Chemical vapor deposition of gallium sulfide: phase control by molecular design

MacInnes, Andrew N.; Power, Michael B.; Barron, Andrew R.

doi:10.1021/cm00033a027

Cited by 94 publications

(60 citation statements)

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“…Both the halite-type, and the zinc blendetype have cubic face-centered lattices, therefore they are difficult to distinguish on diffraction patterns, when preferred orientations may affect reflection intensities. It was not until a year after the first report that the authors discussed this point [107] and proposed the ª¼halite to zinc blende transformation be facile on the surface for the growing film¼º, and that ª¼during deposition on GaAs (100) the substrate surface will promote such a change¼º (GaAs is of the zinc blende-type). ªThus, while a cubic phase is determined by the precursor, its growth is enhanced by the cubic GaAs substrate.º The first experiments have shown that cubic GaS could be grown on a variety of substrates, including not only GaAs, but also borosilicate glass, Si, KBr, and Mo; [102] therefore the halite to zinc blende modification can occur without a zinc blende-type surface.…”

Section: From Alkyl Metal Chalcogenatesmentioning

confidence: 99%

“…In the same article, [107] the authors compare results obtained for the MOCVD of GaS from three structurally distinct precursors, dimeric [( t Bu) 2 Ga(l 2 -S t Bu)] 2 , tetrameric [( t Bu)Ga(l 3 -S)] 4 , and heptameric [( t Bu)Ga(l 3 -S)] 7 , in order to gain further insight into phase control by molecular design. As expected, [( t Bu)Ga(l 3 -S)] 4 yielded the cubic GaS phase, but in a narrow temperature window at about 400 C. At the same temperature, [( t Bu) 2 Ga(l 2 -S t Bu)] 2 yielded the thermodynamically stable GaS hexagonal phase as poorly crystallized films.…”

Section: From Alkyl Metal Chalcogenatesmentioning

confidence: 99%

See 1 more Smart Citation

MOCVD of Chalcogenides, Pnictides, and Heterometallic Compounds from Single-Source Molecule Precursors

Gleizes

2000

Chem. Vap. Deposition

129

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The single-source approach to processing materials as thin films by metal±organic chemical vapor deposition (MOCVD) started with pioneering works in the late 1970s and early 1980s, and has developed considerably during the late 1980s and the 1990s. The literature contains some review and feature articles dedicated to its application to various types of materials, the most recent ones appearing in the mid 1990s. The present review aims at putting together results obtained for very different materials so as to obtain a comparative view of the different approaches. Faced with the considerable amount of data accumulated over more than twenty years, the scope of this article will be deliberately and arbitrarily limited to those compounds mentioned in the title. Materials consisting of elements from the second row of the periodic table, or binary combinations including one element from the second row, will not be considered here. This article will refer to precursors that have actually been used in MOCVD processes, rather than potential MOCVD sources.

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Section: From Alkyl Metal Chalcogenatesmentioning

confidence: 99%

Section: From Alkyl Metal Chalcogenatesmentioning

confidence: 99%

MOCVD of Chalcogenides, Pnictides, and Heterometallic Compounds from Single-Source Molecule Precursors

Gleizes

2000

Chem. Vap. Deposition

129

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“…Since the initial report by McInnes et al 1 concerning a metastable cubic form of GaS, a great deal of work has been devoted to such cubic phases [2][3][4][5][6][7][8] and their role in GaAs surface passivation, 2 and metal-oxide-semiconductor field-effect transistors 5 have been investigated. In most published reports cubic GaS thin films were prepared by metal-organic chemical vapor deposition using ͓͑t-Bu͒GaS͔ 4 cubane, 7 with the purpose of checking if the ͓GaS͔ 4 cubane units of the precursor molecule were preserved in the deposited thin film.…”

Section: Introductionmentioning

confidence: 99%

First-principles study of the electronic structure of cubicGaS: Metallic versus insulating polymorphs

2007

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The electronic structure of different polymorphs of gallium sulphide ͑GaS͒ with cubic structure is investigated by means of first-principles band structure calculations in connection with experimental reports on a metastable semiconducting cubic form of this material. The expected metallic character of simple cubic phases containing one GaS group per unit cell ͑rocksalt or zinc-blende͒ is confirmed by the calculations. A cubanebased zinc-blende structure is found to exhibit a band gap which is compatible with experimental results but the unit cell parameter is much larger than the reported ones. We have also studied cubic phases containing hydrogen. It is found that two insulating polymorphs can be stable: ͑i͒ a simple cubic structure based on ͓HGaS͔ 4 cubane units and ͑ii͒ an insulating zinc-blende structure in which hydrogen atoms occupy the empty sites of the cubic unit cell. The last structure seems to be the more likely structural alternative for the phase so far described as a semiconducting cubic phase of GaS. The presence of hydrogen could explain the reported instability of cubic GaS under thermal annealing.

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“…[4] Of course, the distinction between MBMs and MDMs is not absolute. The thermolysis of [Ga( t Bu) 2 S] 2 , for example, forms the well-known hexagonal GaS, while heating the cubane-structured [Ga( t Bu)S] 4 molecule between 380 and 400 C leads to cubic GaS, a new, metastable form of GaS, which forms the thermodynamically stable hexagonal form upon heating above 400 C. [5] Hence, cubic GaS might be termed an MBM, and hexagonal GaS an MDM. Other examples could be cited where a material can be made as either an MBM or MDM, or an MDM can be converted to an MBM, for example, via intercalation of a molecular component.…”

Section: Introductionmentioning

confidence: 99%

From Molecules to Materials: Current Trends and Future Directions

et al. 1998

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The development, characterization, and exploitation of novel materials based on the assembly of molecular components is an exceptionally active and rapidly expanding field. For this reason, the topic of molecule-based materials (MBMs) was chosen as the subject of a workshop sponsored by the Chemical Sciences Division of the United States Department of Energy. The purpose of the workshop was to review and discuss the diverse research trajectories in the field from a chemical perspective, and to focus on the critical elements that are likely to be essential for rapid progress. The MBMs discussed encompass a diverse set of compositions and structures, including clusters, supramolecular assemblies, and assemblies incorporating biomolecule-based components. A full range of potentially interesting materials properties, including electronic, magnetic, optical, structural, mechanical, and chemical characteristics were considered. Key themes of the workshop included synthesis of novel components, structural control, characterization of structure and properties, and the development of underlying principles and models. MBMs, defined as ªuseful substances prepared from molecules or molecular ions that maintain aspects of the parent molecular frameworkº are of special significance because of the capacity for diversity in composition, structure, and properties, both chemical and physical. Key attributes are the ability in MBMs to access the additional dimension of multiple length scales and available structural complexity via organic chemistry synthetic methodologies and the innovative assembly of such diverse components. The interaction among the assembled components can thus lead to unique behavior. A consequence of the complexity is the need for a multiplicity of both existing and new tools for materials synthesis, assembly, characterization, and theoretical analysis. For some technologically useful properties, e.g., ferro-or ferrimagnetism and superconductivity, the property is not a property of a molecule or ion; it is a cooperative solid-state (bulk) propertyÐa property of the entire solid. Hence, the desired properties are a consequence of the interactions between the molecules or ions, and understanding the solidstate structure as well as methods to predict, control, and modulate the structure are essential to understanding and manipulating such behaviors. As challenging as this is, molecules enable a substantially greater ability of control than atoms as building blocks for new materials and thus are well positioned to contribute significantly to new materials. The diversity of components and processes leads to the recognition of the critical role of cross-disciplinary research, including not only that between traditionally different areas within chemistry, but also between chemistry and biochemistry, physics, and a number of engineering disciplines. Enhancing communication and active collaboration between these groups was seen as a critical goal for the research area.

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Chemical vapor deposition of gallium sulfide: phase control by molecular design

Cited by 94 publications

References 0 publications

MOCVD of Chalcogenides, Pnictides, and Heterometallic Compounds from Single-Source Molecule Precursors

MOCVD of Chalcogenides, Pnictides, and Heterometallic Compounds from Single-Source Molecule Precursors

First-principles study of the electronic structure of cubicGaS: Metallic versus insulating polymorphs

From Molecules to Materials: Current Trends and Future Directions

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