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Title: Transition metal-substituted lead halide perovskite absorbers

Here, lead halide perovskites have proven to be a versatile class of visible light absorbers that allow rapid access to the long minority carrier lifetimes and diffusion lengths desirable for traditional single-junction photovoltaics. We explore the extent to which the attractive features of these semiconductors may be extended to include an intermediate density of states for future application in multi-level solar energy conversion systems capable of exceeding the Shockley–Queisser limit. We computationally and experimentally explore the substitution of transition metals on the Pb site of MAPbX 3 (MA = methylammonium, X = Br or Cl) to achieve a tunable density of states within the parent gap. Computational screening identified both Fe- and Co-substituted MAPbBr 3 as promising absorbers with a mid-gap density of states, and the later films were synthesized via conventional solution-based processing techniques. First-principles density functional theory (DFT) calculations support the existence of mid-gap states upon Co incorporation and enhanced sub-gap absorption, which are consistent with UV-visible-NIR absorption spectroscopy. Strikingly, steady state and time-resolved PL studies reveal no sign of self-quenching for Co-substitution up to 25%, which suggest this class of materials to be a worthy candidate for future application in intermediate band photovoltaics.
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 7; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1352552

Sampson, M. D., Park, J. S., Schaller, R. D., Chan, M. K. Y., and Martinson, A. B. F.. Transition metal-substituted lead halide perovskite absorbers. United States: N. p., Web. doi:10.1039/c6ta09745f.
Sampson, M. D., Park, J. S., Schaller, R. D., Chan, M. K. Y., & Martinson, A. B. F.. Transition metal-substituted lead halide perovskite absorbers. United States. doi:10.1039/c6ta09745f.
Sampson, M. D., Park, J. S., Schaller, R. D., Chan, M. K. Y., and Martinson, A. B. F.. 2017. "Transition metal-substituted lead halide perovskite absorbers". United States. doi:10.1039/c6ta09745f. https://www.osti.gov/servlets/purl/1352552.
@article{osti_1352552,
title = {Transition metal-substituted lead halide perovskite absorbers},
author = {Sampson, M. D. and Park, J. S. and Schaller, R. D. and Chan, M. K. Y. and Martinson, A. B. F.},
abstractNote = {Here, lead halide perovskites have proven to be a versatile class of visible light absorbers that allow rapid access to the long minority carrier lifetimes and diffusion lengths desirable for traditional single-junction photovoltaics. We explore the extent to which the attractive features of these semiconductors may be extended to include an intermediate density of states for future application in multi-level solar energy conversion systems capable of exceeding the Shockley–Queisser limit. We computationally and experimentally explore the substitution of transition metals on the Pb site of MAPbX3 (MA = methylammonium, X = Br or Cl) to achieve a tunable density of states within the parent gap. Computational screening identified both Fe- and Co-substituted MAPbBr3 as promising absorbers with a mid-gap density of states, and the later films were synthesized via conventional solution-based processing techniques. First-principles density functional theory (DFT) calculations support the existence of mid-gap states upon Co incorporation and enhanced sub-gap absorption, which are consistent with UV-visible-NIR absorption spectroscopy. Strikingly, steady state and time-resolved PL studies reveal no sign of self-quenching for Co-substitution up to 25%, which suggest this class of materials to be a worthy candidate for future application in intermediate band photovoltaics.},
doi = {10.1039/c6ta09745f},
journal = {Journal of Materials Chemistry. A},
number = 7,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

Works referenced in this record:

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

Projector augmented-wave method
journal, December 1994

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

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

High Open-Circuit Voltage Solar Cells Based on Organic–Inorganic Lead Bromide Perovskite
journal, March 2013
  • Edri, Eran; Kirmayer, Saar; Cahen, David
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 6, p. 897-902
  • DOI: 10.1021/jz400348q

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013
  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013
  • Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
  • Nature, Vol. 499, Issue 7458, p. 316-319
  • DOI: 10.1038/nature12340

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

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