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Title: Thermal stability of simple tetragonal and hexagonal diamond germanium

Abstract

Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursor materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [1]; ORCiD logo [1]
  1. The Australian National Univ., Acton, ACT (Australia)
  2. Univ. of Melbourne, VIC (Australia)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. The Australian National Univ., Acton, ACT (Australia); RMIT Univ., Melbourne, VIC (Australia)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1409261
Alternate Identifier(s):
OSTI ID: 1407838
Grant/Contract Number:  
AC05-00OR22725; Project No. 7620.
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 122; Journal Issue: 17; Journal ID: ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Huston, Larissa Q., Johnson, Brett C., Haberl, Bianca, Wong, Sherman, Williams, James S., and Bradby, Jodie E. Thermal stability of simple tetragonal and hexagonal diamond germanium. United States: N. p., 2017. Web. doi:10.1063/1.5002705.
Huston, Larissa Q., Johnson, Brett C., Haberl, Bianca, Wong, Sherman, Williams, James S., & Bradby, Jodie E. Thermal stability of simple tetragonal and hexagonal diamond germanium. United States. doi:10.1063/1.5002705.
Huston, Larissa Q., Johnson, Brett C., Haberl, Bianca, Wong, Sherman, Williams, James S., and Bradby, Jodie E. Tue . "Thermal stability of simple tetragonal and hexagonal diamond germanium". United States. doi:10.1063/1.5002705. https://www.osti.gov/servlets/purl/1409261.
@article{osti_1409261,
title = {Thermal stability of simple tetragonal and hexagonal diamond germanium},
author = {Huston, Larissa Q. and Johnson, Brett C. and Haberl, Bianca and Wong, Sherman and Williams, James S. and Bradby, Jodie E.},
abstractNote = {Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursor materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.},
doi = {10.1063/1.5002705},
journal = {Journal of Applied Physics},
number = 17,
volume = 122,
place = {United States},
year = {2017},
month = {11}
}

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Works referenced in this record:

Raman spectra of two new modifications of germanium: Allo-germanium and 4H-Ge
journal, March 1983


Experimental evidence of new tetragonal polymorphs of silicon formed through ultrafast laser-induced confined microexplosion
journal, June 2015

  • Rapp, L.; Haberl, B.; Pickard, C. J.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8555

Hexagonal germanium formed via a pressure-induced phase transformation of amorphous germanium under controlled nanoindentation
journal, March 2013

  • Williams, James S.; Haber, Bianca; Deshmukh, Sarita
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 7, Issue 5
  • DOI: 10.1002/pssr.201307079

Germanium nanoparticles with non-diamond core structures for solar energy conversion
journal, January 2014

  • Vörös, Márton; Wippermann, Stefan; Somogyi, Bálint
  • Journal of Materials Chemistry A, Vol. 2, Issue 25
  • DOI: 10.1039/c4ta01543f

Harder than Diamond: Superior Indentation Strength of Wurtzite BN and Lonsdaleite
journal, February 2009


Pressure induced phase transitions in silicon, germanium and some III–V compounds
journal, May 1962


High-Pressure Transitions of Germanium and a New High-Pressure Form of Germanium
journal, February 1965


Phase transformation pathways in amorphous germanium under indentation pressure
journal, April 2014

  • Deshmukh, S.; Haberl, B.; Ruffell, S.
  • Journal of Applied Physics, Vol. 115, Issue 15
  • DOI: 10.1063/1.4871190

Ordering of amorphous germanium prior to crystallization
journal, October 1983


Evidence for the R 8 Phase of Germanium
journal, February 2013


Hexagonal (Wurtzite) Silicon
journal, August 1977


Nonequilibrium phase transitions and amorphization in Si, Si/GaAs, Ge, and Ge/GaSb at the decompression of high-pressure phases
journal, March 1995


Phase transformation of germanium by processing through high-pressure torsion: strain and temperature effects
journal, November 2016


Structure and properties of silicon XII: A complex tetrahedrally bonded phase
journal, August 1995


Properties of the exotic metastable ST12 germanium allotrope
journal, January 2017

  • Zhao, Zhisheng; Zhang, Haidong; Kim, Duck Young
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms13909

Kinetics of solid phase crystallization in amorphous silicon
journal, January 1988


Pressure-Induced Transitions in Amorphous Silicon and Germanium
journal, October 1981


Electronic Properties of Complex Crystalline and Amorphous Phases of Ge and Si. I. Density of States and Band Structures
journal, March 1973


Ab initio survey of the electronic structure of tetrahedrally bonded phases of silicon
journal, July 2008


High-resolution transmission electron microscopy analysis of nanograined germanium produced by high-pressure torsion
journal, October 2017


Controlled formation of metastable germanium polymorphs
journal, April 2014


The crystal structures of new forms of silicon and germanium
journal, June 1964


Intrinsic and dopant-enhanced solid-phase epitaxy in amorphous germanium
journal, June 2008


Thermal evolution of the metastable r8 and bc8 polymorphs of silicon
journal, January 2015


Stability and crystal structure of BC8 germanium
journal, October 1993


Tensile-Strained GeSn Metal–Oxide–Semiconductor Field-Effect Transistor Devices on Si(111) Using Solid Phase Epitaxy
journal, October 2013

  • Lieten, Ruben R.; Maeda, Tatsuro; Jevasuwan, Wipakorn
  • Applied Physics Express, Vol. 6, Issue 10
  • DOI: 10.7567/APEX.6.101301

Extended X-ray absorption fine-structure analysis of vacuum-deposited amorphous germanium
journal, April 1989

  • Johnson, G. W.; Brodie, D. E.; Crozier, E. D.
  • Canadian Journal of Physics, Vol. 67, Issue 4
  • DOI: 10.1139/p89-063

A New Dense Form of Solid Germanium
journal, January 1963


Electronic structure, equation of state, and lattice dynamics of low-pressure Ge polymorphs
journal, August 2012


Crystal Structures at High Pressures of Metallic Modifications of Silicon and Germanium
journal, February 1963