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Title: Luminescence of defects in the structural transformation of layered tin dichalcogenides

Abstract

Layered tin sulfide semiconductors are both of fundamental interest and attractive for energy conversion applications. Sn sulfides crystallize in several stable bulk phases with different Sn:S ratios (SnS 2, Sn 2S 3, and SnS), which can transform into phases with a lower sulfur concentration by introduction of sulfur vacancies (V S). How this complex behavior affects the optoelectronic properties remains largely unknown but is of key importance for understanding light-matter interactions in this family of layered materials. In this work, we use the capability to induce V S and drive a transformation between few-layer SnS 2 and SnS by electron beam irradiation, combined with in-situ cathodoluminescence spectroscopy and ab-initio calculations to probe the role of defects in the luminescence of these materials. In addition to the characteristic band-edge emission of the endpoint structures, our results show emerging luminescence features accompanying the SnS 2 to SnS transformation. Comparison with calculations indicates that the most prominent emission in SnS 2 with sulfur vacancies is not due to luminescence from a defect level but involves recombination of excitons bound to neutral V S in SnS 2. These results provide insight into the intrinsic and defect-related optoelectronic properties of Sn chalcogenide semiconductors.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [1]
  1. Univ. of Nebraska, Lincoln, NE (United States)
  2. Aalto Univ., Otaniemi (Finland)
  3. Aalto Univ., Otaniemi (Finland); Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany); National Univ. of Science and Technology MISiS, Moscow (Russia)
  4. Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Univ. of Nebraska, Lincoln, NE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1527164
Alternate Identifier(s):
OSTI ID: 1414972
Grant/Contract Number:  
SC0016343
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Applied Physics Letters
Additional Journal Information:
Journal Volume: 111; Journal Issue: 26; Journal ID: ISSN 0003-6951
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Sutter, P., Komsa, H. -P., Krasheninnikov, A. V., Huang, Y., and Sutter, E. Luminescence of defects in the structural transformation of layered tin dichalcogenides. United States: N. p., 2017. Web. doi:10.1063/1.5007060.
Sutter, P., Komsa, H. -P., Krasheninnikov, A. V., Huang, Y., & Sutter, E. Luminescence of defects in the structural transformation of layered tin dichalcogenides. United States. doi:10.1063/1.5007060.
Sutter, P., Komsa, H. -P., Krasheninnikov, A. V., Huang, Y., and Sutter, E. Wed . "Luminescence of defects in the structural transformation of layered tin dichalcogenides". United States. doi:10.1063/1.5007060. https://www.osti.gov/servlets/purl/1527164.
@article{osti_1527164,
title = {Luminescence of defects in the structural transformation of layered tin dichalcogenides},
author = {Sutter, P. and Komsa, H. -P. and Krasheninnikov, A. V. and Huang, Y. and Sutter, E.},
abstractNote = {Layered tin sulfide semiconductors are both of fundamental interest and attractive for energy conversion applications. Sn sulfides crystallize in several stable bulk phases with different Sn:S ratios (SnS2, Sn2S3, and SnS), which can transform into phases with a lower sulfur concentration by introduction of sulfur vacancies (VS). How this complex behavior affects the optoelectronic properties remains largely unknown but is of key importance for understanding light-matter interactions in this family of layered materials. In this work, we use the capability to induce VS and drive a transformation between few-layer SnS2 and SnS by electron beam irradiation, combined with in-situ cathodoluminescence spectroscopy and ab-initio calculations to probe the role of defects in the luminescence of these materials. In addition to the characteristic band-edge emission of the endpoint structures, our results show emerging luminescence features accompanying the SnS2 to SnS transformation. Comparison with calculations indicates that the most prominent emission in SnS2 with sulfur vacancies is not due to luminescence from a defect level but involves recombination of excitons bound to neutral VS in SnS2. These results provide insight into the intrinsic and defect-related optoelectronic properties of Sn chalcogenide semiconductors.},
doi = {10.1063/1.5007060},
journal = {Applied Physics Letters},
issn = {0003-6951},
number = 26,
volume = 111,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
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Cited by: 3 works
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Figures / Tables:

FIG. 1 FIG. 1: Electron-beam induced transformation of few-layer SnS2 to SnS at elevated temperatures. (a) TEM image of SnS2 flakes at 100°C at the initial stages of the electron-beam induced transformation. (b) Electron diffraction pattern showing pure trigonal SnS2 along the [001] zone axis (ZA, equivalent to [0001] in Bravais-Miller 4more » index notation). Similarly, the (010) plane is identical to the ($01\bar1 0$) plane and the (110) plane to the ($11\bar2 0$) plane. (c) HRTEM lattice image of the starting material, showing the characteristic 6-fold symmetry of layered SnS2. 1 (d) TEM image of the same region shown in (a) after exposure to the electron beam at 400°C, which causes a transformation to uniform SnS over large areas along with an overall loss of material. (e) Electron diffraction pattern showing the pure orthorhombic a-SnS crystal structure along the [011] ZA. (d) HRTEM lattice image of the transformed flake, showing the orthorhombic structure of few-layer SnS.« less

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Works referenced in this record:

First principles study of point defects in SnS
journal, January 2014

  • Malone, Brad D.; Gali, Adam; Kaxiras, Efthimios
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 47
  • DOI: 10.1039/C4CP03010A

Electronic and optical properties of single crystal SnS 2 : an earth-abundant disulfide photocatalyst
journal, January 2016

  • Burton, Lee A.; Whittles, Thomas J.; Hesp, David
  • Journal of Materials Chemistry A, Vol. 4, Issue 4
  • DOI: 10.1039/C5TA08214E

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

Electronic Structure and Defect Physics of Tin Sulfides: SnS, Sn 2 S 3 , and Sn S 2
journal, July 2016


SnS thin-films by RF sputtering at room temperature
journal, August 2011

  • Hartman, Katy; Johnson, J. L.; Bertoni, Mariana I.
  • Thin Solid Films, Vol. 519, Issue 21, p. 7421-7424
  • DOI: 10.1016/j.tsf.2010.12.186

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Ultrafast Zero-Bias Photocurrent in GeS Nanosheets: Promise for Photovoltaics
journal, May 2017


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


High-performance top-gated monolayer SnS2 field-effect transistors and their integrated logic circuits
journal, January 2013


Intrinsic Ferroelasticity and/or Multiferroicity in Two-Dimensional Phosphorene and Phosphorene Analogues
journal, April 2016


Design principles for shift current photovoltaics
journal, January 2017

  • Cook, Ashley M.; M. Fregoso, Benjamin; de Juan, Fernando
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14176

Synthesis, Characterization, and Electronic Structure of Single-Crystal SnS, Sn 2 S 3 , and SnS 2
journal, December 2013

  • Burton, Lee A.; Colombara, Diego; Abellon, Ruben D.
  • Chemistry of Materials, Vol. 25, Issue 24
  • DOI: 10.1021/cm403046m

Field effect transistors with layered two-dimensional SnS 2−x Se x conduction channels: Effects of selenium substitution
journal, August 2013

  • Pan, T. S.; De, D.; Manongdo, J.
  • Applied Physics Letters, Vol. 103, Issue 9
  • DOI: 10.1063/1.4819072

Giant piezoelectricity of monolayer group IV monochalcogenides: SnSe, SnS, GeSe, and GeS
journal, October 2015

  • Fei, Ruixiang; Li, Wenbin; Li, Ju
  • Applied Physics Letters, Vol. 107, Issue 17
  • DOI: 10.1063/1.4934750

Optical characterisation of single crystal 2H-SnS 2 synthesised by the chemical vapour transport method at low temperatures
journal, June 1990


Cathodoluminescence in a Scanning Transmission Electron Microscope: A Nanometer-Scale Counterpart of Photoluminescence for the Study of II–VI Quantum Dots
journal, November 2013

  • Mahfoud, Zackaria; Dijksman, Arjen T.; Javaux, Clémentine
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 23
  • DOI: 10.1021/jz402233x

Vapor transport deposition and epitaxy of orthorhombic SnS on glass and NaCl substrates
journal, July 2013

  • Wangperawong, Artit; Herron, Steven M.; Runser, Rory R.
  • Applied Physics Letters, Vol. 103, Issue 5
  • DOI: 10.1063/1.4816746

Electron-Beam Induced Transformations of Layered Tin Dichalcogenides
journal, June 2016


Absorption edge measurements in tin disulphide thin films
journal, June 1982


Annealing of RF-magnetron sputtered SnS2 precursors as a new route for single phase SnS thin films
journal, April 2014


Overcoming Efficiency Limitations of SnS-Based Solar Cells
journal, June 2014

  • Sinsermsuksakul, Prasert; Sun, Leizhi; Lee, Sang Woon
  • Advanced Energy Materials, Vol. 4, Issue 15
  • DOI: 10.1002/aenm.201400496

Impact of growth temperature on the properties of SnS film prepared by thermal evaporation and its photovoltaic performance
journal, August 2015


Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

Atomic Layer Deposition of Tin Monosulfide Thin Films
journal, September 2011

  • Sinsermsuksakul, Prasert; Heo, Jaeyeong; Noh, Wontae
  • Advanced Energy Materials, Vol. 1, Issue 6, p. 1116-1125
  • DOI: 10.1002/aenm.201100330

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Synthesis and Crystallographic Analysis of Shape-Controlled SnS Nanocrystal Photocatalysts: Evidence for a Pseudotetragonal Structural Modification
journal, July 2013

  • Biacchi, Adam J.; Vaughn, Dimitri D.; Schaak, Raymond E.
  • Journal of the American Chemical Society, Vol. 135, Issue 31
  • DOI: 10.1021/ja405203e

Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals
journal, April 2014

  • Zhao, Li-Dong; Lo, Shih-Han; Zhang, Yongsheng
  • Nature, Vol. 508, Issue 7496, p. 373-377
  • DOI: 10.1038/nature13184

Struktur und optische Eigenschaften von epitaxialen SnTe-, SnSe- und SnS-Schichten
journal, January 1968

  • Bilenkii, B. F.; Mikolaichuk, A. G.; Freik, D. M.
  • Physica Status Solidi (b), Vol. 28, Issue 1
  • DOI: 10.1002/pssb.19680280146

Growth and Characterization of Tin Disulfide Single Crystals
journal, June 2006

  • Sharp, Laura; Soltz, David; Parkinson, B. A.
  • Crystal Growth & Design, Vol. 6, Issue 6
  • DOI: 10.1021/cg050335y

High on/off ratio field effect transistors based on exfoliated crystalline SnS 2 nano-membranes
journal, December 2012


3.88% Efficient Tin Sulfide Solar Cells using Congruent Thermal Evaporation
journal, August 2014

  • Steinmann, Vera; Jaramillo, R.; Hartman, Katy
  • Advanced Materials, Vol. 26, Issue 44
  • DOI: 10.1002/adma.201402219

Freestanding Tin Disulfide Single-Layers Realizing Efficient Visible-Light Water Splitting
journal, July 2012

  • Sun, Yongfu; Cheng, Hao; Gao, Shan
  • Angewandte Chemie International Edition, Vol. 51, Issue 35
  • DOI: 10.1002/anie.201204675

Reliable Exfoliation of Large-Area High-Quality Flakes of Graphene and Other Two-Dimensional Materials
journal, September 2015


Temperature-dependent photoreflectance of SnS crystals
journal, December 2013

  • Raadik, T.; Grossberg, M.; Raudoja, J.
  • Journal of Physics and Chemistry of Solids, Vol. 74, Issue 12
  • DOI: 10.1016/j.jpcs.2013.06.002

Tin Disulfide—An Emerging Layered Metal Dichalcogenide Semiconductor: Materials Properties and Device Characteristics
journal, September 2014

  • Huang, Yuan; Sutter, Eli; Sadowski, Jerzy T.
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn504481r

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.