Gallium Chloride Research Articles

Monochlorogallane: physical properties and structure of the gaseous molecule H2Ga(mu-Cl)2GaH2 as determined by vibrational, electron diffraction, and ab initio studies.

Monochlorogallane, synthesized by the metathesis of gallium(III) chloride with an excess of trimethylsilane at ca. 250 K, has been characterized by chemical analysis, by its IR, Raman, and 1H NMR spectra, and by the products of its reaction with trimethylamine. The vibrational spectra of the vapor species isolated in solid Ar, N2, or CH4 matrixes at ca. 12 K imply the presence of only one species, viz. the dimer with an equilibrium structure conforming to D2h symmetry. The structure of this molecule has been determined by gas-phase electron diffraction (GED) measurements augmented by the results of ab initio molecular orbital calculations. An equilibrium structure with D2h symmetry has been assumed in the analysis of the electron diffraction pattern. However, as the molecule has a very low frequency Ga(mu-Cl)2Ga ring-puckering mode, a dynamic model was used to describe it with the aid of a set of pseudoconformers spaced at even intervals (deltadelta = 5 degrees, deltamax, = 20 delta) around the ring-puckering angle delta and Boltzmann-weighted according to a quartic potential V(delta) = V4delta4 + V2delta2. The differences in bond distances and angles between the different pseudoconformers were constrained to the values derived from the ab initio calculations employing second-order Moller-Plesset (MP2) methods (with all the electrons included in the correlation calculations) and a 6-311G(d) basis set. The results for the weighted average of the principal distances (ralpha) and angles (<alpha) (with estimated 1sigma uncertainties) from the combined GED/ab initio study are r(Ga-Cl) 2.350(2) A, r(Ga-H) 1.523(20) A, <Cl-Ga-Cl 89.7(5)degrees, <H-Ga-H 135.1 degrees, V4 3.0 x 10(-6) kcal mol(-1) deg(-4), and V2 6.0 x 10(-4) kcal mol(-1) deg(-2).

Clinical evaluation and microstructural analysis of a direct placement gallium restorative alloy

Objectives: The objective of this study was to assess the clinical performance of a direct placement gallium alloy sealed with an established dentine adhesive system. In addition, microanalysis of a few gallium restorations that failed in clinical service was performed. Clinical factors such as pulpal sensitivity, fracture of the restoration and of the tooth, marginal deterioration, and tarnish were assessed.Methods: Sixty-five restorations of Galloy and 62 of Tytin (49 and 51 Class II restorations, respectively) were placed according to a predetermined scheme for randomisation in 37 patients by two operators using rubber dam isolation. For the Galloy restorations, the enamel and dentine were etched, and then sealed with PAAMA 2 dentine adhesive according to the manufacturer's instructions. After carving, PAAMA 2 was applied to the Galloy and light-cured. Cavity preparations for Tytin received no adhesive sealer. All restorations were polished at least 24h post-operatively. Microstructural analysis of retrieved fragments of failed restorations was conducted using electron probe microanalysis.Results: At 1year, only one Tytin restoration was found to have failed due to an isthmus fracture. The remaining restorations of Tytin were intact with no reported sensitivity. Of the 65 Galloy restorations placed, 28 had to be removed, including restorations in teeth, which were symptomatic, non-vital and/or fractured, and teeth with fractured restorations. Tarnish was present on many of the Galloy restorations. Retrieved fragments of failed Galloy restorations exhibited a dark surface at the pulpal wall interface and small cracks were observed in that surface. Internal cracks and extensive corrosion was observed using the microprobe. Gallium oxides and chlorides were identified as the predominant corrosion products.Conclusions: The gallium alloy, Galloy, sealed with PAAMA 2 dentine adhesive system demonstrated a high clinical failure rate.

The Dramatic Influence of Diamidoamine Ligands on the Structure and Reactivity of Low-Valent Tin and Bismuth Derivatives

The dilithium salts of N-methyl-N′,N′′-bis(diisopropyl)- and -(trimethylsilyl)-diethylenetriamine 1a,b react with SnCl2 affording the corresponding stannylenes 2a,b in 60 and 80% yield, respectively. Compound 1b also reacts with BiCl3 to give the bismuth chloride 5 (90% yield). Derivatives 2b and 5 have a symmetrical bicyclic structure and are monomeric both in solution and in the solid state. When 2b is treated with BiCl3 or PCl3, an oxidation reaction leads to the hypercoordinated tin(IV) dichloride 3 (58% yield), or a transmetallation gives rise to the oniophosphane 4 (95% yield), respectively. Transmetalation reactions also occurred when 5 was treated with AlCl3, GaCl3 or SnCl2 affording the corresponding aluminum chloride 6 (81% yield), gallium chloride 7 (38% yield) or tin dichloride 3 (38% yield). The observed reactivity for 2 and 5 is compared to that reported for Veith's stannylene or bismuth chloride.

Formation of etch pits during carbon doping of gallium arsenide with carbon tetrachloride by metalorganic vapor-phase epitaxy

Scanning tunneling microscopy was used to examine the effects of carbon tetrachloride concentration and temperature on the morphology of carbon-doped gallium arsenide films grown by metalorganic vapor-phase epitaxy. Deposition was carried out at 505–545 °C, a V/III ratio of 75, and IV/III ratios between 0.5 and 5.0. The growth rate declined monotonically with increasing carbon tetrachloride concentration. Step bunching and pinning was observed at a IV/III ratio of approximately 2.5. Increasing this ratio further resulted in the formation of pits ranging from 20 to 50 nm in diameter. These results can be explained by two competing processes that occur at the step edges: (1) the reaction of chlorine with adsorbed gallium from the group III precursor, and (2) the reaction of chlorine with gallium arsenide. Both reactions desorb gallium chlorides and reduce the growth rate, but only the latter reaction produces pits.

Microtubule-disrupting effects of gallium chloride in vitro.

Gallium chloride (GaCl3), an antitumor agent with antagonistic action on iron, magnesium and calcium, was tested for its ability to alter the polymerization of purified tubulin (2.2 mg/ml) in a cell-free system in vitro. GaCl3 (250 microM) does not mimic the effect of 10 microM paclitaxel and, therefore, is not a microtubule (MT)-stabilizing agent that can promote tubulin polymerization in the absence of glycerol and block MT disassembly. In contrast, GaCl3 mimics the effect of 1 microM vincristine (VCR) and inhibits glycerol-induced tubulin polymerization in a concentration-dependent manner (IC50: 125 microM), indicating that GaCl3 is a MT de-stabilizing agent that prevents MT assembly. However, 150 microM GaCl3 must be used to match or surpass the inhibitions of tubulin polymerization caused by 0.25 microM of known MT de-stabilizing agents, such as colchicine (CLC), nocodazole, podophyllotoxin, tubulozole-C and VCR. The inhibitory effect of 250 microM GaCl3 persists in the presence of up to 9 mM MgCl2, suggesting that the exogenous Mg2+ cations absolutely required for the binding of GTP to tubulin and MT assembly cannot overcome the antitubulin action of Ga3+ ions of a higher valence. The binding of [3H]vinblastine (VBL) to tubulin (0.5 mg/ml) is inhibited by unlabeled VBL but enhanced by concentrations of GaCl3 > 200 microM. However, increasing concentrations of GaCl3 mimic the ability of cold CLC to reduce the amount of [3H]CLC bound to tubulin, suggesting that GaCl3 may interact with the CLC binding site to inhibit tubulin polymerization. The binding of [3H]GTP to tubulin is decreased by unlabeled GTP but markedly enhanced by GaCl3, especially when concentrations of this metal salt of 32 microM or higher are added to the reaction mixture before rather than after the radiolabeled nucleotide. These data suggest that changes in protein conformation following GaCl3 binding might increase the interactions of tubulin with nucleotides and Vinca alkaloids. After a 24 h delay, the viability of GaCl3-treated L1210 leukemic cells is reduced in a concentration-dependent manner at days 2 (IC50: 175 microM), 3 (IC50: 35 microM) and 4 (IC50: 16 microM). Since GaCl3 (100-625 microM) increases the percentage of mitotic cells at 2-4 days, it might arrest tumor cell progression in M phase, but its antimitotic activity is much weaker than that of 0.25 microM VCR. Because the concentrations of GaCl3 that inhibit tubulin polymerization also increase the mitotic index and decrease the viability of L1210 cells in vitro, the antitubulin and antimitotic effects of GaCl3 might contribute, at least in part, to its antitumor activity.

Syntheses and Characterization by NMR Spectroscopy and X-ray Diffraction of Complexes Derived from Metals of Groups 2 and 13 and the Ligand Bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine

Reaction of 3,5-di-tert-butylcatechol and aqueous ammonia with boron, aluminum, gallium, or strontium chloride, or with calcium or barium acetate produce, under oxidizing conditions, neutral complexes of stoichiometric formulae ML (M = BCl), ML2, [M = Al (2), Ga (3), Ca (4), and Ba (5)], and ML3H [M = Sr (6)] [L = different oxidation states of bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine]. The structures of 1 and 4–6 were established by 1H- and 13C-NMR spectroscopy and of 2, 3, and 6 by X-ray diffraction. The coordination compound ClBL (1) was obtained by transmetallation of ZnL2 with BCl3. It is a tetracyclic compound with tetracoordinated boron and nitrogen atoms, the ligand being in the reduced form, bis(hydroxyphenyl)amine. The paramagnetic complexes 2 and 3 crystallized in the triclinic system and are hexacoordinated with two orthogonal planar ligands bonded to the metal atoms. The ligands appear in two different oxidation states: one as the monoanion and another as a radical dianion. Based on their X-ray diffraction molecular structures, it is deduced that both ligands have similar structures, confirming electronic delocalization and fast interconversion of their oxidation states. Ca and Ba complexes are diamagnetic and hexacoordinated, both ligands being monoanions The strontium complex crystallized in the monoclinic system, the metal atom is nonacoordinated, having two ligands as monoanions, and a third one is a neutral protonated diquinone. Its structure is a distorted helix with three paddles in a C3 geometry and its unexpected diamagnetic behaviour is due to the presence of a reduced protonated ligand.

Syntheses and Characterization by NMR Spectroscopy and X-ray Diffraction of Complexes Derived from Metals of Groups 2 and 13 and the Ligand Bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine

Reaction of 3,5-di-tert-butylcatechol and aqueous ammonia with boron, aluminum, gallium, or strontium chloride, or with calcium or barium acetate produce, under oxidizing conditions, neutral complexes of stoichiometric formulae ML (M = BCl), ML2, [M = Al (2), Ga (3), Ca (4), and Ba (5)], and ML3H [M = Sr (6)] [L = different oxidation states of bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine]. The structures of 1 and 4–6 were established by 1H- and 13C-NMR spectroscopy and of 2, 3, and 6 by X-ray diffraction. The coordination compound ClBL (1) was obtained by transmetallation of ZnL2 with BCl3. It is a tetracyclic compound with tetracoordinated boron and nitrogen atoms, the ligand being in the reduced form, bis(hydroxyphenyl)amine. The paramagnetic complexes 2 and 3 crystallized in the triclinic system and are hexacoordinated with two orthogonal planar ligands bonded to the metal atoms. The ligands appear in two different oxidation states: one as the monoanion and another as a radical dianion. Based on their X-ray diffraction molecular structures, it is deduced that both ligands have similar structures, confirming electronic delocalization and fast interconversion of their oxidation states. Ca and Ba complexes are diamagnetic and hexacoordinated, both ligands being monoanions The strontium complex crystallized in the monoclinic system, the metal atom is nonacoordinated, having two ligands as monoanions, and a third one is a neutral protonated diquinone. Its structure is a distorted helix with three paddles in a C3 geometry and its unexpected diamagnetic behaviour is due to the presence of a reduced protonated ligand.

Reactions of [ReN(Cl)(Me 2PhP) 2(HEt 2tcb)] with Lewis Acids. Synthesis, Characterization and Structures of [Re(NBBr 3)Br 2(Me 2PhP) 3], [Re(NGaCl 3)Cl(Me 2PhP) 2(H 2Et 2tcb)][GaCl 4] and [Re{NB(C 6F 5) 3}Cl(Me 2PhP) 2(HEt 2tcb)] (H 2Et 2tcb= N,N-diethylthiocarbamoylbenzamidine)

Reactions of [ReN(Cl)(Me 2PhP) 2(HEt 2tcb)] (HEt 2tcb −= N,N-diethylthiocarbamoylbenzamidinate, Me 2PhP=dimethylphenylphosphine) with Lewis acidic compounds such as BBr 3, (C 6F 5) 3B or gallium(III) chloride yield nitrogen-bridged binuclear complexes with covalent bonds between the nitrido ligand and boron or gallium. The reactions go along with activation of the transition metal centre which can lead to ligand re-arrangements and reactions with solvent molecules. The reaction with BBr 3 results in cleavage of the bonds to the chelating ligand. [Re(NBBr 3)Br 2(Me 2PhP) 3] was isolated as the only product with a nitrido bridge. The bis-chelate [ReN(HEt 2tcb) 2] was formed as a side-product. Upon formation of a nitrido bridge to GaCl 3 the first co-ordination sphere of rhenium is retained. The co-ordinated thiocarbamoylbenzamidinate, however, undergoes protonation and is bonded as a neutral, bidentate ligand in the product [Re(NGaCl 3)Cl(Me 2PhP) 2(H 2Et 2tcb)][GaCl 4]. In [Re{NB(C 6F 5) 3}Cl(Me 2PhP) 2(HEt 2tcb)], which can be obtained in good yield from the reaction of [ReN(Cl)(Me 2PhP) 2(HEt 2tcb)] with (C 6F 5) 3B, the co-ordination environment of the metal remains essentially unchanged. X-ray structural studies on the products suggest that the strong structural trans influence of the terminal nitrido ligand in the starting complex decreases significantly as a consequence of the formation of the N–B/Ga bonds. The rhenium–nitrogen multiple bond distances, however, remain almost unchanged.

Ga2Cl4(dioxane)2]x: molecular structure and reactivity of a polymeric gallium(II) halide containing two five-coordinate gallium atoms about a Ga–Ga bond

A polymeric 1,4-dioxane adduct of gallium(II) chloride, [Ga2Cl4(dioxane)2]x, containing two five-coordinate gallium atoms about a Ga–Ga bond [Ga–Ga 2.3825(9) Å], reacts with 1,4-dilithiotetraphenylbutadiene affording an unusual Ga(II)–tetraphenylbutadiene complex.

Gallium Nitride Growth Using Diethylgallium Chloride as an Alternative Gallium Source

Metal organic vapor phase epitaxy (MOVPE) of GaN has been carried out using diethyl gallium chloride (DEGaCl) and ammonia. The growth rate and efficiency of the DEGaCl-based growth decreases with increasing temperature when compared to trimethyl gallium (TMG)-based growth under similar conditions. Both low temperature buffer and the high temperature GaN layers were grown using the DEGaCl-NH3 precursor combination on the basal plane of sapphire and compared to similar structures grown using TMG and NH3. DEGaCl-based growth reveals an improved growth behavior under identical growth conditions to the conventional TMGa and ammonia growth. X-ray, Hall, and atomic force microscopy (AFM) measurements have been carried out on these samples providing a direct comparison of materials properties associated with these growth precursors. For the DEGaCl-based growth, the x-ray rocking curve line width, using the (0002) reflection, is as low as 300 arcsec on a 2.5-micron thick film. A RMS surface roughness of ∼0.5nm measured over a 10×10 micron area.

Epitaxial Lateral Overgrowth of GaN with Chloride-Based Growth Chemistries in Both Hydride and Metalorganic Vapor Phase Epitaxy

Epitaxial lateral overgrowth (ELO) of GaN on SiO2-masked (0001) GaN substrates has been investigated by using chloride-based growth chemistries via hydride vapor phase epitaxy (HVPE) and metal organic vapor phase epitaxy (MOVPE). Diethyl gallium chloride, (C2H5)2GaCl, was used in as the MOVPE Ga precursor. The lateral and vertical growth rates as well as the overgrowth morphology of ELO GaN structures are dependent on growth temperature, V/III ratio and the in-plane orientation of the mask opening. A high growth temperature and low V/III ratio increase the lateral growth rate and produce ELO structures with a planar surface to the GaN prisms. High-quality coalesced and planar ELO GaN has been fabricated by both growth chemistries. The use of the diethyl gallium chloride source allows for the benefits of HVPE growth to be realized within the MOVPE growth environment.

Etch Processing of III-V Nitrides

As III-V nitride devices advance in technological importance, a fundamental understanding of device processing techniques becomes essential. Recent works have exposed various aspects of etch processes. The most recent advances and the greatest remaining challenges in the etching of GaN, AlN, and InN are reviewed. A more detailed presentation is given with respect to GaN high density plasma etching. In particular, the results of parametric and fundamental studies of GaN etching in a high density plasma are described. The effect of ion energy and mass on surface electronic properties is reported. Experimental results identify preferential sputtering as the leading cause of observed surface non-stoichiometry. This mechanism provides excellent surfaces for ohmic contacts to n-type GaN, but presents a major obstacle for Schottky contacts or ohmic contacts to p-type GaN. Chlorine-based discharges minimize this stoichiometry problem by improving the rate of gallium removal from the surface. In an effort to better understand the high density plasma etching process for GaN, in-situ mass spectrometry is employed to study the chlorine-based high density plasma etching process. Gallium chloride mass peaks were monitored in a highly surface sensitive geometry as a function of microwave power (ion flux), total pressure (neutral flux), and ion energy. Microwave power and pressure dependencies clearly demonstrate the importance of reactive ions in the etching of wide band gap materials. The ion energy dependence demonstrates the importance of adequate ion energy to promote a reasonable etch rate (≥100-150 eV). The benefits of ion-assisted chemical etching are diminished for ion energies in excess of 350 V, placing an upper limit to the useful ion energy range for etching GaN. The impact of these results on device processing will be discussed and future needs identified.

Synthesis and Structure of Gallium/Silicon Heterocycles with a Ga2Si2 and a Ga3Si Framework⋆

The reaction of Ga2X4· 2 dioxane with four equivalents of (Me3Si)3SiLi(thf)3 (= hypersilyllithium) affords for X = Br a 1,3,2,4-disiladigalletane together with tetrahedral hypersilylgallium(I). For X = Cl an anionic 1,2,3,4-silatrigalletanate, a four-membered heterocycle with a Ga3 unit, is isolated. These primary examples of gallium/group-14 heterocycles have been investigated by NMR spectroscopy as well as by X-ray single-crystal structure analysis. In addition, the synthesis and structure of bis(hypersilyl)gallium chloride is described. This monomeric molecule has a nearly T-shaped Si2GaCl framework.

Low-pressure chemical vapor deposition of GaN epitaxial films

GaN films were grown epitaxially on sapphire and 6H-SiC substrates by low-pressure chemical vapor deposition (LPCVD) using gallium(III) chloride and ammonia as gallium and nitrogen precursor, respectively. The properties of these samples were examined by X-ray diffraction, Hall effect measurements, secondary-ion mass spectroscopy (SIMS) and photoluminescence (PL). All GaN layers exhibit high free carrier concentrations between n=2×1018 and 5×1019cm−3 caused by unintentional n-type doping. We provide evidence that this high unintentionally doping is linked to the oxygen content in the films. The correlation between the optical properties with respect to position and line shape of the band-edge luminescence and the electrical properties, i.e. the free carrier concentration, is discussed.

The nature of lithium perchlorate and gallium chloride salt effect in cycloaddition reactions

Comparing the acceleration effects of (4+2)-, (3+2)- and (2+2)-cycloaddition reactions in the presence of the salts of two types: gallium chloride in inert solvents and lithium perchlorate (LP) in diethyl ether (DE) it was observed that in the presence of GaCl 3 the acceleration effect is approximately the same (10 4 times) for the studied reactions, while in LPDE medium for the same reactions strong increase (up to 10 4 times), weak increase or even decrease of the rate and equilibrium constants take place even with the common dienophile depending on the nature of the second reagent. It was suggested that the acceleration effect of cycloaddition reactions in the presence of such Lewis acids as aluminum, gallium or boron halides is due to the sharp increase of π-acceptor properties of dienophiles and therefore increasing energy of orbital interaction, whereas LPDE medium demonstrates strong stabilization of static and/or dynamic polar forms and favors reactions with charge control.

A study of the non-aqueous dealumination and gallium impregnation of H-mordenite by chlorinated reagents

The in vacuo dealumination of H-mordenite by carbon tetrachloride followed by gallium impregnation using gallium(III) chloride has been studied by diffuse reflectance IR spectroscopy (DRIFTS), 71Ga, 29Si, and 27Al solid-state magic-angle spinning (MAS) NMR. Comparative studies of the interaction of carbon tetrachloride with silica and γ-alumina were also performed. IR and DRIFTS analyses of silica and γ-alumina samples show that the reaction of carbon tetrachloride at elevated temperatures can completely remove silanol and aluminol moieties at the surface of the respective oxides. The removal of intra-lattice aluminium ions is consistent with abstraction by Al3+ ion pairs. Solid state 1H NMR data, in conjunction with IR and DRIFTS analysis of the dealuminated and gallium-impregnated H-mordenite samples confirms the formation of strong Brønsted acid protons by the reaction of carbon tetrachloride. The in vacuo probe reactions of H-mordenite, dealuminated H-mordenite and gallium impregnated H-mordenite, with methanol vapour, were studied as a function of temperature. The probe reactions show that the conversion of methanol vapour with the treated H-mordenite material is a function of the reaction temperature and the chemical modification to the H-mordenite. The activity of the treated H-mordenite to produce hydrocarbons from methanol follows the series gallium impregnated H-mordenite > dealuminated H-mordenite > H-mordenite. The product distribution supports the observation that the surface adsorbed mechanisms are consistent with a series of ionogenic intermolecular reactions occurring at dual Brønsted acid–base environments within the zeolite channels. These mechanisms account for the formation of higher alcohols from methanol by the combination of carbo-ionogenic moieties and hydrocarbons produced from the dehydration of alcohols.

Etch Processing of III-V Nitrides

AbstractAs III-V nitride devices advance in technological importance, a fundamental understanding of device processing techniques becomes essential. Recent works have exposed various aspects of etch processes. The most recent advances and the greatest remaining challenges in the etching of GaN, AIN, and InN are reviewed. A more detailed presentation is given with respect to GaN high density plasma etching. In particular, the results of parametric and fundamental studies of GaN etching in a high density plasma are described. The effect of ion energy and mass on surface electronic properties is reported. Experimental results identify preferential sputtering as the leading cause of observed surface non-stoichiometry. This mechanism provides excellent surfaces for ohmic contacts to n-type GaN, but presents a major obstacle for Schottky contacts or ohmic contacts to p-type GaN. Chlorine-based discharges minimize this stoichiometry problem by improving the rate of gallium removal from the surface. In an effort to better understand the high density plasma etching process for GaN, in-situ mass spectrometry is employed to study the chlorine-based high density plasma etching process. Gallium chloride mass peaks were monitored in a highly surface sensitive geometry as a function of microwave power (ion flux), total pressure (neutral flux), and ion energy. Microwave power and pressure dependencies clearly demonstrate the importance of reactive ions in the etching of wide band gap materials. The ion energy dependence demonstrates the importance of adequate ion energy to promote a reasonable etch rate (≥ 100-150 eV). The benefits of ion-assisted chemical etching are diminished for ion energies in excess of 350 V, placing an upper limit to the useful ion energy range for etching GaN. The impact of these results on device processing will be discussed and future needs identified.

Gallium Nitride Growth Using Diethylgallium Chloride as an Alternative Gallium Source

AbstractMetal organic vapor phase epitaxy (MOVPE) of GaN has been carried out using diethyl gallium chloride (DEGaCI) and ammonia. The growth rate and efficiency of the DEGaCl-based growth decreases with increasing temperature when compared to trimethyl gallium (TMG)-based growth under similar conditions. Both low temperature buffer and the high temperature GaN layers were grown using the DEGaCI-NH3 precursor combination on the basal plane of sapphire and compared to similar structures grown using TMG and NH3. DEGaCl-based growth reveals an improved growth behavior under identical growth conditions to the conventional TMGa and ammonia growth. X-ray, Hall, and atomic force microscopy (AFM) measurements have been carried out on these samples providing a direct comparison of materials properties associated with these growth precursors. For the DEGaCl-based growth, the x-ray rocking curve line width, using the (0002) reflection, is as low as 300 arcsec on a 2.5-micron thick film. A RMS surface roughness of ∼0.5nm measured over a 10x10 micron area.

Epitaxial Lateral Overgrowth of GaN with Chloride-Based Growth Chemistries in Both Hydride and Metalorganic Vapor Phase Epitaxy

AbstractEpitaxial lateral overgrowth (ELO) of GaN on SiO2-masked (0001) GaN substrates has been investigated by using chloride-based growth chemistries via hydride vapor phase epitaxy (HVPE) and metal organic vapor phase epitaxy (MOVPE). Diethyl gallium chloride, (C2H5)2GaCl, was used in as the MOVPE Ga precursor. The lateral and vertical growth rates as well as the overgrowth morphology of ELO GaN structures are dependent on growth temperature, V/III ratio and the in-plane orientation of the mask opening. A high growth temperature and low V/III ratio increase the lateral growth rate and produce ELO structures with a planar surface to the GaN prisms. High-quality coalesced and planar ELO GaN has been fabricated by both growth chemistries. The use of the diethyl gallium chloride source allows for the benefits of HVPE growth to be realized within the MOVPE growth environment.

Structural Alternatives in R2(Cl)P:GaCl3 Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Systematic NMR studies of (dialkyl/diaryl)chlorophosphine−gallium chloride reaction mixtures reveal three structural alternatives, which are related by equilibria in solution, and their relative stability is dependent on the nature of the substituent (R = Me, Et, iPr, tBu, Ph) and the reaction stoichiometry. The coordination complex R2(Cl)P→GaCl3 is observed in all cases, and a derivative (R = iPr) has been crystallographically characterized. Tetrachlorogallate salts of the diphosphorus cations [R2(Cl)P−PR2]+ are observed for smaller R substituents (R = Me, Et, iPr, Ph), consistent with a previous report. Solid-state 31P CP-MAS NMR spectra distinguish the methyl derivative from the novel salt [Me2(Cl)P−P(Me2)−GaCl3][GaCl4], containing a phosphine−phosphenium−gallium chloride cation, which has been crystallographically characterized. Factors governing the relative stabilities of the structural alternatives are discussed, and comparisons are made between the isomeric forms for R2(Cl)P:GaCl3.