Surface conduction in n -type pyrite FeS2 single crystals

Jeff Walter, Xin Zhang, Bryan Voigt, Ryan Hool, Michael A Manno, Frazier Mork, Eray S. Aydil, Chris Leighton

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Pyrite FeS2 has long been recognized as a high potential photovoltaic material, due to its exceptionally high optical absorption, low toxicity, and the abundance and low cost of its constituents. Despite the suitable band gap (0.95 eV), minority carrier diffusion length (100-1000 nm), and short-circuit current density, power conversion efficiencies in FeS2-based solar cells have never exceeded 3% however, primarily due to low open circuit voltages (Voc∼0.1V). Surface phenomena have been implicated as the root cause of this low Voc, recent experiments on n-type crystals providing evidence for surface conduction, including p-type surface inversion. Here we report a detailed study of electronic transport in a large set (∼120 samples) of thoroughly characterized vapor-transport-grown n-FeS2 single crystals, with both as-prepared and mechanically polished surfaces. Abundant evidence for surface conduction is obtained from the temperature dependence of the resistance and its anisotropy, the thickness dependence of the resistivity, the sensitivity to surface preparation, and the nature of an observed surface insulator-metal transition. While the bulk transport is relatively reproducible, as-grown crystals display striking diversity in surface behavior, which is suppressed by polishing. Via detailed analyses, we demonstrate that the FeS2 surface conduction is truly two dimensional, that it can influence in-plane transport even at room temperature, and that a p-type surface inversion layer can be unambiguously established, with no possibility of artifacts from hopping conduction. A nonlinear Hall effect is also observed, allowing us to constrain a two-channel conduction model we show capable of describing all field- and temperature-dependent transport data. Combined with simple arguments, these results place limits on the thickness of the surface conduction layer, which lie below ∼3 nm. Finally, in some crystals, for unknown reasons, the as-grown surface is definitively n type. These results highlight that while surface conduction is clearly important in pyrite FeS2, and is gradually yielding to understanding, additional work is clearly warranted to further understand and control it.

Original languageEnglish (US)
Article number065403
JournalPhysical Review Materials
Volume1
Issue number6
DOIs
StatePublished - Nov 14 2017

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Pyrites
pyrites
Single crystals
conduction
single crystals
Crystals
pyrite
Surface phenomena
inversions
Inversion layers
crystals
Metal insulator transition
Hall effect
Open circuit voltage
Polishing
short circuit currents
Short circuit currents
diffusion length
minority carriers
Temperature

How much support was provided by MRSEC?

  • Partial

Reporting period for MRSEC

  • Period 4

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Surface conduction in n -type pyrite FeS2 single crystals. / Walter, Jeff; Zhang, Xin; Voigt, Bryan; Hool, Ryan; Manno, Michael A; Mork, Frazier; Aydil, Eray S.; Leighton, Chris.

In: Physical Review Materials, Vol. 1, No. 6, 065403, 14.11.2017.

Research output: Contribution to journalArticle

Walter, Jeff ; Zhang, Xin ; Voigt, Bryan ; Hool, Ryan ; Manno, Michael A ; Mork, Frazier ; Aydil, Eray S. ; Leighton, Chris. / Surface conduction in n -type pyrite FeS2 single crystals. In: Physical Review Materials. 2017 ; Vol. 1, No. 6.
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abstract = "Pyrite FeS2 has long been recognized as a high potential photovoltaic material, due to its exceptionally high optical absorption, low toxicity, and the abundance and low cost of its constituents. Despite the suitable band gap (0.95 eV), minority carrier diffusion length (100-1000 nm), and short-circuit current density, power conversion efficiencies in FeS2-based solar cells have never exceeded 3{\%} however, primarily due to low open circuit voltages (Voc∼0.1V). Surface phenomena have been implicated as the root cause of this low Voc, recent experiments on n-type crystals providing evidence for surface conduction, including p-type surface inversion. Here we report a detailed study of electronic transport in a large set (∼120 samples) of thoroughly characterized vapor-transport-grown n-FeS2 single crystals, with both as-prepared and mechanically polished surfaces. Abundant evidence for surface conduction is obtained from the temperature dependence of the resistance and its anisotropy, the thickness dependence of the resistivity, the sensitivity to surface preparation, and the nature of an observed surface insulator-metal transition. While the bulk transport is relatively reproducible, as-grown crystals display striking diversity in surface behavior, which is suppressed by polishing. Via detailed analyses, we demonstrate that the FeS2 surface conduction is truly two dimensional, that it can influence in-plane transport even at room temperature, and that a p-type surface inversion layer can be unambiguously established, with no possibility of artifacts from hopping conduction. A nonlinear Hall effect is also observed, allowing us to constrain a two-channel conduction model we show capable of describing all field- and temperature-dependent transport data. Combined with simple arguments, these results place limits on the thickness of the surface conduction layer, which lie below ∼3 nm. Finally, in some crystals, for unknown reasons, the as-grown surface is definitively n type. These results highlight that while surface conduction is clearly important in pyrite FeS2, and is gradually yielding to understanding, additional work is clearly warranted to further understand and control it.",
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AU - Mork, Frazier

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AU - Leighton, Chris

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