 10.1039/C9TA04325J

Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites
journal, June 2017

  • Meng, Weiwei; Wang, Xiaoming; Xiao, Zewen
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 13
  • DOI: 10.1021/acs.jpclett.7b01042

Photoconductivity and electroluminescence in lead iodide based natural quantum well structures
journal, November 1992


Tuning the Luminescence of Layered Halide Perovskites
journal, January 2019


Dielectric confinement effect on excitons in PbI 4 -based layered semiconductors
journal, March 1992


Electronic and Excitonic Structures of Inorganic–Organic Perovskite-Type Quantum-Well Crystal (C 4 H 9 NH 3 ) 2 PbBr 4
journal, August 2005

  • Tanaka, Kenichiro; Takahashi, Takayuki; Kondo, Takashi
  • Japanese Journal of Applied Physics, Vol. 44, Issue 8
  • DOI: 10.1143/JJAP.44.5923

Cs 2 InAgCl 6 : A New Lead-Free Halide Double Perovskite with Direct Band Gap
journal, January 2017

  • Volonakis, George; Haghighirad, Amir Abbas; Milot, Rebecca L.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 4
  • DOI: 10.1021/acs.jpclett.6b02682

Some complex chlorides containing gold
journal, May 1922


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

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

The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver–Bismuth Halide Compositions
journal, May 2018


Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets
journal, March 1995


Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors
journal, April 2016

  • Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J.
  • Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867
  • DOI: 10.1021/acs.chemmater.6b00847

Layered Halide Double Perovskites: Dimensional Reduction of Cs 2 AgBiBr 6
journal, March 2018

  • Connor, Bridget A.; Leppert, Linn; Smith, Matthew D.
  • Journal of the American Chemical Society, Vol. 140, Issue 15
  • DOI: 10.1021/jacs.8b01543

Atomically Thin MoS2 A New Direct-Gap Semiconductor
journal, September 2010


Cs 2 AgBiX 6 (X = Br, Cl): New Visible Light Absorbing, Lead-Free Halide Perovskite Semiconductors
journal, February 2016


Defect Tolerance to Intolerance in the Vacancy-Ordered Double Perovskite Semiconductors Cs 2 SnI 6 and Cs 2 TeI 6
journal, June 2016

  • Maughan, Annalise E.; Ganose, Alex M.; Bordelon, Mitchell M.
  • Journal of the American Chemical Society, Vol. 138, Issue 27
  • DOI: 10.1021/jacs.6b03207

A Layered Hybrid Perovskite Solar-Cell Absorber with Enhanced Moisture Stability
journal, September 2014

  • Smith, Ian C.; Hoke, Eric T.; Solis-Ibarra, Diego
  • Angewandte Chemie International Edition, Vol. 53, Issue 42
  • DOI: 10.1002/anie.201406466

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

Colloidal Nanocrystals of Lead-Free Double-Perovskite (Elpasolite) Semiconductors: Synthesis and Anion Exchange To Access New Materials
journal, January 2018


Small-Band-Gap Halide Double Perovskites
journal, August 2018

  • Slavney, Adam H.; Leppert, Linn; Saldivar Valdes, Abraham
  • Angewandte Chemie International Edition, Vol. 57, Issue 39
  • DOI: 10.1002/anie.201807421

Preparations and Characterizations of Luminescent Two Dimensional Organic-inorganic Perovskite Semiconductors
journal, May 2010

  • Zhang, Sanjun; Audebert, Pierre; Wei, Yi
  • Materials, Vol. 3, Issue 5
  • DOI: 10.3390/ma3053385

Structural diversity in substituted-pyridinium iodo- and bromoplumbates: a matter of halide and temperature
journal, January 2016

  • Gómez, Verónica; Fuhr, Olaf; Ruben, Mario
  • CrystEngComm, Vol. 18, Issue 42
  • DOI: 10.1039/C6CE01684G

A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications
journal, February 2016

  • Slavney, Adam H.; Hu, Te; Lindenberg, Aaron M.
  • Journal of the American Chemical Society, Vol. 138, Issue 7
  • DOI: 10.1021/jacs.5b13294

Designing indirect–direct bandgap transitions in double perovskites
journal, January 2017

  • Tran, T. Thao; Panella, Jessica R.; Chamorro, Juan R.
  • Materials Horizons, Vol. 4, Issue 4
  • DOI: 10.1039/C7MH00239D

Decreasing the electronic confinement in layered perovskites through intercalation
journal, January 2017

  • Smith, Matthew D.; Pedesseau, Laurent; Kepenekian, Mikaël
  • Chemical Science, Vol. 8, Issue 3
  • DOI: 10.1039/C6SC02848A

A pencil-and-paper method for elucidating halide double perovskite band structures
journal, January 2019

  • Slavney, Adam H.; Connor, Bridget A.; Leppert, Linn
  • Chemical Science, Vol. 10, Issue 48
  • DOI: 10.1039/C9SC03219C

Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach
journal, January 2016

  • Deng, Zeyu; Wei, Fengxia; Sun, Shijing
  • Journal of Materials Chemistry A, Vol. 4, Issue 31
  • DOI: 10.1039/C6TA05817E

Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015

  • Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
  • Nano Letters, Vol. 15, Issue 6
  • DOI: 10.1021/nl5048779

Band Gaps of the Lead-Free Halide Double Perovskites Cs 2 BiAgCl 6 and Cs 2 BiAgBr 6 from Theory and Experiment
journal, June 2016

  • Filip, Marina R.; Hillman, Samuel; Haghighirad, Amir Abbas
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
  • DOI: 10.1021/acs.jpclett.6b01041

Chemical and Structural Diversity of Hybrid Layered Double Perovskite Halides
journal, November 2019

  • Mao, Lingling; Teicher, Samuel M. L.; Stoumpos, Constantinos C.
  • Journal of the American Chemical Society, Vol. 141, Issue 48
  • DOI: 10.1021/jacs.9b09945