Abstract

Semiconductors with the general formula Al(As 1-xP x)Si 3 have been theoretically studied and synthesized. These new materials are grown on Si(100) at 490-500 °C as single-phase epitaxial layers with monocrystalline diamond-like structures using reactions of Al atomic beams with As(SiH 3) 3 and P(SiH 3) 3 molecular sources. An intriguing outcome of the reaction behavior is that there appears to be no preference in the interaction between Al and the As(SiH 3) 3 and P(SiH 3) 3 coreactants, leading to the organized assembly of the corresponding Al-As-Si 3 and Al-P-Si 3 building blocks into a tetrahedral lattice in which the P/As atoms are arranged in a common third nearest neighbor sublattice in a manner that precludes the formation of energetically unfavorable Al-Al bonds. The translation of these molecular building blocks into the crystalline structures is elucidated using quantum chemistry. A general crystallographic description for the primitive cell is introduced and used to carry out first principle calculations of the structural, thermodynamic and electronic properties of AlP 1-xAs xSi 3. The results indicate that these materials are indirect gap semiconductors with indirect gaps similar to that of Si but with smaller direct gaps, which should increase their absorption coefficients. Raman spectroscopy provides a qualitative confirmation of these predictions as well as important clues on the orientational order of the tetrahedral building blocks that make up these novel materials. In the context of device design, strain analysis of Al(As 1-xP x)Si 3 indicates that the films are tetragonally compressed due to an inherent 0.8% (or less) lattice mismatch with the Si substrate. At the highest mismatch of 1.6%, strain relaxation is observed for thicknesses exceeding 40 nm, producing prototype layers with bulk-like behavior. Collectively, the results demonstrate that it may be feasible to design and prepare a host of similar systems in this general class of semiconductors with potential optoelectronic applications, including photovoltaics.

Original languageEnglish (US)
Pages (from-to)2347-2355
Number of pages9
JournalChemistry of Materials
Volume24
Issue number12
DOIs
StatePublished - Jun 26 2012

Fingerprint

Semiconductor materials
Atomic beams
Strain relaxation
Quantum chemistry
Diamond
Lattice mismatch
Epitaxial layers
Polysilicon
Electronic properties
Optoelectronic devices
Raman spectroscopy
Structural properties
Diamonds
Thermodynamic properties
Crystalline materials
Atoms
Substrates

Keywords

  • group-IV semiconductors
  • III-V compounds
  • semiconductor alloys

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Synthesis and properties of monocrystalline Al(As 1-xP x)Si 3 alloys on Si(100). / Grzybowski, G.; Watkins, T.; Beeler, R. T.; Jiang, L.; Smith, David; Chizmeshya, Andrew; Kouvetakis, John; Menendez, Jose.

In: Chemistry of Materials, Vol. 24, No. 12, 26.06.2012, p. 2347-2355.

Research output: Contribution to journalArticle

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abstract = "Semiconductors with the general formula Al(As 1-xP x)Si 3 have been theoretically studied and synthesized. These new materials are grown on Si(100) at 490-500 °C as single-phase epitaxial layers with monocrystalline diamond-like structures using reactions of Al atomic beams with As(SiH 3) 3 and P(SiH 3) 3 molecular sources. An intriguing outcome of the reaction behavior is that there appears to be no preference in the interaction between Al and the As(SiH 3) 3 and P(SiH 3) 3 coreactants, leading to the organized assembly of the corresponding Al-As-Si 3 and Al-P-Si 3 building blocks into a tetrahedral lattice in which the P/As atoms are arranged in a common third nearest neighbor sublattice in a manner that precludes the formation of energetically unfavorable Al-Al bonds. The translation of these molecular building blocks into the crystalline structures is elucidated using quantum chemistry. A general crystallographic description for the primitive cell is introduced and used to carry out first principle calculations of the structural, thermodynamic and electronic properties of AlP 1-xAs xSi 3. The results indicate that these materials are indirect gap semiconductors with indirect gaps similar to that of Si but with smaller direct gaps, which should increase their absorption coefficients. Raman spectroscopy provides a qualitative confirmation of these predictions as well as important clues on the orientational order of the tetrahedral building blocks that make up these novel materials. In the context of device design, strain analysis of Al(As 1-xP x)Si 3 indicates that the films are tetragonally compressed due to an inherent 0.8{\%} (or less) lattice mismatch with the Si substrate. At the highest mismatch of 1.6{\%}, strain relaxation is observed for thicknesses exceeding 40 nm, producing prototype layers with bulk-like behavior. Collectively, the results demonstrate that it may be feasible to design and prepare a host of similar systems in this general class of semiconductors with potential optoelectronic applications, including photovoltaics.",
keywords = "group-IV semiconductors, III-V compounds, semiconductor alloys",
author = "G. Grzybowski and T. Watkins and Beeler, {R. T.} and L. Jiang and David Smith and Andrew Chizmeshya and John Kouvetakis and Jose Menendez",
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T1 - Synthesis and properties of monocrystalline Al(As 1-xP x)Si 3 alloys on Si(100)

AU - Grzybowski, G.

AU - Watkins, T.

AU - Beeler, R. T.

AU - Jiang, L.

AU - Smith, David

AU - Chizmeshya, Andrew

AU - Kouvetakis, John

AU - Menendez, Jose

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N2 - Semiconductors with the general formula Al(As 1-xP x)Si 3 have been theoretically studied and synthesized. These new materials are grown on Si(100) at 490-500 °C as single-phase epitaxial layers with monocrystalline diamond-like structures using reactions of Al atomic beams with As(SiH 3) 3 and P(SiH 3) 3 molecular sources. An intriguing outcome of the reaction behavior is that there appears to be no preference in the interaction between Al and the As(SiH 3) 3 and P(SiH 3) 3 coreactants, leading to the organized assembly of the corresponding Al-As-Si 3 and Al-P-Si 3 building blocks into a tetrahedral lattice in which the P/As atoms are arranged in a common third nearest neighbor sublattice in a manner that precludes the formation of energetically unfavorable Al-Al bonds. The translation of these molecular building blocks into the crystalline structures is elucidated using quantum chemistry. A general crystallographic description for the primitive cell is introduced and used to carry out first principle calculations of the structural, thermodynamic and electronic properties of AlP 1-xAs xSi 3. The results indicate that these materials are indirect gap semiconductors with indirect gaps similar to that of Si but with smaller direct gaps, which should increase their absorption coefficients. Raman spectroscopy provides a qualitative confirmation of these predictions as well as important clues on the orientational order of the tetrahedral building blocks that make up these novel materials. In the context of device design, strain analysis of Al(As 1-xP x)Si 3 indicates that the films are tetragonally compressed due to an inherent 0.8% (or less) lattice mismatch with the Si substrate. At the highest mismatch of 1.6%, strain relaxation is observed for thicknesses exceeding 40 nm, producing prototype layers with bulk-like behavior. Collectively, the results demonstrate that it may be feasible to design and prepare a host of similar systems in this general class of semiconductors with potential optoelectronic applications, including photovoltaics.

AB - Semiconductors with the general formula Al(As 1-xP x)Si 3 have been theoretically studied and synthesized. These new materials are grown on Si(100) at 490-500 °C as single-phase epitaxial layers with monocrystalline diamond-like structures using reactions of Al atomic beams with As(SiH 3) 3 and P(SiH 3) 3 molecular sources. An intriguing outcome of the reaction behavior is that there appears to be no preference in the interaction between Al and the As(SiH 3) 3 and P(SiH 3) 3 coreactants, leading to the organized assembly of the corresponding Al-As-Si 3 and Al-P-Si 3 building blocks into a tetrahedral lattice in which the P/As atoms are arranged in a common third nearest neighbor sublattice in a manner that precludes the formation of energetically unfavorable Al-Al bonds. The translation of these molecular building blocks into the crystalline structures is elucidated using quantum chemistry. A general crystallographic description for the primitive cell is introduced and used to carry out first principle calculations of the structural, thermodynamic and electronic properties of AlP 1-xAs xSi 3. The results indicate that these materials are indirect gap semiconductors with indirect gaps similar to that of Si but with smaller direct gaps, which should increase their absorption coefficients. Raman spectroscopy provides a qualitative confirmation of these predictions as well as important clues on the orientational order of the tetrahedral building blocks that make up these novel materials. In the context of device design, strain analysis of Al(As 1-xP x)Si 3 indicates that the films are tetragonally compressed due to an inherent 0.8% (or less) lattice mismatch with the Si substrate. At the highest mismatch of 1.6%, strain relaxation is observed for thicknesses exceeding 40 nm, producing prototype layers with bulk-like behavior. Collectively, the results demonstrate that it may be feasible to design and prepare a host of similar systems in this general class of semiconductors with potential optoelectronic applications, including photovoltaics.

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