TY - JOUR
T1 - First-principles analysis of vibrational properties of type ii sige alloy clathrates
AU - Xue, Dong
AU - Myles, Charles W.
N1 - Publisher Copyright:
© 2019 by the authors. Licensee MDPI, Basel, Switzerland.
PY - 2019/5
Y1 - 2019/5
N2 - We have mostly performed vibrational studies of Type-II silicon-germanium clathrate alloys, namely, Si136-xGex (0 < x ≤ 128), using periodic density functional theory (DFT). Our computed lattice constant for various stoichiometric amount, namely, x, of Ge agrees to some extent with the observed X-ray diffraction (XRD) data, along with monotonically increasing dependence on x. According to our bandgap energy calculation via Vienna ab initio simulation package (VASP), Si128Ge8 has a “nearly-direct” bandgap of approximately 1.27 eV, which agrees well with the previously calculated result (~1.23 eV), which was obtained using the Cambridge sequential simulation total energy package (CASTEP). Most of our first-principles calculations focus on exploring the low-energy transverse acoustic (TA) phonons that contribute dominantly to the induction of negative thermal expansion (NTE) behavior. Moreover, our work has predicted that the Si104Ge32 framework exhibits NTE in the temperature range of 3–80 K, compared to the temperature regime (10–140 K) of NTE observed in such pure Si136 . It is posited that the increased number of Ge–Ge bonds may weaken the NTE effect substantially, as the composition, which is denoted as x, in Si136-xGex is elevated from 32 (or 40) to 96 (or 104).
AB - We have mostly performed vibrational studies of Type-II silicon-germanium clathrate alloys, namely, Si136-xGex (0 < x ≤ 128), using periodic density functional theory (DFT). Our computed lattice constant for various stoichiometric amount, namely, x, of Ge agrees to some extent with the observed X-ray diffraction (XRD) data, along with monotonically increasing dependence on x. According to our bandgap energy calculation via Vienna ab initio simulation package (VASP), Si128Ge8 has a “nearly-direct” bandgap of approximately 1.27 eV, which agrees well with the previously calculated result (~1.23 eV), which was obtained using the Cambridge sequential simulation total energy package (CASTEP). Most of our first-principles calculations focus on exploring the low-energy transverse acoustic (TA) phonons that contribute dominantly to the induction of negative thermal expansion (NTE) behavior. Moreover, our work has predicted that the Si104Ge32 framework exhibits NTE in the temperature range of 3–80 K, compared to the temperature regime (10–140 K) of NTE observed in such pure Si136 . It is posited that the increased number of Ge–Ge bonds may weaken the NTE effect substantially, as the composition, which is denoted as x, in Si136-xGex is elevated from 32 (or 40) to 96 (or 104).
KW - Alloy clathrate
KW - Mode Grüneisen parameter
KW - Negative thermal expansion
KW - Quasi-harmonic approximation
UR - http://www.scopus.com/inward/record.url?scp=85067188632&partnerID=8YFLogxK
U2 - 10.3390/nano9050723
DO - 10.3390/nano9050723
M3 - Article
AN - SCOPUS:85067188632
SN - 2079-4991
VL - 9
JO - Nanomaterials
JF - Nanomaterials
IS - 5
M1 - 723
ER -