High-quality InP grown by chemical beam epitaxy

InP films were grown by chemical beam epitaxy using trimethylindium (TMI) and pure phosphine (PH₃) in a flow control mode with hydrogen as the carrier gas, with the TMI flow rate fixed at 3 SCCM. Substrate temperatures were varied between 505 and 580°C and V/III ratios from 3 to 9. InP layers with high optical quality (intense and narrow excitonic transition lines) and high crystalline quality (narrow and symmetric X-ray diffraction peaks) could be grown only within a narrow parameter window around a substrate temperature of 545°C (δT_s ≤ 25°C) and a V/III ratio of 5.5 (δ(V/III) ≤ 2). Carrier densities of 8 × 10¹⁴ cm^-3 with mobilities of 70000 cm²/V.s measured at 77 K were obtained for growth conditions close to the edge of this parameter window towards low V/III ratios. The growth rate of inP was also clearly at its maximum in the given parameter window. Leaving the window, by changing either the growth temperature or the V/III ratio, significantly decreased the growth rate. This reduced growth rate was accompanied by a degradation in the crystalline quality. We also demonstrate that for higher TMI flow the parameter window shifts to higher growth temperatures. The InP could be doped effectively with Si in the range from 9 × 10¹⁵ to 3 × 10¹⁸ cm^-3.     

Floating zone growth of high-quality SrTiO3 single crystals

Strontium titanate single crystals 15–20 mm in diameter and 40–80 mm in length were grown by a floating zone method with radiation heating. Additional crystal heating just below the molten zone by an in-growth annealing furnace was applied in order to lower the temperature gradients and to achieve slower cooling of the grown crystal. The crystal perfection was studied with X-ray topography and double-crystal diffractometry. The most perfect crystals were grown in [0 0 1] direction with single grain rocking curve widths of about 30″ and subgrain misorientations of 1′–3′ over 10×10 mm² areas of the boule cross-section for both (0 0 1)-, (1 1 0)- and (1 1 1)-oriented slices. Such high-quality crystal can be grown reproducibly with starting materials of 4N grade quality.     

SiC epitaxial layer growth in a novel multi-wafer vapor-phase epitaxial (VPE) reactor

Experimental results are presented for SiC epitaxial layer growths employing a unique planetary SiC-VPE reactor. The high-throughput, multi-wafer (7×2″) reactor, was designed for atmospheric and reduced pressure operation at temperatures up to and exceeding 1600°C. Specular epitaxial layers have been grown in the reactor at growth rates ranging from 3–5 μm/h. The thickest layer grown to date is 42 μm thick. The layers exhibit minimum unintentional n-type doping of 1×10¹⁵ cm⁻³, and room temperature mobilities of 1000 cm²/V s. Intentional n-type doping from 5×10¹⁵ cm⁻³ to >1×10¹⁹ cm⁻³ has been achieved. Intrawafer layer thickness and doping uniformities (standard deviation/mean at 1×10¹⁶ cm⁻³) are typically 4 and 7%, respectively, on 35 mm diameter substrates. Moderately doped, 4×10¹⁷ cm⁻³, layers, exhibit 3% doping uniformity. Recently, 3% thickness and 10% doping uniformity (at 1×10¹⁶ cm⁻³) has been demonstrated on 50 mm substrates. Within a run, wafer-to-wafer thickness deviation averages 9%. Doping variation, initially ranging as much as a factor of two from the highest to the lowest doped wafer, has been reduced to 13% at 1×10¹⁶ cm⁻³, by reducing susceptor temperature nonuniformity and eliminating exposed susceptor graphite. Ongoing developments intended to further improve layer uniformity and run-to-run reproducibility, are also presented.     

Effects of growth temperature and V/III ratio on surface structure and ordering in Ga0.5In0.5P

Surface photoabsorption (SPA) measurements were used to clarify the CuPt ordering mechanism in Ga_0.5In_0.5P layers grown by organometallic vapor phase epitaxy. The CuPt ordering is known to be strongly affected by the growth temperature and the input partial pressure of the phosphorus precursor, i.e. the V/III ratio. The SPA peak at 400 nm was found to be a measure of the concentration of [ 10]-oriented phosphorus dimers on the surface, which are characteristic of the (2 × 4) reconstruction. Both ordering, measured using the low temperature photoluminescence peak energy, and the SPA signal difference due to P dimers were studied versus the growth temperature and V/III ratio. The degree of order decreases markedly with increasing growth temperature above 620°C at a constant V/III ratio of 40. This corresponds directly to a decrease of the [ 10]-oriented P dimer concentration on the surface determined using SPA. Below 620°C, the degree of order decreases as the growth temperature decreases, even though the concentration of P dimers increases. The presence of an isotropic “excess P” phase observed in the SPA spectrum at 480 nm might be responsible for the decrease of CuPt ordering, although it has previously been attributed to the slow rearrangement of adatoms. The degree of order is found to decrease monotonically with decreasing V/III ratio in the range from 160 to 8 at 670°C and from 40 to 8 at 620°C. This also corresponds directly to the decrease of the P dimer concentration on the surface measured using SPA. At 620°C and a V/III ratio of 160, the degree of order decreased despite an increase of the P dimer concentration. This may also be due to the formation of the isotropic “excess P” phase on the surface. The direct correlation of the [ 10]-oriented P dimer concentration and the degree of order with changes in temperature ( ≥ 620°C) and V/III ratio (≤ 160 at 670°C and ≤ 40 at 620°C) suggests that, in this range of growth parameters, the (2 × 4) surface reconstruction is necessary to form the CuPt structure, in agreement with published theoretical studies.     

SIMS study of the concentration of dopants in LPCVD silicon thin films

Measurements of solid phase dopant concentration (S) of LPCVD Si thin films as a function of substrate temperature (T_s = 500−640 ° C) and gas phase doping ratio (R = 1 × 10⁻⁵ −4 × 10⁻²) by SIMS indicate different behaviors of P and B in the films. A linear relation S = b(T)R is observed for B-doped film with b(T) varying from 4 to 50 depending on T_s. Boron-doped microcrystalline film has a higher doping efficiency than that of P-doped ones.     

Investigations on the effect of InSb and InAsSb step-graded buffer layers in InAs0.5Sb0.5 epilayers grown on GaAs (0 0 1)

We report the structural and electrical properties of InAsSb epilayers grown on GaAs (0 0 1) substrates with mid-alloy composition of 0.5. InSb buffer layer and InAs_xSb_1−x step-graded (SG) buffer layer have been used to relax lattice mismatch between the epilayer and substrate. A decrease in the full-width at half-maximum (FWHM) of the epilayer is observed with increasing the thickness of the InSb buffer layer. The surface morphology of the epilayer is found to change from 3D island growth to 2D growth and the electron mobility of the sample is increased from 5.2×10³ to 1.1×10⁴ cm²/V s by increasing the thickness of the SG layers. These results suggest that high crystalline quality and electron mobility of the InAs_0.5Sb_0.5 alloy can be achieved by the growth of thick SG InAsSb buffer layer accompanied with a thick InSb buffer layer. We have confirmed the improvement in the structural and electrical properties of the InAs_0.5Sb_0.5 epilayer by quantitative analysis of the epilayer having a 2.09 μm thick InSb buffer layer and 0.6 μm thickness of each SG layers.     

Metastable PbO crystal grown through alcohol-thermal process

An alcohol-thermal route has been developed to the growth of single crystals of yellow metastable PbO in largest dimensions of 11×1×0.1 mm³, using freshly synthesized β-PbO crystallites as seeds. The transformation of metastable β-PbO to stable form (-PbO) can be slowed down by choosing appropriate solvent as the growth medium. The obtained β-PbO crystals have a strong orientational growth parallel to the (0 0 1) plane and exhibit a lath shape. Studies found that cooling rate and NaOH concentration also have great influence on the crystallographic forms of the final products during the alcohol-thermal process.     

Growth of large dimension BaWO4 crystal by the Czochralski method

In this paper, polycrystalline materials of BaWO₄ were synthesized by solid-state phase method, and a single crystal of BaWO₄ was successfully grown along a and c-axis direction by using the Czochralski method. Up to 20×22×80 mm³ BaWO₄ crystal was obtained, and X-ray powder diffraction results show that the as-grown BaWO₄ crystal belongs to the scheelite structure. The effective segregation coefficients of Ba and W of the BaWO₄ crystal were measured by the X-ray fluorescence method, and the effective segregation coefficients of Ba and W were near 1. The rocking curve from (2 0 0) diffraction plane of as-grown BaWO₄ single crystal was measured on the High-resolution X-ray diffractometer D5005, and the full-width at half-maximum value was found to be 26.64′′ The density and hardness of the BaWO₄ crystal was measured, the measured density was in agreement with the calculated result, and the Mohs hardness was about 4.     

Facets formation of pyramidal Si nanocrystals selectively grown on Si(0 0 1) windows in ultrathin SiO2 films

We have used in situ scanning tunneling microscopy (STM) to study the facet formation in the selective growth of pyramidal Si nanocrystals on Si(0 0 1) windows in ultrathin 0.3-nm-thick SiO₂ films. Broad (0 0 1) surfaces developed as the top of the crystals, and {1, 1, (2n+1)} (n=1–6) facets formed the sidewalls. As growth continued, the slope angle of sidewall facets increased, and {1, 1, 9} and {1, 1, (2m+1)} (0 <m < 4) facets often came to coexist on the sidewalls. On well-oriented Si(0 0 1) surfaces, layer-by-layer growth in the [0 0 1] direction was dominant. On vicinal Si(0 0 1) surfaces, lateral step growth took place in the initial stage, and the layer-by-layer growth was suppressed until after a large (0 0 1) surface had formed as the top of the crystal.     

Growth of InP in chemical beam epitaxy with high purity tertiarybutylphosphine

InP layers were grown by chemical beam epitaxy (CBE) using high purity thermally precracked tertiarybutylphosphine (TBP) and trimethylindium (TMI) as the source of the group III element. For optimized substrate temperature and V/III ratio, InP films of good electrical and optical quality have been obtained; the n-type background carrier concentration is (1–2) × 10¹⁵ cm^-3, with a Hall mobility at 77 K being μ₇₇ = 45,000 cm² V^-1 s^-1. Given the low value of the V/III ratio, and according to mass spectrosc measurements, the phosphorus species giving rise to epitaxy is expected to be the dimer P₂. The TBP consumption in CBE is very low when compared to organometallic vapour phase epitaxy (OMVPE), typicaly below 0.25 g/μm of InP layer.     

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.     

Replacement of hydrides by TBAs and TBP for the growth of various III–V materials in production scale MOVPE reactors

Besides the standard group V precursors AsH₃ and PH₃, so-called alternative precursors like TBAs and TBP (tertiary-butyl-arsine and tertiary-butyl-phosphine) are more and more important in today's MOVPE processes. A lot of publications have demonstrated that these precursors can be successfully used for the growth of different III–V materials. In this study we want to demonstrate that TBAs and TBP can be used as the group V precursor in a complete family of production scale reactors. It is shown that these precursors can be used for the growth of InP-based as well as for GaAs-based materials. The reactors that have been employed are medium scale reactors (AIX 200/4; 1 × 2 inch, 3 or 4 inch or 3 × 2 inch capability) and large scale Planetary Reactors®, in particular the AIX 2400 system (15 × 2 inch or 5 × 4 inch). Materials that have been grown are (Al)GaInP on GaAs and GaInAsP on InP. The lower cracking energy of these precursors compared to PH₃ and AsH₃ allows one to use lower growth temperatures and lower V/III ratios, particularly in combination with the high cracking efficiencies of the used reactors. For the growth of GaInAsP on InP, the consumption of TBP and TBAs is up to 8 times lower than using PH₃ and AsH₃. GaInP on GaAs could be grown with a V/III ratio as low as 25 in a Planetary Reactor®. Good crystalline quality is demonstrated by DCXD (e.g. for GaInP: FWHM = 35 arcsec, substrate 32 arcsec). PL intensity and growth rate are not affected by using the alternative precursors. The compositional uniformity is similar to layers grown with arsine and phosphine (e.g. 1.5 nm uniformity for GaInAsP (λ = 1.5 μm) on 2 inch; approximately 1 nm uniformity for GaInP) [1,2]. The purity of the grown layers depends mainly on the quality of the TBP and TBAs. Using high purity TBP, InP revealed background carrier concentration in the mid 10¹⁴ cm⁻³ regime. Our investigation shows that TBP and TBAs can replace phosphine and arsine in state of the art MOVPE reactors. Both for single and multi-wafer production MOVPE reactors these compounds can be used successfully for the growth of the entire material spectrum in the Al---Ga---In---As---P system.     

Optical microscopic, synchrotron X-ray topographic and reticulographic study of homoepitaxial CVD diamond

Surface topography and crystal-lattice perfection of homoepitaxial layers deposited by microwave plasma CVD on (0 0 1) and near-(0 0 1) facets polished on HPHT synthetic diamond are described. Optical micrographic techniques included birefringence, Nomarski and 2-beam interference. The synchrotron X-ray experiments comprised Laue topography plus a recently developed sensitive misorientation-measuring technique, reticulography. Two special circumstances enhanced information yield from the experiments. First, the substrate crystal was unusually strain-free and had a very low dislocation content. Second, epilayer growth had taken place in two stages, depositing thicknesses of 10 μm and 30–34 μm, respectively. This double deposition complicated the observations, but added features of scientific and practical interest. Epilayer cracking finally present had occurred almost entirely before the second growth stage. With assistance from quantitative data provided by reticulography, the X-ray diffraction properties of the substrate and epilayers are analysed. Lattice misorientations on the untreated lower surface of the substrate were only 1 arcsec except close to growth-sector boundaries and dislocation outcrops. The final epilayer growth surface above areas where cracking in the first epilayer was absent or sparse exhibited near-perfect-crystal diffraction behaviour.     

Structure and optical properties of self-assembled InAs/GaAs quantum dots with In0.15Ga0.85As underlying layer

A high density of 1.02×10¹¹ cm⁻² of InAs islands with In_0.15Ga_0.85As underlying layer has been achieved on GaAs (1 0 0) substrate by solid source molecular beam epitaxy. Atomic force microscopy and PL spectra show the size evolution of InAs islands. A 1.3 μm photoluminescence (PL) from InAs islands with In_0.15Ga_0.85As underlying layer and InGaAs strain-reduced layer has been obtained. Our results provide important information for optimizing the epitaxial structures of 1.3 μm wavelength quantum dots devices.     

A new technique for the growth of superconducting YBa2Cu3O6 + δ crystals completely separated from flux

Growth of completely flux-separated YBa₂Cu₃O_{6 + δ} (referred to as 123 phase) crystals using a novel technique is described. The technique employs a modification of the seed pulling method commonly used in crystal growth. The crystals are grown in the temperature range of 960–1000°C using a BaCuO₂ flux. A 123 flux ratio of 1:5 is maintained. Photographs of the crystals and photomicrograph of the surfaces are presented to show complete flux-separation of the crystals measuring 6 mm × 3 mm × 1 mm. The Raman spectra recorded on the as-grown crystals show that they are in the tetragonal phase. Magnetic susceptibility measurements on crystals annealed in an oxygen atmosphere show a superconducting transition starting at 71 K. The present technique offers a possibility of growing large, completely flux-separated crystals of 123 for superconductivity research.     

Metalorganic vapor-phase epitaxy of III/V phosphides with tertiarybutylphosphine and tertiarybutylarsine

Indium phosphide, gallium arsenide phosphide, and aluminum indium phosphide have been deposited by metalorganic vapor-phase epitaxy using tertiarybutylphosphine and tertiarybutylarsine. The effects of growth temperature and V/III ratio on the amount of silicon, sulfur, carbon, and oxygen in InP have been determined. Minimum incorporation was observed at 565 °C and a V/III ratio of 32. In this case, the material contained a background carrier concentration of 2.7×10¹⁴ cm⁻³, and the Hall mobilities were 4970 and 135,000 cm²/V s at 300 and 77 K. The oxygen contamination in AlInP was found to be only 9.0×10¹⁵ cm⁻³ for deposition at 650 °C and a V/III ratio of 35. The relative distribution of arsenic to phosphorus in GaAs_yP_1−y was determined at temperatures between 525 and 575 °C. The distribution coefficient [(N_As/N_P)_film/(P_TBAs/P_TBP)_gas] ranged from 25.4 to 8.4, and exhibited an Arrhenius relationship with an apparent activation energy of 1.2 eV.     

Comparative analysis of characteristics of Si, Mg, and undoped GaN

We have grown undoped, Si- and Mg-doped GaN epilayers using metalorganic chemical vapor deposition. The grown samples have electron Hall mobilities (carrier concentrations) of 798 cm²/V s (7×10¹⁶ cm⁻³) for undoped GaN and 287 cm²/V s (2.2×10¹⁸ cm⁻³) for Si-doped GaN. Mg-doped GaN shows a high hole concentration of 8×10¹⁷ cm⁻³ and a low resistivity of 0.8 Ω cm. When compared with undoped GaN, Si and Mg dopings increase the threading dislocation density in GaN films by one order and two orders, respectively. Besides, it was observed that the Mg doping causes an additional biaxial compressive stress of 0.095 GPa compared with both undoped and Si-doped GaN layers, which is due to the incorporation of large amount of Mg atoms (4–5×10¹⁹ cm⁻³).     

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     

Defect reduction in GaN epilayers and HFET structures grown on (0 0 0 1)sapphire by ammonia MBE

The quality of GaN epilayers grown by molecular beam epitaxy on substrates such as sapphire and silicon carbide has improved considerably over the past few years and in fact now produces AlGaN/GaN HEMT devices with characteristics among the best reported for any growth technique. However, only recently has the bulk defect density of MBE grown GaN achieved levels comparable to that obtained by MOVPE and with a comparable level of electrical performance. In this paper, we report the ammonia-MBE growth of GaN epilayers and HFET structures on (0 0 0 1)sapphire. The effect of growth temperature on the defect density of single GaN layers and the effect of an insulating carbon doped layer on the defect density of an overgrown channel layer in the HFET structures is reported. The quality of the epilayers has been studied using Hall effect and the defect density using TEM, SEM and wet etching. The growth of an insulating carbon-doped buffer layer followed by an undoped GaN channel layer results in a defect density in the channel layer of 2×10⁸ cm⁻². Mobilities close to 490 cm²/Vs at a carrier density of 8×10¹⁶ cm⁻³ for a 0.4 μm thick channel layer has been observed. Growth temperature is one of the most critical parameters for achieving this low defect density both in the bulk layers and the FET structures. Photo-chemical wet etching has been used to reveal the defect structure in these layers.     

Surface reconstructions and growth mode transitions of AlAs(100)

The surface reconstructions of AlAs(100) layers grown by molecular beam epitaxy (MBE) on GaAs(100) were mapped as a function of substrate temperature and arsenic flux. Three main reconstructions were observed - a c(4×4) at lower temperatures and higher arsenic fluxes, a (2×4) at middle temperatures, and a (3×2) at higher temperatures and lower arsenic fluxes. Growth of AlAs on AlAs(100) is layer-by-layer for the high temperature and low temperature reconstructions. In the mid-temperature region, AlAs grows rough on (2×4) reconstructed AlAs(100) as indicated by rapidly damped reflection high-energy electron diffraction (RHEED) intensity oscillations and the appearance of three-dimensional (3D) features. The addition of fractional layers of Ga enhances the smooth growth of AlAs. A metastable (5×2) reconstruction was observed when a fraction of a layer of Ga was present on the surface. The results indicate that Ga segregates during the growth of AlAs on GaAs(100) at temperatures at least as low as 500°C, and that annealing at temperatures above 700°C removes most of the Ga from the surface.