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

Title: Electrochemical Formation of Germanene: pH 4.5

Abstract

Germanene is a single layer allotrope of Ge, with a honeycomb structure similar to graphene. This report concerns the electrochemical formation of germanene in a pH 4.5 solution. The studies were performed using in situ Electrochemical Scanning Tunneling Microscopy (EC-STM), voltammetry, coulometry, surface X-ray diffraction (SXRD) and Raman spectroscopy to study germanene electrodeposition on Au(111) terraces. The deposition of Ge is kinetically slow and stops after 2–3 monolayers. EC-STM revealed a honeycomb (HC) structure with a rhombic unit cell, 0.44 ± 0.02 nm on a side, very close to that predicted for germanene in the literature. Ideally the HC structure is a continuous sheet, with six Ge atoms around each hole. However, only small domains, surrounded by defects, of this structure were observed in this study. The small coherence length and multiple rotations domains made direct observation with surface X-ray diffraction difficult. Raman spectroscopy was used to investigate the multi-layer Ge deposits. A peak near 290 cm -1, predicted to correspond to germanene, was observed on one particular area of the sample, while the rest resembled amorphous germanium. Electrochemical studies of germanene showed limited stability when exposed to oxygen.

Authors:
 [1];  [1];  [1];  [2];  [1];  [1];  [1];  [3];  [3];  [2];  [4];  [4]
  1. Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  3. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  4. Univ. of Georgia, Athens, GA (United States). Department of Chemistry
Publication Date:
Research Org.:
California Inst. of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); Gordon and Betty Moore Foundation (GBMF)
OSTI Identifier:
1418637
Grant/Contract Number:  
SC0004993; CHE-1214152
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 7; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ledina, M. A., Bui, N., Liang, X., Kim, Y. -G., Jung, J., Perdue, B., Tsang, C., Drnec, J., Carla, F., Soriaga, M. P., Reber, T. J., and Stickney, J. L. Electrochemical Formation of Germanene: pH 4.5. United States: N. p., 2017. Web. doi:10.1149/2.1221707jes.
Ledina, M. A., Bui, N., Liang, X., Kim, Y. -G., Jung, J., Perdue, B., Tsang, C., Drnec, J., Carla, F., Soriaga, M. P., Reber, T. J., & Stickney, J. L. Electrochemical Formation of Germanene: pH 4.5. United States. doi:10.1149/2.1221707jes.
Ledina, M. A., Bui, N., Liang, X., Kim, Y. -G., Jung, J., Perdue, B., Tsang, C., Drnec, J., Carla, F., Soriaga, M. P., Reber, T. J., and Stickney, J. L. Sat . "Electrochemical Formation of Germanene: pH 4.5". United States. doi:10.1149/2.1221707jes. https://www.osti.gov/servlets/purl/1418637.
@article{osti_1418637,
title = {Electrochemical Formation of Germanene: pH 4.5},
author = {Ledina, M. A. and Bui, N. and Liang, X. and Kim, Y. -G. and Jung, J. and Perdue, B. and Tsang, C. and Drnec, J. and Carla, F. and Soriaga, M. P. and Reber, T. J. and Stickney, J. L.},
abstractNote = {Germanene is a single layer allotrope of Ge, with a honeycomb structure similar to graphene. This report concerns the electrochemical formation of germanene in a pH 4.5 solution. The studies were performed using in situ Electrochemical Scanning Tunneling Microscopy (EC-STM), voltammetry, coulometry, surface X-ray diffraction (SXRD) and Raman spectroscopy to study germanene electrodeposition on Au(111) terraces. The deposition of Ge is kinetically slow and stops after 2–3 monolayers. EC-STM revealed a honeycomb (HC) structure with a rhombic unit cell, 0.44 ± 0.02 nm on a side, very close to that predicted for germanene in the literature. Ideally the HC structure is a continuous sheet, with six Ge atoms around each hole. However, only small domains, surrounded by defects, of this structure were observed in this study. The small coherence length and multiple rotations domains made direct observation with surface X-ray diffraction difficult. Raman spectroscopy was used to investigate the multi-layer Ge deposits. A peak near 290 cm-1, predicted to correspond to germanene, was observed on one particular area of the sample, while the rest resembled amorphous germanium. Electrochemical studies of germanene showed limited stability when exposed to oxygen.},
doi = {10.1149/2.1221707jes},
journal = {Journal of the Electrochemical Society},
number = 7,
volume = 164,
place = {United States},
year = {2017},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Proposed low-buckled germanene structure. One half of the Ge atoms are 0.07 nm higher than the other half.

Save / Share:

Works referenced in this record:

Electrodeposition from organic solutions of metals that are difficult to deposit from aqueous solutions
journal, July 1981


Electrodeposition of Nanosized Germanium from GeBr[sub 4] and GeCl[sub 4] in an Ionic Liquid
journal, January 2002

  • Endres, Frank
  • Electrochemical and Solid-State Letters, Vol. 5, Issue 3
  • DOI: 10.1149/1.1448185

Two-dimensional materials under electron irradiation
journal, January 2015

  • Sun, Litao; Banhart, Florian; Warner, Jamie
  • MRS Bulletin, Vol. 40, Issue 1
  • DOI: 10.1557/mrs.2014.303

Stability and electronic properties of ultrathin films of silicon and germanium
journal, January 2013

  • Kaltsas, Dimitrios; Tsetseris, Leonidas
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 24
  • DOI: 10.1039/c3cp50944c

Structure of Si atomic chains grown on the Si/Cu(110) c ( 2 × 2 ) surface alloy
journal, March 2001


Nanoscale electrodeposition of germanium on Au(111) from an ionic liquid: an in situ STM study of phase formation
journal, March 2002

  • Endres, Frank; Zein El Abedin, Sherif
  • Physical Chemistry Chemical Physics, Vol. 4, Issue 9
  • DOI: 10.1039/b110560b

Evidence for Germanene growth on epitaxial hexagonal (h)-AlN on Ag(1 1 1)
journal, January 2016


Growth of Straight, Atomically Perfect, Highly Metallic Silicon Nanowires with Chiral Asymmetry
journal, January 2008

  • De Padova, Paola; Quaresima, Claudio; Perfetti, Paolo
  • Nano Letters, Vol. 8, Issue 1
  • DOI: 10.1021/nl072591y

Infrared absorbance of silicene and germanene
journal, June 2012

  • Bechstedt, Friedhelm; Matthes, Lars; Gori, Paola
  • Applied Physics Letters, Vol. 100, Issue 26
  • DOI: 10.1063/1.4731626

Tunable Bandgap in Silicene and Germanene
journal, December 2011

  • Ni, Zeyuan; Liu, Qihang; Tang, Kechao
  • Nano Letters, Vol. 12, Issue 1
  • DOI: 10.1021/nl203065e

Stability and Exfoliation of Germanane: A Germanium Graphane Analogue
journal, March 2013

  • Bianco, Elisabeth; Butler, Sheneve; Jiang, Shishi
  • ACS Nano, Vol. 7, Issue 5
  • DOI: 10.1021/nn4009406

Continuous Germanene Layer on Al(111)
journal, March 2015


Processable aqueous dispersions of graphene nanosheets
journal, January 2008


UV-Assisted Electrodeposition of Germanium from an Air- and Water-Stable Ionic Liquid
journal, August 2012

  • Lahiri, Abhishek; Zein El Abedin, Sherif; Endres, Frank
  • The Journal of Physical Chemistry C, Vol. 116, Issue 33
  • DOI: 10.1021/jp3062543

Surface reconstruction transition of metals induced by molecular adsorption
journal, March 2011


ROD : a program for surface X-ray crystallography
journal, April 2000


Graphene and Graphene Oxide: Synthesis, Properties, and Applications
journal, June 2010

  • Zhu, Yanwu; Murali, Shanthi; Cai, Weiwei
  • Advanced Materials, Vol. 22, Issue 35, p. 3906-3924
  • DOI: 10.1002/adma.201001068

Electrodeposited Germanium Nanowires
journal, August 2014

  • Mahenderkar, Naveen K.; Liu, Ying-Chau; Koza, Jakub A.
  • ACS Nano, Vol. 8, Issue 9
  • DOI: 10.1021/nn503784d

Direct formation of large-scale multi-layered germanene on Si substrate
journal, January 2015

  • Tsai, Hsu-Sheng; Chen, Yu-Ze; Medina, Henry
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 33
  • DOI: 10.1039/C5CP02469B

In situ X-ray analysis under controlled potential conditions: An innovative setup and its application to the investigation of ultrathin films electrodeposited on Ag(111)
journal, July 2006


Electrodeposition of Germanium
journal, January 1951

  • Szekely, G.
  • Journal of The Electrochemical Society, Vol. 98, Issue 8
  • DOI: 10.1149/1.2778214

Electrodeposition of germanium from the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide
journal, January 2013

  • Wu, Minxian; Brooks, Neil R.; Schaltin, Stijn
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 14
  • DOI: 10.1039/c3cp44554b

Room-Temperature Epitaxial Electrodeposition of Single-Crystalline Germanium Nanowires at the Wafer Scale from an Aqueous Solution
journal, January 2014

  • Fahrenkrug, Eli; Gu, Junsi; Jeon, Sunyeol
  • Nano Letters, Vol. 14, Issue 2
  • DOI: 10.1021/nl404228z

Graphene-like silicon nanoribbons on Ag(110): A possible formation of silicene
journal, May 2010

  • Aufray, Bernard; Kara, Abdelkader; Vizzini, Sébastien
  • Applied Physics Letters, Vol. 96, Issue 18
  • DOI: 10.1063/1.3419932

Grains and grain boundaries in single-layer graphene atomic patchwork quilts
journal, January 2011

  • Huang, Pinshane Y.; Ruiz-Vargas, Carlos S.; van der Zande, Arend M.
  • Nature, Vol. 469, Issue 7330, p. 389-392
  • DOI: 10.1038/nature09718

Electrodeposition of germanium at elevated temperatures and pressures from ionic liquids
journal, January 2015

  • Wu, Minxian; Vanhoutte, Gijs; Brooks, Neil R.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 18
  • DOI: 10.1039/C4CP06076H

Growth of Ge Nanofilms Using Electrochemical Atomic Layer Deposition, with a “Bait and Switch” Surface-Limited Reaction
journal, June 2011

  • Liang, Xuehai; Zhang, Qinghui; Lay, Marcus D.
  • Journal of the American Chemical Society, Vol. 133, Issue 21
  • DOI: 10.1021/ja109398t

All-Metallic Vertical Transistors Based on Stacked Dirac Materials
journal, November 2014

  • Wang, Yangyang; Ni, Zeyuan; Liu, Qihang
  • Advanced Functional Materials, Vol. 25, Issue 1
  • DOI: 10.1002/adfm.201402904

Thickness induced metal–nonmetal transition in ultrathin electrodeposited Ge films
journal, August 2003


An Alternative Method to Grow Ge Thin Films on Si by Electrochemical Deposition for Photonic Applications
journal, January 2011

  • Jawad, M. J.; Hashim, M. R.; Ali, N. K.
  • Journal of The Electrochemical Society, Vol. 159, Issue 2
  • DOI: 10.1149/2.090202jes

A Stable “Flat″ Form of Two-Dimensional Crystals: Could Graphene, Silicene, Germanene Be Minigap Semiconductors?
journal, January 2012

  • O’Hare, A.; Kusmartsev, F. V.; Kugel, K. I.
  • Nano Letters, Vol. 12, Issue 2
  • DOI: 10.1021/nl204283q

Silicene and germanene: Silicon and germanium in the “flatland”
journal, January 2015


Germanene termination of Ge 2 Pt crystals on Ge(110)
journal, September 2014


In situ STM studies on germanium tetraiodide electroreduction on Au(111) in the room temperature molten salt 1-butyl-3-methylimidazolium hexafluorophosphate
journal, January 2000

  • Endres, Frank; Schrodt, Claudia
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 24
  • DOI: 10.1039/b007897m

Aqueous Electrodeposition of Ge Monolayers
journal, February 2010

  • Liang, Xuehai; Kim, Youn-Geun; Gebergziabiher, Daniel K.
  • Langmuir, Vol. 26, Issue 4
  • DOI: 10.1021/la902929j

Structure and phases of the Au(111) surface: X-ray-scattering measurements
journal, February 1991


Transfer of Large-Area Graphene Films for High-Performance Transparent Conductive Electrodes
journal, December 2009

  • Li, Xuesong; Zhu, Yanwu; Cai, Weiwei
  • Nano Letters, Vol. 9, Issue 12
  • DOI: 10.1021/nl902623y

Electrodeposition of a thin germanium film on gold from a room temperature ionic liquid
journal, January 2001

  • Endres, Frank
  • Physical Chemistry Chemical Physics, Vol. 3, Issue 15
  • DOI: 10.1039/b102232f

Evidence of graphene-like electronic signature in silicene nanoribbons
journal, June 2010

  • De Padova, Paola; Quaresima, Claudio; Ottaviani, Carlo
  • Applied Physics Letters, Vol. 96, Issue 26
  • DOI: 10.1063/1.3459143

Single-Crystalline Germanium Thin Films by Electrodeposition and Solid-Phase Epitaxy
journal, January 2007

  • Huang, Q.; Bedell, S. W.; Saenger, K. L.
  • Electrochemical and Solid-State Letters, Vol. 10, Issue 11
  • DOI: 10.1149/1.2771097

Germanene: a novel two-dimensional germanium allotrope akin to graphene and silicene
journal, September 2014


Adsorption of alkali metal atoms on germanene: A first-principles study
journal, September 2014


Interplay between ordered growth and intermixing of Pt on patterned Au surfaces
journal, May 2010


Theoretical performance estimation of silicene, germanene, and graphene nanoribbon field-effect transistors under ballistic transport
journal, March 2014

  • Kaneko, Shiro; Tsuchiya, Hideaki; Kamakura, Yoshinari
  • Applied Physics Express, Vol. 7, Issue 3
  • DOI: 10.7567/APEX.7.035102

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


Vibrational properties of silicene and germanene
journal, December 2012


Physics of Silicene Stripes
journal, January 2009

  • Kara, A.; Léandri, C.; Dávila, M. E.
  • Journal of Superconductivity and Novel Magnetism, Vol. 22, Issue 3
  • DOI: 10.1007/s10948-008-0427-8

Many-body effects in silicene, silicane, germanene and germanane
journal, January 2013

  • Wei, Wei; Dai, Ying; Huang, Baibiao
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 22
  • DOI: 10.1039/c3cp51078f

Controlled Electrochemical Formation of Ge x Sb y Te z using Atomic Layer Deposition (ALD)
journal, April 2011

  • Liang, Xuehai; Jayaraju, Nagarajan; Thambidurai, Chandru
  • Chemistry of Materials, Vol. 23, Issue 7
  • DOI: 10.1021/cm102672j

Two- and One-Dimensional Honeycomb Structures of Silicon and Germanium
journal, June 2009


BINoculars : data reduction and analysis software for two-dimensional detectors in surface X-ray diffraction
journal, June 2015

  • Roobol, Sander; Onderwaater, Willem; Drnec, Jakub
  • Journal of Applied Crystallography, Vol. 48, Issue 4
  • DOI: 10.1107/S1600576715009607

Template assisted electrodeposition of germanium and silicon nanowires in an ionic liquid
journal, January 2008

  • Al-Salman, R.; Mallet, J.; Molinari, M.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 41
  • DOI: 10.1039/b809075k

Buckled Germanene Formation on Pt(111)
journal, May 2014


Massive Dirac quasiparticles in the optical absorbance of graphene, silicene, germanene, and tinene
journal, September 2013


In situ x-ray-diffraction and -reflectivity studies of the Au(111)/electrolyte interface: Reconstruction and anion adsorption
journal, October 1992


Integration techniques for surface X-ray diffraction data obtained with a two-dimensional detector
journal, January 2014

  • Drnec, Jakub; Zhou, Tao; Pintea, Stelian
  • Journal of Applied Crystallography, Vol. 47, Issue 1
  • DOI: 10.1107/S1600576713032342

Ultrathin nanostructures: smaller size with new phenomena
journal, January 2013


Electronic properties of two-dimensional hexagonal germanium
journal, February 2010

  • Houssa, M.; Pourtois, G.; Afanas’ev, V. V.
  • Applied Physics Letters, Vol. 96, Issue 8
  • DOI: 10.1063/1.3332588

Low temperature STM/STS study of silicon nanowires grown on the Ag(110) surface
journal, August 2010

  • Ronci, Fabio; Colonna, Stefano; Cricenti, Antonio
  • physica status solidi (c), Vol. 7, Issue 11-12
  • DOI: 10.1002/pssc.200983839

Electrodeposition of germanium from supercritical fluids
journal, January 2012

  • Ke, Jie; Bartlett, Philip N.; Cook, David
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 4
  • DOI: 10.1039/C1CP22555C

Quasi unidimensional growth of Co nanostructures on a strained Au(111) surface
journal, July 2011


Physics and chemistry of silicene nano-ribbons
journal, October 2009


Pushing the boundaries
journal, May 2011

  • Ajayan, Pulickel M.; Yakobson, Boris I.
  • Nature Materials, Vol. 10, Issue 6
  • DOI: 10.1038/nmat3027

Beyond Graphene: Stable Elemental Monolayers of Silicene and Germanene
journal, April 2014

  • Roome, Nathanael J.; Carey, J. David
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 10
  • DOI: 10.1021/am501022x

Few layer epitaxial germanene: a novel two-dimensional Dirac material
journal, February 2016

  • Dávila, María Eugenia; Le Lay, Guy
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep20714

Defects and impurities in graphene-like materials
journal, March 2012


A review on silicene — New candidate for electronics
journal, January 2012


Elemental Analogues of Graphene: Silicene, Germanene, Stanene, and Phosphorene
journal, November 2014


Nanoscale electrodeposition of germanium on Au(111) from an ionic liquid: an in situ STM study of phase formation
journal, March 2002

  • Endres, Frank; Zein El Abedin, Sherif
  • Physical Chemistry Chemical Physics, Vol. 4, Issue 9
  • DOI: 10.1039/b110268k

The rare two-dimensional materials with Dirac cones
journal, February 2015

  • Wang, Jinying; Deng, Shibin; Liu, Zhongfan
  • National Science Review, Vol. 2, Issue 1
  • DOI: 10.1093/nsr/nwu080

Atomic-scale surface science phenomena studied by scanning tunneling microscopy
journal, June 2009


Atomic-Scale Geometry and Electronic Structure of Catalytically Important Pd/Au Alloys
journal, February 2010

  • Baber, Ashleigh E.; Tierney, Heather L.; Sykes, E. Charles H.
  • ACS Nano, Vol. 4, Issue 3
  • DOI: 10.1021/nn901390y

Self-Assembly of a Functionalized Alkylated Isophthalic Acid at the Au(111)/Electrolyte Interface: Structure and Dynamics
journal, May 2009

  • Hai, Nguyen T. M.; Auweraer, Mark Van der; Müllen, Klaus
  • The Journal of Physical Chemistry C, Vol. 113, Issue 27
  • DOI: 10.1021/jp900930p

1D graphene-like silicon systems: silicene nano-ribbons
journal, May 2012


Benchtop Electrochemical Liquid–Liquid–Solid Growth of Nanostructured Crystalline Germanium
journal, August 2011

  • Carim, Azhar I.; Collins, Sean M.; Foley, Justin M.
  • Journal of the American Chemical Society, Vol. 133, Issue 34
  • DOI: 10.1021/ja205299w

Electrodeposition of Co and Ni/Au(111) ultrathin layers. Part I: nucleation and growth mechanisms from in situ STM
journal, May 2004