Nucleation of nanocrystalline diamond by fragmentation of fullerene precursors.
Growth of diamond films from C{sub 60}/Ar microwave discharges results in a nanocrystalline microstructure with crystallite sizes in the range 3-10 nm. Heterogeneous nucleation rates of 10{sup 10} cm{sup {minus}2} sec are required to account for the results. The nucleation mechanism presented here fulfills this requirement and is based on the insertion of carbon dimer, C{sub 2}, molecules, produced by fragmentation of C{sub 60}, into the n-bonded dimer rows of the reconstructed (100) surface of diamond. Density functional theory is used to calculate the energetic of C{sub 2} insertion into carbon clusters that model the (100) surface. The reaction of singlet C{sub 2} with the double bond of the C{sub 9}H{sub 12} cluster leads to either carbene structures or a cyclobutynelike structure. At the HF/6-31G* level, the carbene product has a C{sub 2v} structure, while at the B3LYP/6-31G* levels of theory, it has a C{sub s} structure with the inserted C{sub 2} tilted. No barrier for insertion into the C=C double bond of the C{sub 9}H{sub 12} cluster was found at the HF/6-31G* and B3LYP/6-31G* levels of theory. Thus, calculations including correlation energy and geometry optimization indicate that insertion of C{sub 2} into a C=C double bond leads to a large energy lowering, {approximately}120 kcal/mol for a C{sub 9}H{sub 12} cluster, and there is no barrier for insertion.
- Research Organization:
- Argonne National Lab., IL (US)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 10576
- Report Number(s):
- ANL/CHM/CP-95414; TRN: AH200126%%323
- Resource Relation:
- Conference: 193rd Meeting of the Electrochemical Society, San Diego, CA (US), 05/03/1998--05/08/1998; Other Information: PBD: 4 May 1998
- Country of Publication:
- United States
- Language:
- English
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