Study of the metastable region in the growth of GaN using the Na flux method

It was revealed that the metastable region, in which liquid phase epitaxy (LPE) of GaN single crystals proceeds without the generation of polycrystals, expands with growth temperature in the Na flux method. The metastable region appears when LPE growth proceeds at temperatures above 1073 K, although generation of polycrystals inevitably occurs on a crucible at temperatures less than 1073 K. The highest growth rate of 14 μm/h in a small experimental setup was achieved at a temperature of 1163 K with a nitrogen pressure of 5.5 MPa due to complete suppression of the growth of polycrystals on a crucible, even though the supersaturation at this condition reached a fairly high level.Also, an LPE crystal with a flat surface could easily be obtained under high-temperature conditions.     

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.     

Ambient-condition growth of superconducting YBa2Cu4O8 single crystals using KOH flux

YBa₂Cu₄O₈ is a stoichiometric oxide superconductor of T_c80 K. Unlike YBa₂Cu₃O_7−δ, this compound is free from oxygen vacancy or twin formation and does not have any microscopic disorder in the crystal. Doping with Ca raises its T_c to 90 K. The compound is a promising superconductor for technological application. Up to now, single crystals have not been grown without using specialized apparatus with extremely high oxygen pressure up to 3000 bar and at over 1100 °C due to the limited range of reaction kinetics of the compound. This fact has delayed the progress in the study of its physical properties and potential applications. We present here a simple growth method using KOH as flux that acts effectively for obtaining high-quality single crystals in air/oxygen at the temperature as low as 550 °C. As-grown crystals can readily be separated from the flux and exhibit a perfect orthorhombic morphology with sizes up to 0.7×0.4×0.2 mm³. Our results are reproducible and suggest that the crystals can be grown using a conventional flux method under ambient condition.     

Growth and characterization of CdSe single crystals by modified vertical vapor phase method

Good quality, large single crystals of CdSe were grown by the modified growth method (i.e., vertical unseeded vapor phase growth with multi-step purification of the starting material in the same quartz ampoule without any manual transfer between the steps). Lower temperature gradients (8–9°C/cm) at the growth interface were used for the crystal growth. As-grown CdSe crystals was characterized by X-ray diffraction, scanning electron microscopy, energy dispersive analyzer of X-rays, high-resistance instrument measurement, and etch-pit observation. It is found that there are two cleavage faces of (1 0 0) and (1 1 0) orientations on the crystal, the resistivity is about 10⁸ Ω cm, and the density of etch pits is about 10^3–4/cm². The crystal was cut into wafers and was fabricated into detectors. The detectors were tested using an ²⁴¹Am radiation source. γ-ray spectra at 59.5 keV were obtained. The results demonstrated that the quality of the as-grown crystals was good. The crystals were useful for fabrication of room-temperature-operating nuclear radiation detectors. Therefore, the modified growth technique is a promising, convenient, new method for the growth of high-quality CdSe single crystals.     

Growth and properties of Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals directly from melt

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by a modified Bridgman method directly from melt using an allomeric Pb[(Mg_1/3Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal as a seed. X-ray diffraction (XRD) measurement confirmed that the as-grown PZNT91/9 single crystals are of pure perovskite structure. Electrical properties and thermal stabilization of PZNT91/9 crystals grown directly from melt exhibit different characters from those of PZNT91/9 crystals grown from flux, although segregation and the variation of chemical composition are not seriously confirmed by X-ray fluorescence analysis (XPS). The [0 0 1]-oriented PZNT91/9 crystals cut from the middle part of the as-grown crystal boules exhibit broad dielectric-response peaks at around 105 °C, accompanied by apparent frequency dispersion. The values of piezoelectric constant d₃₃, remnant polarization P_r, and induced strain are about 1800–2200 pC/N, 38.8 μC/cm², and 0.3%, respectively, indicating that the quality of PZNT crystals grown directly from melt can be comparable to those of PZNT91/9 single crystals grown from flux. However, further work deserves attention to improve the dielectric properties of PZNT crystals grown directly from melt. Such unusual characterizations of dielectric properties of PZNT crystals grown directly from melt are considered as correlating with defects, microinhomogeneities, and polar regions.     

Growth, dielectric, ferroelectric and optical properties of Ca0.28Ba0.72Nb2O6 single crystals

Calcium barium niobate Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystals were grown by the Czochralski method. The effective segregation coefficients of Ca, Ba, Na elements in CBN-28 crystal growth were measured, and the rocking curve from 0 0 2 reflection of CBN-28 wafer was also measured by the high-resolution X-ray diffractometer D5005, and the full-width at half-maximum value was measured to be 70.6″. The measured dependence of dielectric constants on temperature showed the Curie temperature of the CBN-28 crystals is between 246.8 and 260 °C. Typical polarization–electric field (P–E) hysteresis loops were measured at room temperature. Ferroelectric 180° domains were observed by scanning electron microscopy (SEM) on the etched (0 0 1) surface of the CBN-28 crystals. The transmittance of [0 0 1]-oriented CBN-28 crystals was measured and the result shows that optical properties of CBN-28 crystal are almost the same as those of SBN for wavelengths between 2500 and 7500 nm.     

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.     

Growth and morphology of ruby crystals with unusual chromium concentration

Single crystals of ruby have been obtained from fluxed melts based on the systems Li₂O–MoO₃, Li₂O–WO₃, Na₂O–WO₃, 2PbO–3V₂O₅, PbO–V₂O₅–WO₃, PbF₂–Bi₂O₃ and Na₃AlF₆ by both the TSSG method and spontaneous crystallization at the temperatures 1330–900 °C. Al₂O₃ solubility has been measured for the flux composition of 2Bi₂O₃–5PbF₂ in the temperature range 1200–1000 °C and dissolution enthalpy has been defined as 29.4 KJ/Mol. The composition of grown crystals was studied by electron microprobe analysis. The synthetic ruby contains from 0.51 to 6.38 at% of chromium admixture depending on the crystal growth conditions. Experimental results on growth conditions, composition and morphology of grown crystals are presented for each flux and temperature interval.     

GaN/GaAs(1 0 0) superlattices grown by metalorganic vapor phase epitaxy using dimethylhydrazine precursor

Superlattices of cubic gallium nitride (GaN) and gallium arsenide (GaAs) were grown on GaAs(1 0 0) substrates using metalorganic vapor phase epitaxy (MOVPE) with dimethylhydrazine (DMHy) as nitrogen source. Structures grown at low temperatures with varying layer thicknesses were characterized using high resolution X-ray diffraction and atomic force microscopy. Several growth modes of GaAs on GaN were observed: step-edge, layer-by-layer 2D, and 3D island growth. A two-temperature growth process was found to yield good crystal quality and atomically flat surfaces. The results suggest that MOVPE-grown thin GaN layers may be applicable to novel GaAs heterostructure devices.     

The temperature gradient technique (TGT) growth and optical properties of Yb-doped YAlO3 single crystal

The dark-brown colored 5 at% Yb-doped YAlO₃ (Yb:YAP) single crystal was grown successfully by temperature gradient technique (TGT) for the first time. The TGT-grown Yb:YAP crystal with the perovskite structure and excellent crystallization perfection were confirmed by the X-ray diffractions techniques. The dark-brown color of TGT-Yb:YAP crystal turned into the colorless after annealing in the air at 1200 °C for 10 h. The absorption spectra, LD-excited infrared emission and X-ray excited luminescence spectra of the air-annealed Yb:YAP single crystal were investigated at the room temperature. The results indicate that the TGT-Yb:YAP single crystals can be used for the laser and scintillation applications.     

Growth of AlN films on SiC substrates by RF-MBE and RF-MEE

Epitaxial AlN films have been grown on SiC substrate by molecular beam epitaxy (MBE) and migration-enhanced epitaxy (MEE) using radio frequency (RF) plasma-excited nitrogen. In the RF-MBE growth, the growth rates have been found to be almost constant and the crystal quality improved with increasing the substrate temperature up to 850°C. Further increases of substrate temperature decreased the growth rate and degraded the crystal quality. Using the optimum substrate temperature of 850°C and optimizing the shutter open time, smooth AlN films with atomic force microscope roughness as low as 0.2 nm have been grown by RF-MEE growth.     

Effect of the N/Al ratio of AlN buffer on the crystal properties and stress state of GaN film grown on Si(1 1 1) substrate

The effect of the N/Al ratio of AlN buffers on the optical and crystal quality of GaN films, grown by metalorganic chemical vapor deposition on Si(1 1 1) substrates, has been investigated. By optimizing the N/Al ratio during the AlN buffer, the threading dislocation density and the tensile stress have been decreased. High-resolution X-ray diffraction exhibited a (0 0 0 2) full-width at half-maximum as low as 396 acrsec. The variations of the tensile stress existing in the GaN films were approved by the redshifts of the donor bound exiton peaks in the low-temperature photoluminescence measurement at 77 K.     

Influence of cooling rate on the liquid-phase epitaxial growth of Zn3P2

We report the liquid-phase epitaxial growth of Zn₃P₂ on InP (1 0 0) substrates by conventional horizontal sliding boat system using 100% In solvent. Different cooling rates of 0.2–1.0 °C/min have been adopted and the influence of supercooling on the properties of the grown epilayers is analyzed. The crystal structure and quality of the grown epilayers have been studied by X-ray diffraction and high-resolution X-ray rocking measurements, which revealed a good lattice matching between the epilayers and the substrate. The supercooling-induced morphologies and composition of the epilayers were studied by scanning electron microscopy and energy dispersive X-ray analysis. The growth rate has been calculated and found that there exists a linear dependence between the growth rate and the cooling rate. Hall measurements showed that the grown layers are unintentionally doped p-type with a carrier mobility as high as 450 cm²/V s and a carrier concentration of 2.81×10¹⁸ cm⁻³ for the layers grown from 6 °C supercooled melt from the cooling rate of 0.4 °C/min.     

Growth and characterization of 2-amino-5-chlorobenzophenone (2A-5CB) single crystals

Organic nonlinear optical single crystals of 2-amino-5-chlorobenzophenone (2A-5CB) were grown in ethanol by slow solvent evaporation technique. The grown crystals were characterized by single-crystal XRD, FTIR, FT-Raman and UV–vis–NIR techniques. The UV–vis–NIR spectrum ascertains the cut-off wavelength of the sample as 390 nm. The powder second harmonic generation (SHG) technique reveals that 2A-5CB crystal has its SHG efficiency nearly three times that of KDP. The dielectric response of the sample was studied in the frequency region of 50 Hz–1 MHz at varying temperatures. The photoconductivity studies indicate that the 2A-5CB crystal exhibits negative photoconductivity. TGA–DTA studies confirm the melting point of the sample as 101.5 °C.     

High-quality a-plane GaN grown with flow-rate modulation epitaxy on r-plane sapphire substrate

We use the flow-rate modulation epitaxy (FME) technique to improve the crystal quality of a pit-free a-plane GaN (1 1 2¯ 0) film grown on r-plane sapphire (1 1¯ 0 2) substrate. With the FME technique, the width of the rocking curve in X-ray diffraction measurement is significantly reduced. Also, the surface roughness in either atomic-force-microscopy scanning or -step profiling is decreased. Here, the FME technique means to alternatively turn on and off the supply of Ga atoms, while N atoms are continuously supplied without changing the flow rate. Under the used growth conditions, the optimized FME parameters include the on/off periods at 10/10 s. During the period of closing the flow of trimethylgallium (TMGa), the continuous supply of nitrogen can lead to the formation of stoichiometry structure under the high-Ga growth condition, which is required for pit-free growth. Also, during this period, Ga atoms can further migrate to result in a flatter surface. Therefore, the crystal quality of the a-plane GaN sample can be improved.     

Environmental SEM investigation on surface defects in 0.92Pb(Zn1/3Nb2/3)O3–0.08PbTiO3 single crystal

In this paper, the technique of environmental scanning electron microscopy (ESEM) has been employed to investigate the surface defects of the (1 1 1) appearing face in 0.92Pb(Zn_1/3Nb_2/3)O₃–0.08PbTiO₃ (PZN–8%PT) crystals. From the ESEM images, we succeeded in observing and studying the growth hillocks and etch pits, low-angle grain boundaries, and sub-grain boundaries in (1 1 1) face, which were related to the generation of dislocation and stacking faults, respectively. On the other hand, an image of a unique multi-layer lamellar structure and fine step structure obtained in the (1 1 1) face reveals that the dominant fast growth mechanism of PZN–8%PT crystal grown by the flux method is a sub-step mechanism, unlike the screw dislocation growth mechanism.     

X-ray characterization of detached-grown germanium crystals

Germanium (1 1 1)-oriented crystals have been grown by the vertical Bridgman technique, in both detached and attached configurations. Microstructural characterization of these crystals has been performed using synchrotron white beam X-ray topography (SWBXT) and double axis X-ray diffraction. Dislocation densities were measured from X-ray topographs obtained using the reflection geometry. For detached-grown crystals, the dislocation density is on the order of 10⁴ cm⁻² in the seed region, and decreases in the direction of growth to less than 10³ cm⁻², and in some crystals reaches less than 10² cm⁻². For crystals grown in the attached configuration, dislocation densities were on the order of 10⁴ cm⁻² in the middle of the crystals, increasing to greater than 10⁵ cm⁻² near the edge. The measured dislocation densities are in excellent agreement with etch pit density (EPD) results. Broadening and splitting of the rocking curve linewidths was observed in the vicinity of subgrain boundaries identified by X-ray topography in some of the attached-grown crystal wafers. The spatial distribution of rocking curve linewidths across the wafers corresponds to the spatial distribution of defect densities measured in the X-ray topographs and EPD micrographs.     

Growth and spectroscopic properties of Er single doped and Er–Yb co-doped YAl3(BO3)4 crystals

Er³⁺-doped and Er³⁺–Yb³⁺ co-doped yttrium aluminum borate (YAB) single crystals have been grown by the top-seeded solution growth method using a new flux system, namely NaF–MoO₃–B₂O₃. The Er³⁺ concentrations were 1.3 mol% for both single doped and co-doped crystals and the Yb³⁺ concentration in the Er³⁺–Yb³⁺ co-doped crystal was 20.0 mol% in the raw materials. The distribution coefficients of Er³⁺ single doped and Er³⁺–Yb³⁺ co-doped crystals were measured. The polarized absorption and fluorescence spectra of Er³⁺–Yb³⁺ co-doped crystal were recorded and compared with those of Er³⁺ single doped crystal. The results demonstrate that Er³⁺–Yb³⁺ co-doped YAB crystal is a potential candidate for 1.55 μm laser materials.     

Homoepitaxial growth and electrical characterization of GaN-based Schottky and light-emitting diodes

Homoepitaxial growth of GaN epilayers on free-standing hydride vapor phase epitaxy (HVPE) GaN substrates offered a better control over surface morphology, defect density, and doping concentration compared to conventional heteroepitaxial growth. The FWHM of the (0 0 0 2) X-ray diffraction (XRD) rocking curve from homoepitaxial GaN was measured to be as low as 79 arcsec, much smaller than 230 arcsec for GaN grown on sapphire. Schottky diodes grown on GaN substrates exhibited sharper breakdown characteristics and much lower reverse leakage than diodes on sapphire. However, the homoepitaxial devices had poor scalability due to the presence of yield-killing defects originating from the substrate surface. Vertical InGaN/GaN light-emitting diodes (LEDs) on GaN substrates showed reduced series resistance and reverse leakage compared to lateral LEDs on sapphire. Wafer mapping demonstrated that the distribution of leaky homoepitaxial devices correlated well with that of macroscopic defects in the GaN substrates.     

Impedance spectroscopy analysis of AlGaN/GaN HFET structures

For HFET application a series of samples with 30 nm Al_xGa_1−xN (x=0.02–0.4) layers deposited at 1040°C onto optimised 2 μm thick undoped GaN buffers were fabricated. The Al_xGa_1−xN/GaN heterostructures were grown on c-plane sapphire in an atmospheric pressure, single wafer, vertical flow MOVPE system. Electrical properties of the Al_xGa_1−xN/GaN heterostructures and thick undoped GaN layers were evaluated by impedance spectroscopy method performed in the range of 80 Hz–10 MHz with an HP 4192A impedance meter using a mercury probe. The carrier concentration distribution through the layer thickness and the sheet carrier concentration were evaluated. A non-destructive, characterisation technique for verification of device heterostucture quality from the measured C–V and G–V versus frequency characteristics of the heterostructure is proposed.