Blue emission from arsenic doped gallium nitride

We have observed strong blue emission at room temperature from arsenic doped GaN samples grown by molecular beam epitaxy. Similar results were obtained for samples doped with both arsenic dimers and tetramers. The origin of this blue emission is discussed and a growth model proposed to account for our observations. We propose that arsenic doped GaN may be a suitable replacement for (InGa)N as the active region for blue light emitting devices.     

Deposition of bulk GaN from solution in gallium under high N2 pressure on silicon carbide and sapphire substrates

Results of high-pressure directional growth of GaN on foreign substrates: SiC, sapphire and GaN/sapphire MOCVD templates are presented. The role of nitrogen pressure and supersaturation in the growth process is discussed. The conditions for stable growth of the nitride are determined. The results of the crystallization process are compared with those obtained for directional growth on pressure grown GaN crystals.     

Sublimation crystal growth of yttrium nitride

The sublimation–recombination crystal growth of bulk yttrium nitride crystals is reported. The YN source material was prepared by reacting yttrium metal with nitrogen at 1200 °C and 800 Torr total pressure. Crystals were produced by subliming this YN from the source zone, and recondensing it from the vapor as crystals at a lower temperature (by 50 °C). Crystals were grown from 2000 to 2100 °C and with a nitrogen pressure from 125 to 960 Torr. The highest rate was 9.64×10⁻⁵ mol/h (9.92 mg/h). The YN sublimation rate activation energy was 467.1±21.7 kJ/mol. Individual crystals up to 200 μm in dimension were prepared. X-ray diffraction confirmed that the crystals were rock salt YN, with a lattice constant of 4.88 Å. The YN crystals were unstable in air; they spontaneously converted to yttria (Y₂O₃) in 2–4 h. A small fraction of cubic yttria was detected in the XRD of a sample exposed to air for a limited time, while non-cubic yttria was detected in the Raman spectra for a sample exposed to air for more than 1 h.     

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).     

Nucleation of AlN on SiC substrates by seeded sublimation growth

The nucleation of aluminum nitride (AlN) on silicon carbide (SiC) seed by sublimation growth was investigated. Silicon-face, 8 off-axis 4H-SiC (0 0 0 1) and on-axis 6H-SiC (0 0 0 1) were employed as seeds. Initial growth for 15 min and extended growth for 2 h suggested that 1850 °C was the optimum temperature of AlN crystal growth: on an 8 off-axis substrate, AlN grew laterally forming a continuous layer with regular “step” features; on the on-axis substrate, AlN grew vertically as well as laterally, generating an epilayer with hexagonal sub-grains of different sizes. The layer's c-lattice constant was larger than pure AlN, which was caused by the compression of the AlN film and impurities (Si, C) incorporation. Polarity sensitive and defect selective etchings were performed to examine the surface polarity and dislocation density. All the samples had an Al-polar surface and no N-polar inversion domains were observed. Threading dislocations were present regardless of the substrate misorientation. Basal plane dislocations (BPDs) were revealed only on the AlN films on the 8 off-axis substrates. The total dislocation density was in the order of when the film was 20– thick.     

Evidence of free carrier concentration gradient along the c-axis for undoped GaN single crystals

Results of measurements of infrared reflectivity and micro-Raman scattering on the undoped GaN high pressure grown single crystals are reported. These crystals have usually a high electron concentration due to unintentional doping by oxygen. We show, by the shift of the plasma edge (infrared reflectivity measurements), that the free electron concentration is always higher on the (0 0 0  )N face of the GaN single crystal than on the (0 0 0 1)Ga face. In order to determine the profile of the free carrier concentration, we performed transverse micro-Raman scattering measurements along the (0 0 0 1) c-axis of the crystal with spatial resolution of 1 μm. Micro-Raman experiments give a quantitative information on the free carrier concentration via the longitudinal optical phonon–plasmon (LPP) coupling modes. Thus, by studying the behavior of the LPP mode along the c-axis, we found the presence of a gradient of free electrons. We suppose that this gradient of electrons is due to the gradient of the main electron donor, in undoped GaN single crystals, i.e. oxygen impurity. We propose a growth model which explains qualitatively the incorporation of oxygen during the growth of GaN crystal under high pressure of nitrogen.     

Liquid phase epitaxy (LPE) of GaN on c- and r-faces of AlN substrates

We present the optical properties of MBE-grown GaAs–AlGaAs core–shell nanowires (NWs) grown on anodized-aluminum-oxide (AAO) patterned-Si (1 1 1) substrate using photoluminescence and Raman scattering spectroscopy. The GaAs NWs were grown via the vapor–liquid–solid method with Au-nanoparticles as catalysts. Enhancement in emission of at least an order of magnitude was observed from the GaAs–AlGaAs core–shell NWs as compared to the bare GaAs NWs grown under similar conditions, which is an indication of improved radiative efficiency. The improvement in radiative efficiency is due to the passivating effect of the AlGaAs shell. Variation in bandgap emission energy as a function of temperature was analyzed using the semi-empirical Bose–Einstein model. Results show that the free exciton energy of the GaAs core–shell agrees well with the known emission energy of zinc blende (ZB) bulk GaAs. Further analysis on the linear slope of the temperature dependence curve of photoluminescence emission energy at low temperatures shows that there is no difference between core–shell nanowires and bulk GaAs, strongly indicating that the grown NWs are indeed predominantly ZB in structure. The Raman modes show downshift and asymmetrical broadening, which are characteristic features of NWs. The downshift is attributed to lattice defects rather than the confinement or shape effect.     

Study on the properties of CuInSe2 ingots grown from the melt using stoichiometric and non-stoichiometric charges

CuInSe₂ (CIS) ingots have been prepared by direct reaction of stoichiometric and non-stoichiometric proportions of high-purity Cu, In and Se. Two approaches, namely the one-ampoule process (quartz crucible) and two-ampoule process (graphite crucible) were investigated to grow the crystals, using starting charges with excess copper, and (nearly stoichiometric and with excess indium), respectively. The effect of deviation from stoichiometry in the charge on the physical properties of the resulting polycrystals is presented. Compositional analysis of the best part of the ingots with starting metals ratio (Cu/In) greater than or equal to 1 showed that the matrix preserved the original character of the charge and evidenced that the CIS chalcopyrite structure, -CIS, tolerates well a large In excess. In contrast, the composition of the crystal prepared with a 10% Cu excess was nearly-stoichiometric, with chemical images revealing the formation of heterogeneous phases besides -CIS. The inclusions precipitation was found to increase toward the ingot base. Interestingly, powder X-ray diffraction measurements revealed the presence of secondary phases rather in all the samples. The corresponding diffraction peaks were however few and very weak, with intensities of less than 3% the maximum value recorded for the CIS (1 1 2) plane.     

Optical probing of low-pressure solution grown GaN crystal properties

The structural and optical properties of self-nucleated crystals grown by a near atmospheric pressure solution growth method are presented. High-resolution room temperature Raman scattering studies demonstrate that stress-free crystals with low free-electron background have been produced. Low and room temperature photoluminescence experiments confirm the presence of shallow donors and an unknown shallow acceptor. Large relative intensity variations of the emission bands assigned to recombination process involving donors and acceptor, resulting from significant changes in the incorporation and/or activation of defect associated with each recombination channel, reflect major changes in the intrinsic material properties.     

Growth and spectral properties of Nd:LaVO4 crystal

This paper reports the growth and spectral properties of 3.5 at% Nd³⁺:LaVO₄ crystal with diameter of 20×15 mm² which has been grown by the Czochralski method. The spectral parameters were calculated based on Judd–Ofelt theory. The intensity parameters Ω_λ are: Ω₂=2.102×10⁻²⁰ cm², Ω₄=3.871×10⁻²⁰ cm², Ω₆=3.235×10⁻²⁰ cm². The radiative lifetime τ_r is 209 μs and calculated fluorescence branch ratios are: β₁(0.88μm)=45.2, β₂(1.06μm)=46.7, β₃(1.34μm)=8.1. The measured fluorescence lifetime τ_f is 137 μm and the quantum efficiency η is 65.6%. The absorption band at 808 nm wavelength has an FWHM of 20 nm. The absorption and emission cross sections are 3×10⁻²⁰ and 6.13×10⁻²⁰ cm², respectively.     

Role of non-stoichiometry in the cracking of oxide crystals

The cracking and stoichiometric deviations frequently observed in crystals of mixed oxides have generally been perceived to be unrelated phenomena. The present study pertains to the cracking in Czochralski grown crystals of three different materials, viz. CdWO₄, PbWO₄ and ZnWO₄. The results obtained on the single-crystal growth as well as on the thermal stability of melts of these materials and of their constituent oxides demonstrate, for the first time, that stoichiometric deviations manifest as cracks in the crystals. An important outcome of this investigation is that materials exhibiting a small degree of super-cooling with stable melting and solidification temperatures should be less prone to cracking.     

A simple method to synthesize α-Si3N4, β-SiC and SiO2 nanowires by carbothermal route

α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are synthesized via the direct current arc discharge method with a mixture of silicon, activated carbon and silicon dioxide as the precursor. The α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are about 50–200 nm in stem diameter and 10–100 μm in length. α-Si₃N₄ nanowires and β-SiC nanowires consist of a solid single-crystalline core along the [0 0 1] and [1 1 1] directions, respectively, wrapped within an amorphous SiO_x layer. The direct current arc plasma-assisted self-catalytic vapor–solid and/or vapor–liquid–solid (VLS) growth processes are proposed as the growth mechanism of the nanowires.     

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.     

Growth and spectral properties of Nd-doped Sr3Y(BO3)3 crystal

A new crystal of Nd³⁺:Sr₃Y(BO₃)₃ with dimension up to 25×35 mm² was grown by Czochralski method. Absorption and emission spectra of Nd³⁺: Sr₃Y(BO₃)₃ were investigated . The absorption band at 807 nm has a FWHM of 18 nm. The absorption and emission cross sections are 2.17×10⁻²⁰ cm² at 807 nm and 1.88×10⁻¹⁹ cm² at 1060 nm, respectively. The luminescence lifetime τ_f is 73 μs at room temperature     

AlN bulk single crystal growth on 6H-SiC substrates by sublimation method

Large and thick AlN bulk single crystals up to 43 mm in diameter and 10 mm in thickness have been successfully grown on 6H-SiC (0 0 0 1) substrates by the sublimation method using a TaC crucible. Raman spectrum indicates that the polytype of the grown AlN single crystals is a Wurtzite-2H type structure, and the crystals do not include any impurity phases. The quality at the top of the crystal improves as crystal thickness increases along the 〈0 0 0 1〉 direction during growth: a low etch pit density (7×10⁴ cm⁻²) and a small full width at half maximum for a 0002 X-ray rocking curve (58 arcsec) have been achieved at a thickness of ∼8 mm. The possible mechanism behind the improvement in the AlN crystal quality is also discussed.     

Possibility of AlN growth using Li–Al–N solvent

The possibility of AlN growth using Li–Al–N solvent was investigated. Based on theoretical prediction, we selected Li₃N as a suitable nitrogen source for AlN growth. First, vapor phase epitaxy using Li₃N and Al as source materials was performed to confirm the following reaction on the growth surface: Li₃N+Al=AlN+3Li. The results suggest that the reaction proceeds to form AlN on the substrate under appropriate conditions. Next, AlN growth using Li–Al–N solvent was carried out. The Li–Al–N solvent was prepared by annealing of mixtures composed of Li₃N and Al. The results imply that AlN was formed under an Al-rich condition. Moreover, it was found that Li was swept out from AlN grains during growth. The results suggest that AlN growth using Li–Al–N solvent might be a key technology to obtain an AlN crystal boule.     

Thermal and laser properties of Yb:YAl3(BO3)4 crystal

Large optical-quality Yb:YAl₃(BO₃)₄(Yb:YAB) crystals have been grown by the flux method. The thermal properties of Yb:YAB crystal were measured for the first time. The thermal properties of Yb:YAB crystal with different Yb³⁺ ion concentrations are also reported. The results show that the ytterbium concentration influences the properties of Yb:YAB crystal. The specific heat decreases with the increase of Yb³⁺ ion concentrations in the experiment range. Apparently, the thermal expansion coefficient increases along the c-direction with the increase of Yb³⁺ ion concentrations, while it changes slightly along the a-direction. The output laser in 1120–1140 nm ranges has been demonstrated pumped by InGaAs laser. The slope efficiency is 3.8%. The self-frequency-doubling output power of 1 mW is achieved.     

Pattern formation mechanism of a periodically faceted interface during crystallization ofSi

We investigated the pattern formation mechanism of a periodically faceted crystal–melt interface during the crystallization of Si by in situ observation. It was directly proved that spacing between the reentrants of adjacent zigzag facets increases with the unification of adjacent facets when a facet with a higher growth velocity catches up with the one with a lower growth velocity. The spacing becomes stable after unification, and the stable spacing was found to increase with increase in growth velocity. The experimental results was discussed by taking the negative temperature gradient in front of the growth interface into account.     

Synthesis and optical properties of purified translucent,orthorhombic boron nitride films

Large-area (>1 cm²) freestanding translucent orthorhombic boron nitride (oBN) films have been synthesized by magnetron sputtering at a low radio-frequency power of 120 W. The structural characterizations were performed by means of X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. It is demonstrated that oBN is a direct band gap semiconductor (E_g∼3.43 eV). Excited by ultraviolet laser (wavelength at 325 nm), the oBN films emit strong white light, which can be seen by the naked eyes in the dark. In the photoluminescence spectrum, besides the ultraviolet near-band-edge radiative recombination emission, there are three visible emission bands (centered at 400, 538, and 700 nm) arising from the defect-related deep-level centers of oBN, which are mixed to form the white light emission. The hardness and elastic modulus of oBN films are 11.5 and 94 GPa, respectively, examined by nanoindentation measurements.     

Phase relations around langasite (La3Ga5SiO14) in the system La2O3–Ga2O3–SiO2 in air

Phase relations around langasite (LGS, La₃Ga₅SiO₁₄) were studied on the basis of phase assemblage observed during calcination and crystallization process of samples of various compositions in the ternary system La₂O₃–Ga₂O₃–SiO₂. A ternary compound of apatite structure, La₁₄Ga_xSi_9–xO_39–x/2 was found for the first time. Crystallization of this compound was observed in the cooling process of molten samples of stoichiometric LGS as well as LGS single crystal, demonstrating that LGS is an incongruent-melting compound. A phase diagram was established primarily based on the crystallization sequence in the cooling process.