Novel methods for CVD of Ge4C and (Ge4C)(x)Si(y) diamond-like semiconductor heterostructures: Synthetic pathways and structures of trigermyl-(GeH3)3CH and tetragermyl-(GeH3)4C methanes

John Kouvetakis, Arne Haaland, Dmitry J. Shorokhov, Hans Vidar Volden, Georgii V. Girichev, Vasili I. Sokolov, Phillip Matsunaga

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

GeX2·dioxane (X = Cl, Br) complexes insert completely into CBr4 to afford the sterically crowded cluster compounds (BrCl2Ge)4C (1) and (Br3Ge)4C (2) in 80% and 95% yields, respectively. These display physical, spectroscopic, and structural properties that are indicative of highly symmetric molecules with a remarkably strained carbon center. Compounds 1 and 2 react with LiAlH4 to produce the hydrides (H3Ge)3CH (3) and (H3Ge)4C (4) which are readily identified and characterized by spectroscopic methods and gas-phase electron diffraction. Compound 3 is also conveniently prepared from.the LiAlH4 reduction of (GeBr3)3CH (5) which in turn is obtained by insertion of GeBr2·dioxane into the C-Br bonds of bromoform. Refinement of the diffraction data for 3 confirmed a model of C3 symmetry, with local C(3v) symmetry of the GeH3 groups, and gave a Ge-C bond length of 1.96 Å. The structure refinement of 4 was based on a model of T symmetry and displayed a rather normal Ge-C bond distance of 1.97 Å, which is substantially shorter than that (2.049 Å) of the strained (Br3Ge)4C (2) compound. Density functional calculations closely reproduced the observed molecular structures for 3 and 4. The thermal dehydrogenation of 4 on (100) Si surfaces at 500°C resulted in the growth of a diamond-structured material with an approximate composition of Ge4C. Reactions of 4 with (SiH3)2 on Si yielded heteroepitaxial growth of metastable, monocrystalline (Ge4C)(x)Si(y) alloy semiconductors that are intended to have band gaps wider than those of pure Si and Si(1-x)Ge(x) alloys and strained superlattices. The covalent cluster species described here not only are of intrinsic molecular interest but also provide a unique route to a new class of semiconductor materials and form a model for local carbon sites in Ge-C crystals and related electronic materials based on the diamond structure.

Original languageEnglish (US)
Pages (from-to)6738-6744
Number of pages7
JournalJournal of the American Chemical Society
Volume120
Issue number27
DOIs
StatePublished - Jul 15 1998

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Semiconductors
Diamond
Methane
Heterojunctions
Chemical vapor deposition
Diamonds
Carbon
Semiconductor materials
Growth
Molecular Structure
Hot Temperature
Gases
Superlattices
Bond length
Electrons
Dehydrogenation
Epitaxial growth
Hydrides
Electron diffraction
Molecular structure

ASJC Scopus subject areas

  • Chemistry(all)

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Novel methods for CVD of Ge4C and (Ge4C)(x)Si(y) diamond-like semiconductor heterostructures : Synthetic pathways and structures of trigermyl-(GeH3)3CH and tetragermyl-(GeH3)4C methanes. / Kouvetakis, John; Haaland, Arne; Shorokhov, Dmitry J.; Volden, Hans Vidar; Girichev, Georgii V.; Sokolov, Vasili I.; Matsunaga, Phillip.

In: Journal of the American Chemical Society, Vol. 120, No. 27, 15.07.1998, p. 6738-6744.

Research output: Contribution to journalArticle

Kouvetakis, John ; Haaland, Arne ; Shorokhov, Dmitry J. ; Volden, Hans Vidar ; Girichev, Georgii V. ; Sokolov, Vasili I. ; Matsunaga, Phillip. / Novel methods for CVD of Ge4C and (Ge4C)(x)Si(y) diamond-like semiconductor heterostructures : Synthetic pathways and structures of trigermyl-(GeH3)3CH and tetragermyl-(GeH3)4C methanes. In: Journal of the American Chemical Society. 1998 ; Vol. 120, No. 27. pp. 6738-6744.
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title = "Novel methods for CVD of Ge4C and (Ge4C)(x)Si(y) diamond-like semiconductor heterostructures: Synthetic pathways and structures of trigermyl-(GeH3)3CH and tetragermyl-(GeH3)4C methanes",
abstract = "GeX2·dioxane (X = Cl, Br) complexes insert completely into CBr4 to afford the sterically crowded cluster compounds (BrCl2Ge)4C (1) and (Br3Ge)4C (2) in 80{\%} and 95{\%} yields, respectively. These display physical, spectroscopic, and structural properties that are indicative of highly symmetric molecules with a remarkably strained carbon center. Compounds 1 and 2 react with LiAlH4 to produce the hydrides (H3Ge)3CH (3) and (H3Ge)4C (4) which are readily identified and characterized by spectroscopic methods and gas-phase electron diffraction. Compound 3 is also conveniently prepared from.the LiAlH4 reduction of (GeBr3)3CH (5) which in turn is obtained by insertion of GeBr2·dioxane into the C-Br bonds of bromoform. Refinement of the diffraction data for 3 confirmed a model of C3 symmetry, with local C(3v) symmetry of the GeH3 groups, and gave a Ge-C bond length of 1.96 {\AA}. The structure refinement of 4 was based on a model of T symmetry and displayed a rather normal Ge-C bond distance of 1.97 {\AA}, which is substantially shorter than that (2.049 {\AA}) of the strained (Br3Ge)4C (2) compound. Density functional calculations closely reproduced the observed molecular structures for 3 and 4. The thermal dehydrogenation of 4 on (100) Si surfaces at 500°C resulted in the growth of a diamond-structured material with an approximate composition of Ge4C. Reactions of 4 with (SiH3)2 on Si yielded heteroepitaxial growth of metastable, monocrystalline (Ge4C)(x)Si(y) alloy semiconductors that are intended to have band gaps wider than those of pure Si and Si(1-x)Ge(x) alloys and strained superlattices. The covalent cluster species described here not only are of intrinsic molecular interest but also provide a unique route to a new class of semiconductor materials and form a model for local carbon sites in Ge-C crystals and related electronic materials based on the diamond structure.",
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T1 - Novel methods for CVD of Ge4C and (Ge4C)(x)Si(y) diamond-like semiconductor heterostructures

T2 - Synthetic pathways and structures of trigermyl-(GeH3)3CH and tetragermyl-(GeH3)4C methanes

AU - Kouvetakis, John

AU - Haaland, Arne

AU - Shorokhov, Dmitry J.

AU - Volden, Hans Vidar

AU - Girichev, Georgii V.

AU - Sokolov, Vasili I.

AU - Matsunaga, Phillip

PY - 1998/7/15

Y1 - 1998/7/15

N2 - GeX2·dioxane (X = Cl, Br) complexes insert completely into CBr4 to afford the sterically crowded cluster compounds (BrCl2Ge)4C (1) and (Br3Ge)4C (2) in 80% and 95% yields, respectively. These display physical, spectroscopic, and structural properties that are indicative of highly symmetric molecules with a remarkably strained carbon center. Compounds 1 and 2 react with LiAlH4 to produce the hydrides (H3Ge)3CH (3) and (H3Ge)4C (4) which are readily identified and characterized by spectroscopic methods and gas-phase electron diffraction. Compound 3 is also conveniently prepared from.the LiAlH4 reduction of (GeBr3)3CH (5) which in turn is obtained by insertion of GeBr2·dioxane into the C-Br bonds of bromoform. Refinement of the diffraction data for 3 confirmed a model of C3 symmetry, with local C(3v) symmetry of the GeH3 groups, and gave a Ge-C bond length of 1.96 Å. The structure refinement of 4 was based on a model of T symmetry and displayed a rather normal Ge-C bond distance of 1.97 Å, which is substantially shorter than that (2.049 Å) of the strained (Br3Ge)4C (2) compound. Density functional calculations closely reproduced the observed molecular structures for 3 and 4. The thermal dehydrogenation of 4 on (100) Si surfaces at 500°C resulted in the growth of a diamond-structured material with an approximate composition of Ge4C. Reactions of 4 with (SiH3)2 on Si yielded heteroepitaxial growth of metastable, monocrystalline (Ge4C)(x)Si(y) alloy semiconductors that are intended to have band gaps wider than those of pure Si and Si(1-x)Ge(x) alloys and strained superlattices. The covalent cluster species described here not only are of intrinsic molecular interest but also provide a unique route to a new class of semiconductor materials and form a model for local carbon sites in Ge-C crystals and related electronic materials based on the diamond structure.

AB - GeX2·dioxane (X = Cl, Br) complexes insert completely into CBr4 to afford the sterically crowded cluster compounds (BrCl2Ge)4C (1) and (Br3Ge)4C (2) in 80% and 95% yields, respectively. These display physical, spectroscopic, and structural properties that are indicative of highly symmetric molecules with a remarkably strained carbon center. Compounds 1 and 2 react with LiAlH4 to produce the hydrides (H3Ge)3CH (3) and (H3Ge)4C (4) which are readily identified and characterized by spectroscopic methods and gas-phase electron diffraction. Compound 3 is also conveniently prepared from.the LiAlH4 reduction of (GeBr3)3CH (5) which in turn is obtained by insertion of GeBr2·dioxane into the C-Br bonds of bromoform. Refinement of the diffraction data for 3 confirmed a model of C3 symmetry, with local C(3v) symmetry of the GeH3 groups, and gave a Ge-C bond length of 1.96 Å. The structure refinement of 4 was based on a model of T symmetry and displayed a rather normal Ge-C bond distance of 1.97 Å, which is substantially shorter than that (2.049 Å) of the strained (Br3Ge)4C (2) compound. Density functional calculations closely reproduced the observed molecular structures for 3 and 4. The thermal dehydrogenation of 4 on (100) Si surfaces at 500°C resulted in the growth of a diamond-structured material with an approximate composition of Ge4C. Reactions of 4 with (SiH3)2 on Si yielded heteroepitaxial growth of metastable, monocrystalline (Ge4C)(x)Si(y) alloy semiconductors that are intended to have band gaps wider than those of pure Si and Si(1-x)Ge(x) alloys and strained superlattices. The covalent cluster species described here not only are of intrinsic molecular interest but also provide a unique route to a new class of semiconductor materials and form a model for local carbon sites in Ge-C crystals and related electronic materials based on the diamond structure.

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