Hydride-assisted growth of GaN nanowires on Au/Si(0 0 1) via the reaction of Ga with NH3 and H2

High quality, straight GaN nanowires (NWs) with diameters of 50 nm and lengths up to 3 μm have been grown on Si(0 0 1) using Au as a catalyst and the direct reaction of Ga with NH₃ and N₂:H₂ at 900 °C. These exhibited intense, near band edge photoluminescence at 3.42 eV in comparison to GaN NWs with non-uniform diameters obtained under a flow of Ar:NH₃, which showed much weaker band edge emission due to strong non-radiative recombination. A significantly higher yield of β-Ga₂O₃ NWs with diameters of ≤50 nm and lengths up to 10 μm were obtained, however, via the reaction of Ga with residual O₂ under a flow of Ar alone. The growth of GaN NWs depends critically on the temperature, pressure and flows in decreasing order of importance but also the availability of reactive species of Ga and N. A growth mechanism is proposed whereby H₂ dissociates on the Au nanoparticles and reacts with Ga giving Ga_xH_y thereby promoting one-dimensional (1D) growth via its reaction with dissociated NH₃ near or at the top of the GaN NWs while suppressing at the same time the formation of an underlying amorphous layer. The higher yield and longer β-Ga₂O₃ NWs grow by the vapor liquid solid mechanism that occurs much more efficiently than nitridation.     

Theoretical investigation on the decomposition process of GaN(0 0 0 1) surface under a hydrogen atmosphere

The activation energies for Ga and N desorption from a GaN surface were calculated using the density functional theory to understand the detailed decomposition process of the hydrogen terminated GaN(0 0 0 1) Ga and N surfaces under a hydrogen atmosphere. It was found that the Ga atoms on the hydrogen terminated GaN(0 0 0 1) Ga surface desorbed as GaH molecules from the surface while the N atoms on the hydrogen terminated GaN(0 0 0 1) N surface desorbed as NH₃ molecules from the surface. The desorption energies of GaH and NH₃ on the hydrogen terminated surface were more consistent with the previous experimental values than those on the ideal surface. These results suggest that the initial surface structure of the GaN(0 0 0 1) surface is terminated with hydrogen.     

Ca3N2 as a flux for crystallization of GaN

In this work Ca₃N₂ was investigated as a potential flux for crystallization of GaN. Melting temperature of the potential flux at high N₂ pressure evaluated by thermal analysis as 1380 °C is in good agreement with the theoretical prediction. It is shown that Ca₃N₂ present in the liquid gallium in small amount (1 at%) dramatically accelerates synthesis of GaN from its constituents. On the other hand, it does not influence significantly the rate of GaN crystallization from solution in gallium in temperature gradient for both unseeded and seeded configurations. However the habit and color of the spontaneously grown GaN crystals change drastically. For 10 mol% Ca₃N₂ content in the liquid Ga it was found that the GaN thick layer and GaN crystals (identified by micro-Raman scattering measurements) were grown on the substrate. For growth from molten Ca₃N₂ (100%) with GaN source, the most important observations were (i) GaN source material was completely dissolved in the molten Ca₃N₂ flux and (ii) after experiment, GaN crystals were found on the sapphire substrate.     

Thermogravimetric analysis and microstructural observations on the formation of GaN from the reaction between Ga2O3 and NH3

Thermogravimetric analysis (TGA) and microstructural observations were carried to investigate the nitridation mechanism of β-Ga₂O₃ powder to GaN under an NH₃/Ar atmosphere. Non-isothermal TGA showed that nitridation of β-Ga₂O₃ starts at ∼650 °C, followed by decomposition of GaN at ∼1100 °C. Isothermal TGA showed that nitridation follows linear kinetics in the temperature range 800–1000 °C. At an early stage of nitridation, small GaN particles (∼5 nm) are deposited on the β-Ga₂O₃ crystal surface and they increase with time. We proposed a mechanism for the nitridation of Ga₂O₃ by NH₃ whereby nitridation of β-Ga₂O₃ proceeds via the intermediate vapor species Ga₂O(g).     

Ammonothermal epitaxy of wurtzite GaN using an NH4I mineralizer

Purely wurtzite phase needle crystals and epitaxial layers of GaN were grown by the ammonothermal method using an NH₄I mineralizer. The inclusion of zincblende phase GaN was effectively eliminated by increasing the growth temperature higher than 500 °C. Accordingly, an approximately 20-μm-thick GaN epitaxial layer was achieved on the Ga-polar face of a c-plane GaN seed wafer at 520 °C. Although the characteristic deep state emission band dominated the room temperature photoluminescence spectrum, the near-band-edge emission of GaN was observed for both the needle crystals and the epitaxial layers. These results encourage one to grow better quality GaN crystals at a high growth rate under high-temperature growth conditions.     

In situ gravimetric monitoring of surface reactions between sapphire and NH3

Surface reactions between a (0 0 0 1) C-plane sapphire and NH₃, with He as an inert carrier gas, were investigated at high temperatures over 1200 °C using the in situ gravimetric monitoring method. Although the sapphire substrate was stable up to 1400 °C under a He atmosphere, decomposition started to occur at 1300 °C under a 0.1 atm NH₃+He and the decomposition rates were found to be lower than those in 0.1 atm H₂+He at each temperature. These results imply that sapphire can be decomposed by NH₃ and/or hydrogen generated by the decomposition of NH₃ over 1300 °C. The decomposition rate in NH₃+He was decreased with increase in NH₃ flow time, and the decomposition rate became constant after 60 min of NH₃ flow. Moreover, the activation energy for sapphire decomposition before 60 min of NH₃ flow was different from that after 60 min of NH₃ flow time, which indicates that the surface reaction between sapphire and NH₃ and/or hydrogen generated from NH₃ changes depending on the time of NH₃ flow. The dependence of the surface reactions and rate-limiting reactions between sapphire and NH₃ on the time of NH₃ flow is discussed.     

Growth of InxGa1−xN quantum dots by nitridation of nano-alloyed droplet method using MOCVD

In_xGa_1−xN quantum dots (QDs) were grown on GaN/sapphire (0 0 0 1) substrates by employing nitridation of nano-alloyed droplet (NNAD) method using metal-organic chemical vapor deposition (MOCVD). In+Ga alloy droplets were initially formed by flowing the precursors TMIn and TMGa. Density of the In+Ga alloy droplets was increased with increasing precursors flow rate; however, the droplet size was scarcely changed in the range of about 100–200 nm. Two cases of In_xGa_1−xN QDs growth were investigated by varying the nitridation time and the growth temperature. It was observed that the In_xGa_1−xN QDs size can be easily changed by controlling the nitridation process at the temperature between 680 and 700 °C for the time of 5–30 min. Self-assembled In_xGa_1−xN QDs were successfully grown by employing NNAD method.     

Effect of NH3 flow rate on m-plane GaN growth on m-plane SiC by metalorganic chemical vapor deposition

This paper reports a study of the effect of NH₃ flow rate on m-plane GaN growth on m-plane SiC with an AlN buffer layer. It is found that a reduced NH₃ flow rate during m-plane GaN growth can greatly improve the recovery of in situ optical reflectance and the surface morphology, and narrow down the on-axis (1 0 1¯ 0) X-ray rocking curve (XRC) measured along the in-plane a-axis. The surface striation along the in-plane a-axis, a result of GaN island coalescence along the in-plane c-axis, strongly depends on the NH₃ flow rate, an observation consistent with our recent study of kinetic Wulff plots. The pronounced broadening of the (1 0 1¯ 0) XRC measured along the c-axis is attributed to the limited lateral coherence length of GaN domains along the c-axis, due to the presence of a high density of basal-plane stacking faults, most of which are formed at the GaN/AlN interface, according to transmission electron microscopy.     

Preparation of GaN crystals by heating a Li3N‐added Ga melt in Na vapor and their photoluminescence

GaN crystals were prepared by heating a Ga melt with 1 at% Li₃N against Ga at 750 °C in Na vapor under N₂ pressures of 0.4–1.0 MPa. The GaN crystals grown at 1.0 MPa of N₂ were colorless and transparent prismatic, having a size of approximately 0.7 mm in length. A secondary ion mass spectrometry (SIMS) showed the contaminant of lithium in the obtained crystals. A large broad yellow band emission peak of 2.28 eV was observed at room temperature in the photoluminescence spectrum in addition to the near band emission peak of GaN at 3.39 eV and a small broad satellite emission at 3.24 eV. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of (CH3)2NH2CuCl3 single crystals using evaporation method with different temperatures and solvents

The bulk single crystals of low-dimensional magnet (CH₃)₂NH₂CuCl₃ (DMACuCl₃ or MCCL) are grown by a slow evaporation method with different kinds of solvents, different degrees of super-saturation of solution and different temperatures of solution, respectively. Among three kinds of solvent, methanol, alcohol and water, alcohol is found to be the best one for growing MCCL crystals because of its structural similarity to the raw materials and suitable evaporation rate. The best growth temperature is in the vicinity of 35 °C. The problem of the crystals deliquescing in air has been solved through recrystallization process. The crystals are characterized by means of X-ray diffraction, specific heat and magnetic susceptibility.     

Effect of Al additive on the formation of cubic boron nitride in Li3N–hBN system under HPHT

We have investigated the effect of Al on cBN formation in Li₃N–hBN system at 5.0 GPa and 1300–1650 °C. Regular cBN single crystals of 0.2–0.5 mm in size were obtained. It appears that the presence of Al in hBN powder facilitates the formation of cBN crystals with regular shape, although it does not have any catalytic action for hBN–cBN phase transformation. With increasing Al concentration, the color of cBN changed darker from amber to black and the threshold temperature for cBN formation became higher. X-ray diffraction and Raman spectroscopy indicate that AlN formed by reaction of Li₃N and Al and some B liberated in system.     

Bulk single-crystal growth of ternary AlxGa1−xN from solution in gallium under high pressure

We have successfully grown bulk, single crystals of Al_xGa_1−xN with the Al content x ranging from 0.5 to 0.9. Samples were grown from Ga melt under high nitrogen pressure (up to 10 kbar) and at high temperature (up to 1800 °C) using a gas pressure system. The homogeneity and Al content of the crystals were investigated by X-ray diffraction and laser ablation mass spectrometry. On the basis of the high-pressure experiments, the corresponding pressure–temperature (p–T) phase diagram of Al–Ga–N was derived. The bandgap of the material was determined by the femtosecond two-photon absorption autocorrelation method and is equal to 5.81±0.01 eV for the Al_0.86Ga_0.14N crystals.     

Optical properties of Ga3PO7 single crystals

Ga₃PO₇ crystal with size 18×15×12 mm³ and good optical quality has been grown by the top-seeded solution growth (TSSG) slow-cooling method from a Li₂O–3MoO₃ flux system. The Vickers microhardness and optical properties of the as-grown Ga₃PO₇ crystal have been carefully studied. The results show that the Ga₃PO₇ crystal belongs to the harder materials, and Meyer's index numbers for (1 1 0) and (0 0 1) planes were about 1.45 and 1.60, respectively. The Ga₃PO₇ crystal has a wide transmission range from 215 to 4300 nm. The smaller difference between the refractive indices values of n_o and n_e indicated that the Ga₃PO₇ crystal is an optically uniaxial negative crystal.     

Phase separation and crystallization in the system SiO2-Al2O3-P2O5-B2O3-Na2O glasses

The phase separation and crystallization behavior in the system (80 − X)SiO₂ · X(Al₂O₃ + P₂O₅) · 5B₂O₃ · 15Na₂O (mol%) glasses was investigated. Glasses with X = 20 and 30 phase separated into two phases, one of which is rich in Al₂O₃-P₂O₅-SiO₂ and forms a continuous phase. Glasses containing a larger amount of Al₂O₃-P₂O₅ (X = 40 and 50) readily crystallize and precipitates tridymite type AlPO₄ crystals. It is estimated that the phase separation occurs forming continuous Al₂O₃-P₂O₅-SiO₂ phase at first, and then tridymite type AlPO₄ crystals precipitate and grow in this phase. Highly transparent glass-ceramics comparable to glass can be successfully obtained by controlling heat treatment precisely. The crystal size and percent crystallinity of these transparent glass-ceramics are 20-30 nm and about 50%, respectively.     

On the kinetics of nitrogen incorporation in GaP LPE layers using NH3 vapour doping

The partial substitution of N for P in GaP has a considerable effect on the luminescence quantum efficiency of GaP epitactic layers. The incorporation of N in GaP liquid phase epitactic layers using NH₃ vapour doping has been studied at different H₂ partial pressures in argon gas. It is shown that the incorporation of N in different ambients is conveniently described by just one parameter. The reaction of NH₃ with Ga is found to be an equilibrium process. The N concentration in the layer is directly proportional to the GaN concentration in the melt. From the correlation of the dissociation of NH₃ with the formation of GaN it is concluded that the NH₃ pressure, as measured in the exit gas, is not representative of the NH₃ pressure at the melt. The dissociation of NH₃ is found to be strongly retarded by H₂ owing to adsorption of H₂ on the surface of reactor materials which catalyse the dissociation.     

Flux growth and characterizations of NdPO4 single crystals

Neodymium phosphate single crystals, NdPO₄, have been grown by a flux growth method using Li₂CO₃-2MoO₃ as a flux. The as-grown crystals were characterized by X-ray powder diffraction(XRPD), differential thermal analysis (DTA) and thermogravimetric analysis (TG) techniques. The results show that the as-grown crystals were well crystallized. The crystal was stable over the temperature range from 26 to 1200 °C in N₂. The specific heat of NdPO₄ crystal at room temperature was 0.41 J/g °C. The absorption and the fluorescence spectra of NdPO₄ crystal were also measured at room temperature.     

The comparative structure, properties, and ionic conductivity of LiI + Li2S + GeS2 glasses doped with Ga2S3 and La2S3

The well known and characterized fast ion conducting (FIC) LiI + Li₂S + GeS₂ glass-forming system has been further optimized for higher ionic conductivity and improved thermal and chemical stability required for next generation solid electrolyte applications by doping with Ga₂S₃ and La₂S₃. These trivalent dopants are expected to eliminate terminal and non-bridging sulfur (NBS) anions thereby increasing the network connectivity while at the same time increasing the Li⁺ ion conductivity by creating lower basicity [(Ga or La)S_4/2]⁻ anion sites. Consistent with the finding that the glass-forming range for the Ga₂S₃ doped compositions is larger than that for the La₂S₃ compositions, the addition of Ga₂S₃ is found to eliminate NBS units to create bridging sulfur (BS) units that not only gives an improvement to the thermal stability, but also maintains and in some cases increases the ionic conductivity. The compositions with the highest Ga₂S₃ content showed the highest T_gs of ∼325 °C. The addition of La₂S₃ to the base glasses, by comparison, is found to create NBS by forming high coordination octahedral LaS₆³⁻ sites, but yet still improved the chemical stability of the glass in dry air and retained its high ionic conductivity and thermal stability. Significantly, at comparable concentrations of Li₂S and Ga₂S₃ or La₂S₃, the La₂S₃-doped glasses showed the higher conductivities. The addition of the LiI to the glass compositions not only improved the glass-forming ability of the compositions, but also increased the ionic conductivity glasses. LiI concentrations from 0 to 40 mol% improved the conductivities of the Ga₂S₃ glasses from ∼10⁻⁵ to ∼10⁻³ (Ω cm)⁻¹ and of the La₂S₃ glasses from ∼10⁻⁴ to ∼10⁻³ (Ω cm)⁻¹ at room temperature. A maximum conductivity of ∼10⁻³ (Ω cm)⁻¹ at room temperature was observed for all of the glasses and this value is comparable to some of the best Li ion conductors in a sulfide glass system. Yet these new compositions are markedly more thermally and chemically stable than most Li⁺ ion conducting sulfide glasses. LiI additions decreased the T_gs and T_cs of the glasses, but increased the stability towards crystallization (T_c − T_g).     

The influence of indium on the growth of GaN from solution under high pressure

The influence of significant fraction (10–50 mole%) indium in liquid gallium on GaN crystallization from a ternary Ga–In–N solution was analyzed. Crystallization experiments of GaN on GaN-sapphire templates from Ga–In solutions, at 1350–1450 °C, with prior to the growth seed wetting at 1500 °C, and 1.0 GPa N₂ pressure, without solid GaN source showed faster growth of GaN on the seed (by a factor of 1.5–2) than using pure gallium solvent. Nevertheless the new grown crystals were morphologically unstable. The instability was reduced by decrease of the wetting temperature down to 1100 °C or by omitting the wetting procedure entirely, which indicated that GaN dissolves much faster in Ga–In melt than in pure Ga and that the unstable growth was caused most likely by complete dissolution of GaN template before the growth. It was observed that the crystals grown on bulk GaN substrates did not show morphological instability observed for GaN-sapphire templates. The influence of indium on thermodynamic and thermal properties of the investigated system is discussed.     

Synthesis of gallium nitride by ammonia injection into gallium melt

Gallium nitride (GaN) was synthesized by injecting ammonia gas into molten gallium at 900–980°C under atmospheric pressure. A large amount of GaN powder was reproducibly obtained using a simple apparatus. The synthesized powder was characterized by scanning electron microscopy, X-ray diffraction, photoluminescence and energy dispersive X-ray spectroscopy, and was found to consist of fine crystals of hexagonal GaN of good quality. The total of GaN obtained was far more than the amount calculated from expected saturation solubility in the Ga melt at that temperature. We speculate that the GaN crystals were largely formed by direct reaction between Ga and the gaseous N source at the surface of the NH₃ bubbles in the melt. GaN synthesized by this method may be useful as a starting material for bulk growth.     

Growth and property of Zn-doped near-stoichiometric LiTaO3 crystal

Near-stoichiometric LiTaO₃ (SLT) and Zn-doped near-stoichiometric LiTaO₃ (Zn:SLT) crystals with 10–15 mm in diameter and 10 mm in length were grown by using TSSG technique with K₂O as the flux. The effect of adding amount of K₂O was discussed in the growing process. The crystals were characterized by inductively coupled plasma-optical emission (ICP-OES), X-ray diffraction (XRD) and differential thermal analysis (DTA). The lattice constants of Zn:SLT were smaller than those of SLT and Curie temperature was higher than that of SLT. It was found that Zn doping is an efficient way to improve the optical damage resistance ability of SLT crystal. Compared with SLT crystal, Zn:SLT exhibited a much higher optical damage threshold, more than 500 MW/cm², which was attributed to Zn self-compensated effect that formed the charge compensated complexes, (Zn_Ta)³⁻–3(Zn_Li)⁺ in SLT crystal.