TY - JOUR
T1 - First-principles computational design and synthesis of hybrid carbon-silicon clathrates
AU - Chan, Kwai S.
AU - Miller, Michael A.
AU - Liang, Wuwei
AU - Ellis-Terrell, Carol
AU - Peng, Xihong
N1 - Funding Information:
Acknowledgements This work was supported by The Internal Research Program of Southwest Research Institute (KSC, MAM, WL, and C E-T) and Faculty Scholarship Award from the School of Letters and Sciences (XP) at Arizona State University (ASU). We acknowledge the Texas Advanced Computing Center of the TerraGrid Network and the Extreme Science and Engineering Discovery Environment (XSEDE) High Performance Computing Facilities for providing the computational resources for the CPMD calculations. We also acknowledge the ASU Advanced Computing Center for providing computational resources on Saguaro Cluster for the VASP calculations. Clerical assistance by Ms. L. Salas, SwRI, in the preparation of this manuscript is acknowledged.
PY - 2014/4
Y1 - 2014/4
N2 - Type I and Type II silicon clathrates (Si46 and Si 136), which can be considered as analogs of carbon fullerene materials, are composed with face-sharing Si20, Si24, and Si28 cages linked through sp 3-covalent bonds. Besides silicon clathrates, theoretical computations have shown that both Type I carbon clathrate (C46) and Type II carbon clathrate (C136) may exist as metastable phases under high pressures. However, the energies of formation for the Type I and Type II carbon clathrates are extremely high and neither Type I nor Type II carbon clathrates have been synthesized. The objective of this investigation was to develop Type I hybrid carbon-silicon clathrates by substituting atoms on the silicon clathrate framework with C atoms. A first-principles computational approach was first utilized to design the framework structure and to identify appropriate guest atoms that are amenable to the formation of hybrid carbon-silicon clathrate compounds. A new class of Type I clathrates based on the carbon-silicon system was discovered as potential candidates. Some of the promising candidate clathrates were synthesized using an industrial arc-melting technique. The yield and stability of these newly discovered clathrates were evaluated. In addition, the electronic properties of selected clathrate materials were predicted using first-principles computations, which showed profound influences of the electronic properties by C atom substitution on the Si framework and insertion of guest atoms into the cage structure.
AB - Type I and Type II silicon clathrates (Si46 and Si 136), which can be considered as analogs of carbon fullerene materials, are composed with face-sharing Si20, Si24, and Si28 cages linked through sp 3-covalent bonds. Besides silicon clathrates, theoretical computations have shown that both Type I carbon clathrate (C46) and Type II carbon clathrate (C136) may exist as metastable phases under high pressures. However, the energies of formation for the Type I and Type II carbon clathrates are extremely high and neither Type I nor Type II carbon clathrates have been synthesized. The objective of this investigation was to develop Type I hybrid carbon-silicon clathrates by substituting atoms on the silicon clathrate framework with C atoms. A first-principles computational approach was first utilized to design the framework structure and to identify appropriate guest atoms that are amenable to the formation of hybrid carbon-silicon clathrate compounds. A new class of Type I clathrates based on the carbon-silicon system was discovered as potential candidates. Some of the promising candidate clathrates were synthesized using an industrial arc-melting technique. The yield and stability of these newly discovered clathrates were evaluated. In addition, the electronic properties of selected clathrate materials were predicted using first-principles computations, which showed profound influences of the electronic properties by C atom substitution on the Si framework and insertion of guest atoms into the cage structure.
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U2 - 10.1007/s10853-013-7973-6
DO - 10.1007/s10853-013-7973-6
M3 - Article
AN - SCOPUS:84893698204
SN - 0022-2461
VL - 49
SP - 2723
EP - 2733
JO - Journal of Materials Science
JF - Journal of Materials Science
IS - 7
ER -