skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on October 9, 2020

Title: Tunable electronic structure in gallium chalcogenide van der Waals compounds

Abstract

Transition-metal monochalcogenides comprise a class of two-dimensional materials with electronic band gaps that are highly sensitive to material thickness and chemical composition. Here, we explore the tunability of the electronic excitation spectrum in GaSe by using angle-resolved photoemission spectroscopy. The electronic structure of the material is modified by in situ potassium deposition as well as by forming GaS xSe 1-x alloy compounds. We find that potassium-dosed samples exhibit a substantial change of the dispersion around the valence-band maximum (VBM). The observed band dispersion resembles that of a single tetralayer and is consistent with a transition from the direct-gap character of the bulk to the indirect-gap character expected for monolayer GaSe. Upon alloying with sulfur, we observe a phase transition from AB to AA' stacking. Alloying also results in a rigid energy shift of the VBM towards higher binding energies, which correlates with a blueshift in the luminescence. The increase of the band gap upon sulfur alloying does not appear to change the dispersion or character of the VBM appreciably, implying that it is possible to engineer the gap of these materials while maintaining their salient electronic properties.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [4];  [3];  [3];  [3];  [5];  [3];  [6]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Aarhus Univ., Aarhus (Denmark). Interdisciplinary Nanoscience Center (iNANO)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  4. Arizona State Univ., Tempe, AZ (United States)
  5. Univ. of California, Berkeley, CA (United States)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); German Academic Exchange Service (DAAD)
OSTI Identifier:
1574341
Grant/Contract Number:  
AC02-05CH11231; DMR-1807233; 15375
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 100; Journal Issue: 16; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Shevitski, Brian, Ulstrup, Søren, Koch, Roland J., Cai, Hui, Tongay, Sefaattin, Moreschini, Luca, Jozwiak, Chris, Bostwick, Aaron, Zettl, Alex, Rotenberg, Eli, and Aloni, Shaul. Tunable electronic structure in gallium chalcogenide van der Waals compounds. United States: N. p., 2019. Web. doi:10.1103/physrevb.100.165112.
Shevitski, Brian, Ulstrup, Søren, Koch, Roland J., Cai, Hui, Tongay, Sefaattin, Moreschini, Luca, Jozwiak, Chris, Bostwick, Aaron, Zettl, Alex, Rotenberg, Eli, & Aloni, Shaul. Tunable electronic structure in gallium chalcogenide van der Waals compounds. United States. doi:10.1103/physrevb.100.165112.
Shevitski, Brian, Ulstrup, Søren, Koch, Roland J., Cai, Hui, Tongay, Sefaattin, Moreschini, Luca, Jozwiak, Chris, Bostwick, Aaron, Zettl, Alex, Rotenberg, Eli, and Aloni, Shaul. Wed . "Tunable electronic structure in gallium chalcogenide van der Waals compounds". United States. doi:10.1103/physrevb.100.165112.
@article{osti_1574341,
title = {Tunable electronic structure in gallium chalcogenide van der Waals compounds},
author = {Shevitski, Brian and Ulstrup, Søren and Koch, Roland J. and Cai, Hui and Tongay, Sefaattin and Moreschini, Luca and Jozwiak, Chris and Bostwick, Aaron and Zettl, Alex and Rotenberg, Eli and Aloni, Shaul},
abstractNote = {Transition-metal monochalcogenides comprise a class of two-dimensional materials with electronic band gaps that are highly sensitive to material thickness and chemical composition. Here, we explore the tunability of the electronic excitation spectrum in GaSe by using angle-resolved photoemission spectroscopy. The electronic structure of the material is modified by in situ potassium deposition as well as by forming GaSxSe1-x alloy compounds. We find that potassium-dosed samples exhibit a substantial change of the dispersion around the valence-band maximum (VBM). The observed band dispersion resembles that of a single tetralayer and is consistent with a transition from the direct-gap character of the bulk to the indirect-gap character expected for monolayer GaSe. Upon alloying with sulfur, we observe a phase transition from AB to AA' stacking. Alloying also results in a rigid energy shift of the VBM towards higher binding energies, which correlates with a blueshift in the luminescence. The increase of the band gap upon sulfur alloying does not appear to change the dispersion or character of the VBM appreciably, implying that it is possible to engineer the gap of these materials while maintaining their salient electronic properties.},
doi = {10.1103/physrevb.100.165112},
journal = {Physical Review B},
number = 16,
volume = 100,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on October 9, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Recent advances in investigations of the electronic and optoelectronic properties of group III, IV, and V selenide based binary layered compounds
journal, January 2017

  • Wasala, Milinda; Sirikumara, Hansika I.; Raj Sapkota, Yub
  • Journal of Materials Chemistry C, Vol. 5, Issue 43
  • DOI: 10.1039/C7TC02866K

Metallic Few-Layered VS 2 Ultrathin Nanosheets: High Two-Dimensional Conductivity for In-Plane Supercapacitors
journal, November 2011

  • Feng, Jun; Sun, Xu; Wu, Changzheng
  • Journal of the American Chemical Society, Vol. 133, Issue 44
  • DOI: 10.1021/ja207176c

Direct-bandgap properties and evidence for ultraviolet lasing of hexagonal boron nitride single crystal
journal, May 2004

  • Watanabe, Kenji; Taniguchi, Takashi; Kanda, Hisao
  • Nature Materials, Vol. 3, Issue 6
  • DOI: 10.1038/nmat1134

Synthesis of Few-Layer GaSe Nanosheets for High Performance Photodetectors
journal, June 2012

  • Hu, PingAn; Wen, Zhenzhong; Wang, Lifeng
  • ACS Nano, Vol. 6, Issue 7
  • DOI: 10.1021/nn300889c

Polytypes and Excitons in GaSe 1- x S x Mixed Crystals
journal, February 1980

  • Serizawa, Hiroshi; Sasaki, Yoshiro; Nishina, Yuichiro
  • Journal of the Physical Society of Japan, Vol. 48, Issue 2
  • DOI: 10.1143/JPSJ.48.490

Electronic band structure of GaSe(0001):  Angle-resolved photoemission and ab initio theory
journal, September 2003


Tight-binding study of the electronic states in GaSe polytypes
journal, May 1979

  • Nagel, S.; Baldereschi, A.; Maschke, K.
  • Journal of Physics C: Solid State Physics, Vol. 12, Issue 9
  • DOI: 10.1088/0022-3719/12/9/006

Intrinsic defects in gallium sulfide monolayer: a first-principles study
journal, January 2015


Electron diffraction study of melt- and vapour-grown GaSe1−xSx single crystals
journal, February 1976

  • Arancia, G.; Grandolfo, M.; Manfredotti, C.
  • Physica Status Solidi (a), Vol. 33, Issue 2
  • DOI: 10.1002/pssa.2210330215

Enhanced superconductivity in atomically thin TaS2
journal, March 2016

  • Navarro-Moratalla, Efrén; Island, Joshua O.; Mañas-Valero, Samuel
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11043

Band Engineering by Controlling vdW Epitaxy Growth Mode in 2D Gallium Chalcogenides
journal, June 2016


Tunable quasiparticle band gap in few-layer GaSe/graphene van der Waals heterostructures
journal, July 2017


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

van der Waals Epitaxy of GaSe/Graphene Heterostructure: Electronic and Interfacial Properties
journal, October 2016


Strongly enhanced charge-density-wave order in monolayer NbSe2
journal, July 2015

  • Xi, Xiaoxiang; Zhao, Liang; Wang, Zefang
  • Nature Nanotechnology, Vol. 10, Issue 9, p. 765-769
  • DOI: 10.1038/nnano.2015.143

Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004


Low-Frequency Electronic Noise in Quasi-1D TaSe 3 van der Waals Nanowires
journal, December 2016


Structural studies of compounds in the series GaSxSe1−x (0⩽x⩽1) grown by iodine vapour transport
journal, November 1978

  • Whitehouse, C. R.; Balchin, A. A.
  • Journal of Materials Science, Vol. 13, Issue 11
  • DOI: 10.1007/BF00808054

Van der Waals Epitaxial Growth of Two-Dimensional Single-Crystalline GaSe Domains on Graphene
journal, July 2015


Controlling the Electronic Structure of Bilayer Graphene
journal, August 2006


Brillouin-zone-selection effects in graphite photoelectron angular distributions
journal, May 1995


Substrate engineering of graphene reactivity: towards high-performance graphene-based catalysts
journal, January 2018


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


Recent development of two-dimensional transition metal dichalcogenides and their applications
journal, April 2017


Size-induced effects in gallium selenide electronic structure: The influence of interlayer interactions
journal, August 2011


Transition from parabolic to ring-shaped valence band maximum in few-layer GaS, GaSe, and InSe
journal, December 2014

  • Rybkovskiy, Dmitry V.; Osadchy, Alexander V.; Obraztsova, Elena D.
  • Physical Review B, Vol. 90, Issue 23
  • DOI: 10.1103/PhysRevB.90.235302

Electronic structure of GaSe, GaS, InSe and GaTe
journal, November 1979


Photoluminescence of two-dimensional GaTe and GaSe films
journal, July 2015


Ab initio electronic band structure study of III–VI layered semiconductors
journal, August 2013

  • Olguín, Daniel; Rubio-Ponce, Alberto; Cantarero, Andrés
  • The European Physical Journal B, Vol. 86, Issue 8
  • DOI: 10.1140/epjb/e2013-40141-1

Characterization of graphene through anisotropy of constant-energy maps in angle-resolved photoemission
journal, May 2008


Polytype phase transition in the series GaSe1−xSx
journal, January 1982

  • Terhell, J. C. J. M.; Brabers, V. A. M.; van Egmond, G. E.
  • Journal of Solid State Chemistry, Vol. 41, Issue 1
  • DOI: 10.1016/0022-4596(82)90039-1

Characterization of collective ground states in single-layer NbSe2
journal, November 2015

  • Ugeda, Miguel M.; Bradley, Aaron J.; Zhang, Yi
  • Nature Physics, Vol. 12, Issue 1
  • DOI: 10.1038/nphys3527

GaS and GaSe Ultrathin Layer Transistors
journal, June 2012


Synthesis and Photoresponse of Large GaSe Atomic Layers
journal, May 2013

  • Lei, Sidong; Ge, Liehui; Liu, Zheng
  • Nano Letters, Vol. 13, Issue 6
  • DOI: 10.1021/nl4010089

Fermi surface, charge-density-wave gap, and kinks in 2 H TaSe 2
journal, September 2005


Tunable Graphene-GaSe Dual Heterojunction Device
journal, January 2016

  • Kim, Wonjae; Li, Changfeng; Chaves, Ferney A.
  • Advanced Materials, Vol. 28, Issue 9
  • DOI: 10.1002/adma.201504514

Valence band inversion and spin-orbit effects in the electronic structure of monolayer GaSe
journal, September 2018


Interlayer Interaction and Electronic Screening in Multilayer Graphene Investigated with Angle-Resolved Photoemission Spectroscopy
journal, May 2007


Epitaxy and Photoresponse of Two-Dimensional GaSe Crystals on Flexible Transparent Mica Sheets
journal, January 2014

  • Zhou, Yubing; Nie, Yufeng; Liu, Yujing
  • ACS Nano, Vol. 8, Issue 2
  • DOI: 10.1021/nn405529r

Red-to-Ultraviolet Emission Tuning of Two-Dimensional Gallium Sulfide/Selenide
journal, September 2015


Electronic structure of the layer compounds GaSe and InSe in a tight-binding approach
journal, March 2002


Superconducting Density of States and Vortex Cores of 2H- NbS 2
journal, October 2008


Growth and quality of gallium selenide (GaSe) crystals
journal, October 2013


Electronic Structure of a Quasi-Freestanding MoS 2 Monolayer
journal, February 2014

  • Eknapakul, T.; King, P. D. C.; Asakawa, M.
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl4042824