Growth mechanisms in excimer laser photolytic deposition of gallium nitride at 500°C

The mechanisms of controlling laser-induced chemical vapour deposition of GaN at substrate temperatures between 350 and 650°C have been investigated. Ultraviolet (193 nm) photolytic decomposition of trimethylgallium (TMGa) and ammonia (NH₃) precursors was examined in this range. Laser-induced fluorescence studies support the view that the dissociated intermediate fragments GaCH₃ and NH are the reacting species in GaN film formation, irrespective of substrate temperature. It was found that two crystal phases coexist in films grown at substrate temperatures below 500°C, wurtzite crystal structure with (0002) orientation forms at substrate temperatures above 500°C. The growth rate increases with both NH₃/TMGa ratio, and TMGa flow rate, while the temperature dependence shows a thermal activation energy of 0.2 eV which is smaller by a factor of five than that of films prepared by conventional thermal CVD. The large NH₃/TMGa ratios needed to achieve stoichiometry are interpreted in terms of the two-photon dissociation cross section of NH₃.     

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.     

Microampere laser threshold at 80°C with InGaAs/GaAs/InGaP buried heterostructre strained quantum well lasers

An extremely low CW threshold current of 670 μA and a high slope efficiency of 0.14 W/A at a high junction temperature of 80°C were obtained with a 200 μm long Al-free InGaAs/GaAs/InGaP buried heterostructure (BH) quantum well laser grown by three-step metal organic vapor phase epitaxy (MOVPE). The maximum energy conversion efficiency of a 500 μm long laser was as high as 50% at a output power level of 1 mW. Regrowth conditions of InGaP layers were found to be crucial for planarizing the grown surface to realize the high performances.     

Single-crystal growth of sulphospinel CuIr2S4 from Bi solution

Single crystals of a sulphospinel CuIr₂S₄ have been grown from bismuth solution by a slow cooling method for the first time. The grown crystals have a maximum edge of about 1 mm in size and a mirror-like shining surface. Optimum growth conditions are fairly strict. The specific weight of starting materials for the crystal growth is found to be 0.30 g of CuIr₂S₄ and 10.0 g of Bi in order to obtain good quality crystals. The starting and finishing temperatures for the slow cooling step in the temperature control are 1000 and 500°C. The pertinent cooling rate is 2°C/h. Since the volume of bismuth itself expands in the transition from liquid phase to solid phase, a simple method of separation of the grown crystals from the liquid solution will be proposed for avoiding the mechanical damages to the grown crystals. The single crystals have the normal-spinel structure of the lattice constant a=9.849 Å at room temperature. A step-like anomaly in the susceptibility of the single crystals, corresponding to the metal–insulator transition in the resistivity, occurs much sharply than in the powder specimen.     

Behaviour of vicinal InP surfaces grown by MOVPE: exploitation of AFM images

InP substrates and epilayers grown by MOVPE have been studied by AFM. For different misorientation angles, we observed the surface of the substrate after annealing under phosphine (PH₃) and of the epilayers under different growth conditions such as growth temperature T_g and trimethylindium (TMI) partial pressure. After annealing the terrace width corresponds to the nominal value of misorientation angle measured by X-ray diffraction. We observed different topographies and roughnesses for the grown layers corresponding to different growth modes. We propose, taking into account the roughness of the surface, a calculation of the step height and terrace width. For 2D nucleation (θ ≤ 0.2° and T_g = 500°C) and step flow mode, the roughness is low while it is increased by step bunching (θ ≥ 0.5° and T_g ≥ 580°C). Moreover we have examined the surface morphology for different misorientation angles and determined the influence of growth conditions (growth temperature, indium partial pressure) on the growth mechanism. At T_g = 580°C the increase of the TMI partial pressure in the reactor enhances the step bunching and leads to larger terraces.     

Low temperature growth of AlGaAs by MOMBE (CBE) using trimethylamine alane

In order to gain further insight into the surface chemistry of AlGaAs growth by metalorganic molecular beam epitaxy, we have investigated the deposition behavior and material quality of AlGaAs grown at temperatures from 350 to 500°C using trimethylamine alane (TMAA), triethylgallium (TEG) and arsine (AsH₃). Though the Al incorporation rate decreases with decreasing temperature, Ga-alkyl pyrolysis, and hence Ga incorporation rate, declines more rapidly. Thus the Al content increases from X_AlAs = 0.25 at 500°C to X_AlAs = 0.57 at 350°C. Below 450°C, the Ga incorporation rate appears to be determined by the desorption of diethylgallium species, rather than interaction with adsorbed AlH₃. Similarly, carbon incorporation is enhanced by 2 orders of magnitude over this temperature range due to the increasingly inefficient pyrolysis of the Ga-C bond in TEG. Additionally, active hydrogen from the TMAA1, which normally is thought to getter the surface alkyls, is possibly less kinetically active at lower growth temperatures. Contrary to what has been observed in other growth methods, low growth temperatures produced a slight decrease in oxygen concentration. This effect is likely due to reduced interaction between Ga alkoxides (inherent in the TEG) and the atomic hydrogen blocked Al species on the growth surface. This reduction in oxygen content and increase in carbon concentration causes the room temperature PL intensity to actually increase as the temperature is reduced from 500 to 450°C. Surprisingly, the crystalline perfection as measured by ion channeling analysis is quite good, χ_min≤5%, even at growth temperatures as low as 400°C. At 350°C, the AlGaAs layers exhibit severe disorder. This disorder is indicative of insufficient Group III surface mobility, resulting in lattice site defects. The disorder also supports our conclusions of kinetically limited surface mobility of all active surface components.     

Epitaxial growth of ZnO thin films on Si substrates by PLD technique

Epitaxial ZnO thin films have been grown on Si(1 1 1) substrates at temperatures between 550 and 700 °C with an oxygen pressure of 60 Pa by pulsed laser deposition (PLD). A ZnO thin film deposited at 500 °C in no-oxygen ambient was used as a buffer layer for the ZnO growth. In situ reflection high-energy electron diffraction (RHEED) observations show that ZnO thin films directly deposited on Si are of a polycrystalline structure, and the crystallinity is deteriorated with an increase of substrate temperature as reflected by the evolution of RHEED patterns from the mixture of spots and rings to single rings. In contrast, the ZnO films grown on a homo-buffer layer exhibit aligned spotty patterns indicating an epitaxial growth. Among the ZnO thin films with a buffer layer, the film grown at 650 °C shows the best structural quality and the strongest ultraviolet (UV) emission with a full-width at half-maximum (FWHM) of 86 meV. It is found that the ZnO film with a buffer layer has better crystallinity than the film without the buffer layer at the same substrate temperature, while the film without the buffer layer shows a more intense UV emission. Possible reasons and preventive methods are suggested to obtain highly optical quality films.     

Growth of InAs on GaAs(1 0 0) by low-pressure metalorganic chemical vapor deposition employing in situ generated arsine radicals

InAs was grown by low-pressure metalorganic chemical vapor deposition on vicinal GaAs(1 0 0) substrates misoriented by 2° toward [0 0 1]. We observed InAs crystal growth, at substrate temperatures down to 300°C, employing in situ plasma-generated arsine radicals as the arsenic source. The in situ generated arsine was produced by placing solid arsenic downstream of a microwave driven hydrogen plasma. Trimethylindium (TMIn) feedstock carried by hydrogen gas was used as the indium source. The Arrhenius plot of InAs growth rate vs. reciprocal substrate temperature displayed an activation energy of 46.1 kcal/mol in the temperature range of 300–350°C. This measured activation energy value is very close to the energy necessary to remove the first methyl radical from the TMIn molecule, which has never been reported in prior InAs growth to the best of authors’ knowledge. The film growth mechanism is discussed. The crystallinity, infrared spectrum, electrical properties and impurity levels of grown InAs are also presented.     

Growth of InP/InGaAs multiple quantum well structures by chemical beam epitaxy

InP/InGaAs multiple quantum well structures with up to 200 periods have been grown by CBE. These structures exhibit exceptional lateral uniformity, measured as ±1 Å in period, ±13 ppm in lattice mismatch and ±0.5 nm in wavelength across a 2 inch wafer. Good surface morphology, sharp interfaces and excellent growth control have all been demonstrated.     

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.     

Laser-assisted chemical beam epitaxy for selective growth

A recent exciting development in the growth of compound semiconductors is the use of light to modify the film growth rate in the irradiation area. We report Ar⁺-laser-assisted CBE of GaAs, InP, GaP and InGaAs to generate various patterned films without lithography. A linked-circle pattern is formed by laser beam scanning and a 0.85 μm pitch corrugation pattern formed by a holographic interference technique. Relationships between the growth rate and substrate temperature for the materials are compared. The mechanism of the growth rate enhancement is revealed to be photolytic decomposition of metalorganic molecules. In the case of InGaAs, laser irradiation above 500°C results in new phenomena of growth rate suppression and composition variation.     

The growth of InGaAsP by CBE for SCH quantum well lasers operating at 1.55 and 1.4 μm

InGaAsP has been grown by CBE at compositions of 1.1, 1.2 and 1.4 μm for the development of MQW-SCH lasers. The observed incorporation coefficients for TMI and TEG show strong temperature sensitivity while the phosphorus and arsenic incorporation behavior is constant over the substrate temperature range explored, 530 to 580°C setpoint. For higher substrate temperatures the growth rate increases with the largest growth rates occurring for the 1.4 μm quaternary. Low temperature photoluminescence indicates the possibility of compositional grading or clustering for the 1.1 μm material and also for the 1.2 μm material grown at the lowest substrate temperature. The final laser structure was grown with the InP cladding regions grown at 580°C with the inner cladding and active regions grown at 555°C. Using this approach we have successfully grown MQW-SCH lasers with the composition of the active In_xGa_1−xAs ranging from x=0.33 to x=0.73. Threshold current densities as low as 689 A/cm² have been measured for an 800 μm×90 μm broad area device with x=0.68.     

Crystallization of lithium metasilicate from lithium disilicate glass

The crystallization behavior of lithium disilicate glass powder heated in molten LiNO₃ salt was investigated using X-ray diffraction techniques. Heat treatment at 500°C with LiNO₃ molten salt caused a lithium metasilicate, Li₂SiO₃, crystal phase to appear after 5–96 h. By contrast, glass powder heat-treated in air at 500°C remained amorphous after 5 h and turned into lithium disilicate, Li₂Si₂O₅, crystal after 40 h. Qualitatively similar results were obtained at 400°C. Glass powder heat-treated at 575°C in both molten salt and in air turned into lithium disilicate crystal. Metasilicate crystallization occurs with LiNO₃ molten salt at 500 and 400°C due to the incorporation of lithium into the sample glass powder from the melt during crystallization. An increase in lithium content in the sample after molten salt heat treatment was confirmed by chemical analysis using dc plasma emission spectroscopy.     

Structural, thermal and dielectric studies on a new solution grown 4-dimethylaminopyridinium dihydrogen phosphate crystal

Single crystals of 4-dimethylaminopyridinium dihydrogen phosphate (DMAPDP) (C₇H₁₃N₂PO₄) were grown by the solvent evaporation method. The three-dimensional structure was solved by the single-crystal X-ray diffraction method which belongs to triclinic crystal system and the molecular arrangements in the crystal were studied. The thermal behaviour was investigated using differential scanning calorimetry (DSC) and no phase transition was identified in the temperature region −150 to 230 °C. The thermal parameters—thermal diffusivity (), thermal effusivity (e), thermal conductivity (K) and heat capacity (C_p) of DMAPDP were measured by an improved photopyroelectric technique at room temperature. Dielectric constant and dielectric loss of the grown crystal were evaluated for the frequency range 1–200 KHz in the temperature region 28–135 °C. The Vicker's hardness was measured as 42.2 for a load of 98.07 mN. The laser induced surface damage threshold of DMAPDP crystal was found to be 4.8 GW/cm² with nanosecond Nd:YAG laser.     

Energy transfer and annealing behavior of luminescence in Dy-doped PbWO4 single crystal

The Dy³⁺: PWO single crystal was subsequently annealed in air atmosphere at a temperature of 500°C, 550°C, 600°C, 700°C, 800°C, 900°C, and 1000°C, respectively. X-ray excited luminescence spectra were measured before and after each step of annealing. Annealing experiments confirmed the energy transfer-taking place from PbWO₄ (PWO) host to Dy³⁺ ions, followed by the enhancing characteristic emission of Dy³⁺ ions. In the process of annealing, the luminescence of PWO host was significantly reduced while that of Dy³⁺ was increased simultaneously. Annealing at a temperature below 700°C suppressed the blue luminescence of the PWO host and enhanced its green components, while the emission of Dy³⁺ is increased to some extent. Further annealing at higher temperature strongly reduced the luminescence of the PWO host, while the emission of Dy³⁺ was greatly increased. Interstitial oxygen O_i could play an important role in the luminescence. Annealing could modify the luminescence of Dy³⁺ ions in PWO, which may be useful in terms of some application purposes.     

Synthesis, structure and ferroelectric property of a new niobate: Sr6CrNb9O30

A new niobate Sr₆CrNb₉O₃₀ was found in the ternary system SrO---Cr₂O₃---Nb₂O₅. The transparent crystal which has a green color and a need-like shape can be grown by the flux method. The crystal structure was determined by x-ray diffraction analysis and dielectric measurement, and it belongs to the orthorhombic tungsten bronze structure at room temperature with space group Cmm2, and unit cell parameters A=1.7505(4) nm, B=1.7510(1) nm, C=7.768(4)nm, Z=4. Dielectric constant measurement show that Sr₆CrNb₉O₃₀ has two phase transitions, paraelectric to ferroelectric at 110°C and ferroelectric to ferroelastic at 205°C.     

Low-temperature synthesis of C60 thin films by ionized cluster beam deposition technique

C₆₀ films on Si(1 1 1) have been grown at low substrate temperature of 100°C by ionized cluster beam deposition technique. Fourier transform infrared (FTIR) transmission spectroscopy, Raman measurements and X-ray diffraction are employed to investigate the structure of deposited films. The results show that the acceleration voltage plays an important role in the growth of the films. As the acceleration voltage is moderate (100 V), a pristine C₆₀ film with face-centered-cubic (fcc) crystal structure can be grown. Further increase of the acceleration voltage leads to the formation of amorphous carbon (a-C) in the grown films. When the acceleration voltage is increased to 600 V, the deposited film has a complete amorphous carbon (a-C) structure.     

Bridgman growth and properties of potassium lithium niobate single crystals

Transparent KLN crystals 10mm in diameter and 25 to 45mm in length have been grown by the modified vertical Bridgman technique from different melts in the range of 3035mol% K₂O, 1723mol% Li₂O and 4350mol% Nb₂O₅. The growth conditions are a growth rate of less than 0.25 mm/hr, temperature gradient in solid-liquid interface of 23 °C/mm and growth direction of <110>. As-grown KLN crystals have tetragonal tungsten bronze structure. Most of the as-grown crystals do not crack when cooling through the paraelectric/ferroelectric phase transition. 180° domain structures are observed after the KLN crystal was etched in boiling 2HNO₃:Hf. Dielectric properties and transmission spectrum of the as-grown KLN crystals are measured.     

Magnesium-doped InGaAs using (C2H5C5H4)2Mg: application to InP-based HBTs

Heavily magnesium-doped p-type-InGaAs layers on InP(100) substrates were successfully grown, for the first time, by low-pressure metalorganic chemical vapor deposition (MOCVD) using bis-ethylcyclopentadienyl-magnesium, (C₂H₅C₅H₄)₂Mg (EtCp₂Mg), as organometallic precursor for the Mg. It was experimentally verified that the room-temperature hole concentration of Mg into InGaAs increased with increase of the V/III ratio and decrease of the growth temperature. A maximum hole concentration of over 4 × 10¹⁹ cm⁻³ was obtained. The diffusion coefficient of Mg in InGaAs was experimentally derived to be 10⁻¹² cm²/s at 800°C, which was comparable to that of Be. Finally, InP/InGaAs heterojunction bipolar transistors (HBTs) with Mg-doped bases were fabricated successfully. Measured maximum current gain was about 320 with a 90 nm thick base and a sheet resistance of the base layer of 1.28 kΩ/sq.     

Growth of Bi-Sr-Ca-Cu-O based superconducting whiskers

Superconducting whiskers of the Bi system have been grown by heating a glassy melt-quenched plate in a stream of O₂ gas. We have examined the growing phase and superconductivity of the whiskers grown at the different heating and cooling conditions. The Bi₂Sr₂CaCu₂O₈ (2212 phase) whiskers are grown from a wide range of initial compositions when the melt-quenched plates are heated at 840°C. The Bi₂Sr₂CuO₆ (2201) phase is dominant in the whiskers grown at lower temperature, 820 and 810°C. The growing pure 2223 whiskers have not been obtained so far. For the superconductivity of the 2212 whiskers, high oxygen partial pressure (P_O2, rapid cooling and higher heating temperature are preferable. Low P_O2 and slow cooling are preferable for the 2223 phase contained in the 2212 whiskers as a minor part. Heating time does not give remarkable effects on the growing phase and superconductivity.