Germanium (Ge) plays a crucial role in setting up important functionalities for silicon-compatible photonics. Diamond cubic germanium is an extensively studied semiconductor, although its other exotic forms, like BC8, ST8, ST12 phases, may possess distinct electronic properties. We have fabricated stable ST12-Ge nanowires via a self-seeded bottom-up three phase growth in a confined supercritical toluene environment. Here, we report on the direct evidence of the presence of the ST12 phase by a combination of Raman spectroscopy and first-principles calculations using density functional theory (DFT). It is important to remark that the DFT calculation predicts all the Raman active optical phonon modes of the P structure, and it is in very good agreement with the experimental results. The phonon dynamics as a function of temperature is investigated through Raman measurements at temperatures varying from 80 to 300 K. First-order temperature coefficients for all the observed Raman modes are estimated from the linear temperature dependence of the phonon shifts. A complete set of isobaric Grüneisen parameters is reported for all Raman modes of ST12-Ge nanowire, and the values are lower compared to the same for Si, dc-Ge bulk, and Ge nanowire. These results have important implications for understanding thermal properties of ST12-Ge nanowire.
References
1.
P.
Staudinger
, M.
Sistani
, J.
Greil
, E.
Bertagnolli
, and A.
Lugstein
, “Ultrascaled germanium nanowires for highly sensitive photodetection at the quantum ballistic limit
,” Nano Lett.
18
, 5030
–5035
(2018
).2.
L. N.
Quan
, J.
Kang
, C.-Z.
Ning
, and P.
Yang
, “Nanowires for photonics
,” Chem. Rev.
119
, 9153
–9169
(2019
).3.
C. K.
Chan
, H.
Peng
, G.
Liu
, K.
McIlwrath
, X. F.
Zhang
, R. A.
Huggins
, and Y.
Cui
, “High-performance lithium battery anodes using silicon nanowires
,” Nat. Nanotechnol.
3
, 31
–35
(2008
).4.
A. M.
Chockla
, K. C.
Klavetter
, C. B.
Mullins
, and B. A.
Korgel
, “Solution-grown germanium nanowire anodes for lithium-ion batteries
,” ACS Appl. Mater. Interfaces
4
, 4658
–4664
(2012
).5.
N.
Shehada
, J. C.
Cancill
, J. S.
Torrecilla
, E. S.
Pariente
, G.
Brönstrup
, S.
Christiansen
, D. W.
Johnson
, M.
Leja
, M. P. A.
Davies
, O.
Liran
, N.
Peled
, and H.
Haick
, “Silicon nanowire sensors enable diagnosis of patients via exhaled breath
,” ACS Nano
10
, 7047
–7057
(2016
).6.
L.
Hrachowinaa
, G.
Domènech-Gil
, A.
Pardo
, M. S.
Seifner
, I.
Gràcia
, C.
Cané
, A.
Romano-Rodríguez
, and S.
Barth
, “Site-specific growth and in situ integration of different nanowire material networks on a single chip: Toward a nanowire-based electronic nose for gas detection
,” ACS Sens.
3
, 727
–734
(2018
).7.
D.
Marris-Morini
, V.
Vakarin
, J. M.
Ramirez
, Q.
Liu
, A.
Ballabio
, J.
Frigerio
, M.
Montesinos
, C.
Alonso-Ramos
, X.
Le
, S.
Serna
, D.
Benedikovic
, D.
Chrastina
, L.
Vivien
, and G.
Isella
, “Germanium-based integrated photonics from near- to mid-infrared applications
,” Nanophotonics
7
, 1781
–1793
(2018
).8.
S.
Liao
, N.-N.
Feng
, D.
Feng
, P.
Dong
, R.
Shafiiha
, C.-C.
Kung
, H.
Liang
, W.
Qian
, Y.
Liu
, J.
Fong
, J. E.
Cunningham
, Y.
Luo
, and M.
Asghari
, “36 GHz submicron silicon waveguide germanium photodetector
,” Opt. Express
19
, 10967
–10972
(2011
).9.
C.
Monmeyran
, I. F.
Crowe
, R. M.
Gwilliam
, J.
Michel
, L. C.
Kimerling
, and A. M.
Agarwal
, “Strategies for increased donor electrical activity in germanium (opto-) electronic materials: A review
,” Int. Mater. Rev.
62
, 334
–347
(2017
).10.
Z.
Qi
, H.
Sun
, M.
Luo
, Y.
Jung
, and D.
Nam
, “Strained germanium nanowire optoelectronic devices for photonic-integrated circuits
,” J. Phys.
30
, 334004
(2018
).11.
Y. J.
Cho
, H. S.
Im
, H. S.
Kim
, Y.
Myung
, S. H.
Back
, Y. R.
Lim
, C. S.
Jung
, D. M.
Jang
, J.
Park
, E. H.
Cha
, W. I.
Cho
, F.
Shojaei
, and H. S.
Kang
, “Tetragonal phase germanium nanocrystals in lithium ion batteries
,” ACS Nano
7
, 9075
–9084
(2013
).12.
Y.
Ikoma
, T.
Toyota
, Y.
Ejiri
, K.
Saito
, Q.
Guo
, and Z.
Horita
, “Allotropic phase transformation and photoluminescence of germanium nanograins processed by high-pressure torsion
,” J. Mater. Sci.
51
, 138
–143
(2016
).13.
B. D.
Malone
and M. L.
Cohen
, “Electronic structure, equation of state, and lattice dynamics of low-pressure Ge polymorphs
,” Phys. Rev. B
86
, 054101
(2012
).14.
D.
Selli
, I. A.
Baburin
, R.
Martoňák
, and S.
Leoni
, “Novel metastable metallic and semiconducting germaniums
,” Sci. Rep.
3
, 1466
(2013
).15.
A.
Grüttner
, R.
Nesper
, and H. G. V.
Schnering
, “Novel metastable germanium modifications allo-Ge and 4H-Ge from
,” Angew. Chem., Int. Ed.
21
, 912
–913
(1982
).16.
S.
Minomura
, “Pressure-induced transitions in amorphous silicon and germanium
,” J. Phys. Colloq.
42
, C4-181
–C4-188
(1981
).17.
S. B.
Qadri
, E. F.
Skelton
, and A. W.
Webb
, “High pressure studies of Ge using synchrotron radiation
,” J. Appl. Phys.
54
, 3609
–3611
(1983
).18.
F. P.
Bundy
and J. S.
Kasper
, “A new dense form of solid germanium
,” Science
139
, 340
–341
(1963
).19.
M.
Imai
, T.
Mitamura
, K.
Yaoita
, and K.
Tsuji
, “Pressure-induced phase transition of crystalline and amorphous silicon and germanium at low temperatures
,” High Pressure Res.
15
, 167
–189
(1996
).20.
F.
Coppari
, J. C.
Chervin
, A.
Congeduti
, M.
Lazzeri
, A.
Polian
, E.
Principi
, and A. D.
Cicco
, “Pressure-induced phase transitions in amorphous and metastable crystalline germanium by Raman scattering, x-ray spectroscopy, and ab initio calculations
,” Phys. Rev. B
80
, 115213
(2009
).21.
J. V.
Zaikina
, E.
Muthuswamy
, K. I.
Lilova
, Z. M.
Gibbs
, M.
Zeilinger
, G. J.
Snyder
, T. F.
Fässler
, A.
Navrotsky
, and S. M.
Kauzlarich
, “Thermochemistry, morphology, and optical characterization of germanium allotropes
,” Chem. Mater.
26
, 3263
–3271
(2014
).22.
S.
Sato
, S.
Nozaki
, and H.
Morisaki
, “Tetragonal germanium films deposited by the cluster-beam evaporation technique
,” Appl. Phys. Lett.
66
, 3176
(1995
).23.
R.
Nelmes
, H.
Liu
, S.
Belmonte
, J.
Loveday
, M.
McMahon
, D.
Allan
, D.
Häusermann
, and M.
Hanfland
, “Imma phase of germanium at ∼80 GPa
,” Phys. Rev. B
53
, R2907
–R2909(R)
(1996
).24.
X.
Chen
, C.
Zhang
, Y.
Meng
, R.
Zhang
, H.
Lin
, V.
Struzhkin
, and H.
Mao
, “β−tin→Imma→sh phase transitions of germanium
,” Phys. Rev. Lett.
106
, 135502
(2011
).25.
A. G.
Lyapin
, V. V.
Brazhkin
, S. V.
Popova
, and A. V.
Sapeliki
, “Nonequilibrium phase transformations in diamond and zincblende semiconductors under high pressure
,” Phys. Status Solidi B
198
, 481
–490
(1996
).26.
Y. K.
Vohra
, K. E.
Brister
, S.
Desgreniers
, A. L.
Ruoff
, K. J.
Chang
, and M. L.
Cohen
, “Phase-transition studies of germanium to 1.25 Mbar
,” Phys. Rev. Lett.
56
, 1944
–1947
(1986
).27.
K.
Takemura
, U.
Schwarz
, K.
Syassen
, M.
Hanfland
, N. E.
Christensen
, D. L.
Novikov
, and I.
Loa
, “High-pressure Cmca and hcp phases of germanium
,” Phys. Rev. B
62
, R10603(R)
(2000
).28.
C. H.
Bates
, F.
Dachille
, and R.
Roy
, “High-pressure transitions of germanium and a new high-pressure form of germanium
,” Science
147
, 860
–862
(1965
).29.
B. C.
Johnson
, B.
Haberl
, S.
Deshmukh
, D.
Brad Malone
, M. L.
Cohen
, J. C.
McCallum
, J. S.
Williams
, and J. E.
Bradby
, “Evidence for the R8 phase of germanium
,” Phys. Rev. Lett.
110
, 085502
(2013
).30.
R. J.
Nelmes
, M. I.
McMahon
, N. G.
Wright
, D. R.
Allan
, and J. S.
Loveday
, “Stability and crystal structure of BC8 germanium
,” Phys. Rev. B
48
, 9883(R)
(1993
).31.
J. D.
Joannopoulos
and M. L.
Cohen
, “Electronic properties of complex crystalline and amorphous phases of Ge and Si. I. Density of states and band structures
,” Phys. Rev. B
7
, 2644
–2657
(1973
).32.
Z.
Zhao
, H.
Zhang
, D. Y.
Kim
, W.
Hu
, E. S.
Bullock
, and T. A.
Strobel
, “Properties of the exotic metastable ST12 germanium allotrope
,” Nat. Commun.
8
, 13909
(2017
).33.
L. Q.
Hutson
, B. C.
Johnson
, B.
Haberl
, S.
Wong
, J. S.
Williams
, and J. E.
Bradby
, “Thermal stability of simple tetragonal and hexagonal germanium
,” J. Appl. Phys.
122
, 175108
(2017
).34.
A.
Mujica
and R. J.
Needs
, “First-principles calculations of the structural properties, stability, and band structure of complex tetrahedral phases of germanium: ST12 and BC8
,” Phys. Rev. B
48
, 17010
–17017
(1993
).35.
M.
Shishkin
and G.
Kresse
, “Self-consistent GW calculations for semiconductors and insulators
,” Phys. Rev. B
75
, 235102
(2007
).36.
S. J.
Kim
, O. K.
Quy
, L.-S.
Chang
, E. A.
Stach
, C. A.
Handwerker
, and A.
Wei
, “Formation of the ST12 phase in nanocrystalline Ge at ambient pressure
,” J. Mater. Chem.
20
, 331
–337
(2010
).37.
S.
Sato
, S.
Nazaki
, and H.
Morisaki
, “Density of states of the tetragonal-phase germanium nanocrystals using x-ray photoelectron spectroscopy
,” Appl. Phys. Lett.
72
, 2460
–2462
(1998
).38.
Y.
Saito
, “Crystal structure and habit of silicon and germanium particles grown in argon gas
,” J. Cryst. Growth
47
, 61
–72
(1979
).39.
C.
Jia
, Z.
Lin
, Y.
Huang
, and X.
Duan
, “Nanowire electronics: From nanoscale to macroscale
,” Chem. Rev.
119
, 9074
–9135
(2019
).40.
C. K.
Chan
, X. F.
Zhang
, and Y.
Cui
, “High capacity Li ion battery anodes using Ge nanowires
,” Nano Lett.
8
, 307
–309
(2008
).41.
T.
Kennedy
, E.
Mullane
, H.
Geaney
, M.
Osiak
, C. O.
Dwyer
, and K. M.
Ryan
, “High-performance germanium nanowire-based lithium-ion battery anodes extending over 1000 cycles through in situ formation of a continuous porous network
,” Nano Lett.
14
, 716
–723
(2014
).42.
F.
Shen
, J.
Wang
, Z.
Xu
, Y.
Wu
, Q.
Chen
, L.
Xiaoguang
, X.
Jie
, L.
Li
, M.
Yao
, X.
Guo
, and T.
Zhu
, “Rapid flu diagnosis using silicon nanowire sensor
,” Nano Lett.
12
, 3722
–3730
(2012
).43.
S.
Barth
, R.
Jimenez-Diaz
, J.
Samà
, J. D.
Prades
, I.
Gracia
, J.
Santander
, C.
Canec
, and A.
Romano-Rodriguez
, “Localized growth and in situ integration of nanowires for device applications
,” Chem. Commun.
48
, 4734
–4736
(2012
).44.
A. M.
Chockla
and B. A.
Korgel
, “Seeded germanium nanowire synthesis in solution
,” J. Mater. Chem.
19
, 996
–1001
(2009
).45.
J. S.
Kasper
and S. M.
Richards
, “The crystal structures of new forms of silicon and germanium
,” Acta Crystallogr.
17
, 752
–755
(1964
).46.
S.
Bao
, D.
Kim
, C.
Onwukaeme
, S.
Gupta
, K.
Saraswat
, K. H.
Lee
, Y.
Kim
, D.
Min
, Y.
Jung
, H.
Qiu
, H.
Wang
, E. A.
Fitzgerald
, C. T.
Seng
, and D.
Nam
, “Low-threshold optically pumped lasing in highly strained germanium nanowires
,” Nat. Commun.
8
, 1845
(2017
).47.
C.
Adamo
and V.
Barone
, “Toward reliable density functional methods without adjustable parameters: The pbe0 model
,” J. Chem. Phys.
110
, 6158
–6170
(1999
).48.
A. S.
Cooper
, “Precise lattice constants of germanium, aluminum, gallium arsenide, uranium, sulphur, quartz and sapphire
,” Acta Crystallogr.
15
, 578
–582
(1962
).49.
M.
Balkanski
, R. F.
Wallis
, and E.
Haro
, “Anharmonic effects in light scattering due to optical phonons in silicon
,” Phys. Rev. B
28
, 1928
–1934
(1983
).50.
D.
Majumdar
, S.
Biswas
, T.
Ghoshal
, J. D.
Holmes
, and A.
Singha
, “Probing thermal flux in twinned Ge nanowires through Raman spectroscopy
,” ACS Appl. Mater. Interfaces
7
, 24679
–24685
(2015
).51.
A.
Cassidy
, N.
Tsud
, S.
Bercha
, V.
Feyer
, K. C.
Prince
, and O.
Plekan
, “Adsorption of 5-Fluorouracil on Au (111) and Cu (111) surfaces
,” AIP Adv.
9
, 085318
(2019
).52.
R.
Singha
, S.
Samanta
, S.
Chatterjee
, A.
Pariari
, D.
Majumdar
, B.
Satpati
, L.
Wang
, A.
Singha
, and P.
Mandal
, “Probing lattice dynamics and electron-phonon coupling in the topological nodal-line semimetal ZrSiS
,” Phys. Rev. B
97
, 094112
(2018
).53.
A. D.
Cicco
, A. C.
Frasini
, M.
Minicucci
, E.
Principi
, J.
Itiè
, and P.
Munsch
, “High-pressure and high-temperature study of phase transitions in solid germanium
,” Phys. Status Solidi B
240
(1
), 19
–28
(2003
).54.
M.
Omar
, “Models for mean bonding length, melting point and lattice thermal expansion of nanoparticle materials
,” Mater. Res. Bull.
47
, 3518
–3522
(2012
).55.
S.
Mamand
, M.
Omar
, and A.
Muhammad
, “Nanoscale size dependence parameters on lattice thermal conductivity of wurtzite GaN nanowires
,” Mater. Res. Bull.
47
, 1264
–1272
(2012
).56.
M.
Omar
and H.
Taha
, “Lattice dislocation in Si nanowires
,” Physica B
404
, 5203
–5206
(2009
).57.
D. S.
Kim
, H. L.
Smith
, J. L.
Niedziela
, C. W.
Li
, D. L.
Abernathy
, and B.
Fultz
, “Phonon anharmonicity in silicon from 100 to 1500 K
,” Phys. Rev. B
91
, 014307
(2015
).© 2021 Author(s). Published under an exclusive license by AIP Publishing.
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