Transport Evidence for Sulfur Vacancies as the Origin of Unintentional n-Type Doping in Pyrite FeS 2

Bryan Voigt, William Moore, Michael A Manno, Jeff Walter, Jeff D. Jeremiason, Eray S. Aydil, Chris Leighton

Research output: Contribution to journalArticlepeer-review

36 Scopus citations


Pyrite FeS 2 has long been considered a potential earth-abundant low-cost photovoltaic material for thin-film solar cells but has been plagued by low power conversion efficiencies and open-circuit voltages. Recent efforts have identified a lack of understanding and control of doping, as well as uncontrolled surface conduction, as key roadblocks to the development of pyrite photovoltaics. In particular, while n-type bulk behavior in unintentionally doped single crystals and thin films is speculated to arise from sulfur vacancies (V S ), proof remains elusive. Here, we provide strong evidence, from extensive electronic transport measurements on high-quality crystals, that V S are deep donors in bulk pyrite. Otherwise identical crystals grown via chemical vapor transport under varied S vapor pressures are thoroughly characterized structurally and chemically, and shown to exhibit systematically different electronic transport. Decreased S vapor pressure during growth leads to reduced bulk resistivity, increased bulk Hall electron density, reduced transport activation energy, onset of positive temperature coefficient of resistivity, and approach to an insulator-metal transition, all as would be expected from increased V S donor density. Impurity analyses show that these trends are uncorrelated with metal impurity concentration and that extracted donor densities significantly exceed total impurity concentrations, directly evidencing a native defect. Well-controlled, wide-range n-doping of pyrite is thus achieved via the control of V S concentration, with substantial implications for photovoltaic and other applications. The location of the V S state within the gap, the influence of specific impurities, unusual aspects to the insulator-metal transition, and the influence of doping on surface conduction are also discussed.

Original languageEnglish (US)
Pages (from-to)15552-15563
Number of pages12
JournalACS Applied Materials and Interfaces
Issue number17
StatePublished - May 1 2019

Bibliographical note

Funding Information:
This work was supported by the customers of Xcel Energy through a grant from the Renewables Development Fund and in part by the National Science Foundation (NSF) through the University of Minnesota MRSEC under DMR-1420013. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. The authors thank D. Ray, L. Gagliardi, K. Reich, and B. Shklovskii for informative discussions.

Publisher Copyright:
© 2019 American Chemical Society.


  • crystal growth
  • defects
  • doping
  • electronic transport
  • insulator-metal transition
  • photovoltaic absorbers
  • semiconductors
  • solar cells
  • sulfur vacancies

MRSEC Support

  • Partial

PubMed: MeSH publication types

  • Journal Article


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