Optimal crystal growth conditions of thin films of Bi2Te3 semiconductors

Crystal growth conditions of Bi₂Te₃ narrow bandgap semiconductors have been studied using molecular beam epitaxy method. It was applied to the growth of Bi₂Te₃ on Bridgman single-crystal substrate Sb₂Te₃. Substrate ingots were taken from the natural cleavage along the (0001) plane. The deposited conditions have been studied as a function of substrate temperature (T_s) and flux ratio (F_R=F(Te)/F(Bi)). The quality of deposited layers was controlled by X-ray diffraction, scanning electron microscope (SEM), secondary ion mass spectroscopy (SIMS) depth profiling and energy-dispersive X-ray (EDX) microanalyser. The sticking coefficients K_s(Te) and K_s(Bi) of the elements that compose Bi₂Te₃ were determined. It was found that the stoichiometry of deposited layers depended on substrate temperature and flux ratio. It was observed that all deposited layers were single-crystal in the orientation of their substrates with a small shift due to the stress in layer.     

Growth of GaN/AlN and AlGaN by MOCVD using triethylgallium and tritertiarybutylaluminium

Films of aluminium nitride (AIN) with thicknesses in the range from 200 to 3600 Å have been deposited at 1050°C by low-pressure MOCVD. Using an alternative precursor, tritertiarybutylaluminium (^tBu₃Al), and ammonia (NH₃), we have grown AlN on sapphire (c-Al₂O₃). At a growth rate of 0.35 μm/h, the FWHM of the rocking curve measured by X-ray diffraction was 150 arcsec. Therefore, we used the thin AlN films as buffer layers for the deposition of gallium nitride (GaN) at 950°C using triethylgallium (Et₃Ga). Aluminium gallium nitride (Al_xGa_1−xN) with aluminium contents x from 0 to 0.5 were grown using a mixture of Et₃Ga and ^tBu₃Al. The strctural and optical properties of GaN, AlGaN and AlN were verified by X-ray diffraction (XRD), spectrally resolved photoconductivity (SPC), photothermal deflection (PDS) and photoluminescence spectroscopies.     

Structural investigation of gallium oxide (β-Ga2O3) nanowires grown by arc-discharge

Gallium oxide nanowires were synthesized by electric arc discharge of GaN powders mixed with a small amount of Ni and Co. The crystal structure of nanowires was determined by multi-channel X-ray diffractometry (MC-XRD), FT-Raman spectroscopy and transmission electron microscopy (TEM). The analyzed results clearly show that the synthesized nanowires are monoclinic gallium oxide (β-Ga₂O₃). Final morphology and microstructure of β-Ga₂O₃ nanowires were changed depending on the presence of the transition metals into the nanowires. The β-Ga₂O₃ nanowires grown by the assistance of transition metals demonstrate a smooth edge surface while containing twin defects at the center. The transition metals have enhanced the step growth of nanowires. However, in the case of the β-Ga₂O₃ nanowires, where the transition metals are not shown on the surface, the nanowires demonstrate rather thin and long shapes with amorphous gallium oxide layers on the nanowire surface.     

Properties of (Ga0.47In0.53)As epitaxial layers grown by metalorganic vapor phase epitaxy (MOVPE) using alternative arsenic precursors

In this study, the use of novel, liquid, organic arsenic precursors as substitutes for the highly toxic hydride gas arsine (AsH₃) in low pressure metalorganic vapor phase epitaxy (LP-MOVPE) of (GaIn)As lattice matched on InP has been investigated. The model precursors out of the classes of (alkyl)3-nAsH_n (n = 0,1,2) are tertiarybutyl arsine (TBAs), ditertiarybutyl arsine (DitBAsH) and diethyltertiarybutyl arsine (DEtBAs). The MOVPE growth has been investigated in the temperature range of 570–650°C using V/III ratios from 2 to 20. The obtained epitaxial layer quality as examined by means of optical and scanning electron microscopy (SEM), high resolution double crystal X-ray diffraction, temperature-dependent van der Pauw-Hall, as well as photoluminescence (PL) measurements, will be compared for the different source molecules. Under optimized conditions almost uncompensated n-type (GaIn)As layers with carrier concentrations below 1 × 10¹⁵ cm⁻³ and corresponding mobilities above 80 000 cm²/V · s have been realized. For TBAs and DitBAsH in combination with the corresponding P sources TBP and DitBuPH, respectively, we have worked out a process parameter area for the growth of layers with device quality, as proven by the realization of a pin-detector structure.     

Structural and optical properties of CuGaSe2 layers grown by the hot wall epitaxy method

Copper gallium selenide (CuGaSe₂, CGS) layers were grown by the hot wall epitaxy method. The optimum temperatures of the substrate and source for growth turned out to be 450 and 610 °C, respectively. The CGS layers were epitaxially grown along the 1 1 0 direction and consisted of Ga-rich components indicating the slight stoichiometric deviations. Based on the absorption measurement, the band-gap variation of CGS was well interpreted by the Varshni's equation. The band-gap energies at low temperatures, however, had a higher value than those of other CGS. It suggests that the band-gap increase is influenced by the slightly Ga-rich composition. From the low-temperature photoluminescence experiment, sharp and intensive free- and bound-exciton peaks were observed. By analyzing these emissions, a band diagram of the observed optical transitions was obtained. From the solar cell measurement, an 11.17% efficiency on the n-CdS/p-CGS junction was achieved.     

MOVPE growth of GaInP/GaAs hetero-bipolar-transistors using CBr4 as carbon dopant source

Carbon doping of GaAs with carbon tetrabromide (CBr₄) in low pressure MOVPE has been investigated and applied to the fabrication of GaInP/GaAs HBTs. Especially the hydrogen incorporation and the associated acceptor passivation has been studied. The hydrogen found in single GaAs:C layers is predominantly incorporated during cooling the sample under AsH₃ after growth, n-Type capping layers can block this H indiffusion and GaAs:C base layers in HBTs show much lower H concentrations than GaAs:C single layers without a cap. A further reduction of acceptor passivation is possible by optimization of the growth procedure. First HBTs processed from layers with a base that was doped using CBr₄ show promising DC and HF performance (β = 45, for 2 × 20 μm² devices).     

Characteristic crystal growth from amorphous WO3 film by vacuum heating

Selective growth of WO₂, W and WO_3−x crystals from amorphous WO₃ film by vacuum heating at 400–900°C was clarified. The grown WO_3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO₂ crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO₂ crystal consumes WO₃ microcrystallites with various orientations. The growth speed of the WO₂ depended on WO₃ microcrystallites orientation. The origin of the wavy growth front of WO₂ was due to an orientation dependence of the WO₃ microcrystallites.     

Vapor phase epitaxy of pure VO2 and V1−xCrxO2

The vapor phase epitaxy of thin epilayers of VO₂ and V_1−xCrxO₂ on TiO₂ transparent substrates is described. Chemical vapor deposition occurs by reacting a (VOCL₃/CrO₂Cl₂/H₂O/H₂) mixture at about 800°C using argon as a carrier gas. The preparation of pure VO₂ requires special care to make it homogeneously stoichiometric and to obtain steep concentration profiles at the TiO₂/VO₂ interface. Layers were obtained which had electrical and optical properties comparable to the best bulk crystals grown by other techniques. Homogeneous solid solutions of V_1−xCr_xO₂ epilayers were also grown for the first time in the range o < x < 0.17. Chromium concentration and homogeneity were determined by electron microprobe analysis. The separation coefficient k was also found to vary with x. It is close to unity below x = 0.001 and above this value Cr is incorporated more easily. High quality heteroepitaxial layers (1 cm² area, 1 to 30 μm thickness) of V_1−xCr_xO₂ have for the first time allowed the measurement of the optical absorption coefficient.     

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.     

In-situ RHEED study on the effect of light irradiation on Ge/Si heteroepitaxial growth by GeH4 source MBE

Effects of light irradiation on growth processes in the initial stage of growth of Ge films on (100)Si substrates by gas source molecular beam epitaxy using GeH₄ have been investigated by in-situ RHEED observations. It has been found that the growth rate is enhanced by an Ar⁺ ion laser and a D₂ lamp irradiation, and, moreover, that the growth process sequence of the Ge films irradiated by the Ar⁺ laser and D₂ lamp is the same as that without irradiation. The irradiation effect on the photolysis of GeH₄ gas has been examined by mass spectroscopy. The increase of the growth rate is due to the photolysis of GeH₄ and the excitation of substrate surfaces by vacuum-ultraviolet light in the D₂ lamp irradiation, and is due to only the excitation of substrate surfaces in the Ar⁺ laser irradiation.     

Model for defect-free epitaxial lateral overgrowth of Si over SiO2 by liquid phase epitaxy

A growth model for defect-free epitaxial lateral overgrowth by liquid phase epitaxy is presented. Growth in the pure step flow mode and a preferential development of (111) planes in liquid phase epitaxy permit one to quantitatively predict the overgrowth. The shape and size of the Si lamellae which grow over SiO₂ depend on the crystallographic orientations of the substrate growth face and of the seeding windows. Overgrowth experiments with Si on oxidized, (111)- and (100)-oriented Si wafers serve to verify the model. Growth experiments from In and Bi solutions in temperature intervals between 950 and 800°C yield overgrowth widths up to 120 μm and aspect ratios of 40:1 on (111) oriented wafers.     

p-Type GaAs doped by diiodomethane (CI2H2) in molecular beam epitaxy, metalorganic molecular beam epitaxy, and chemical beam epitaxy

Highly p-type carbon-doped GaAs epitaxial layers were obtained using diiodomethane (CI₂H₂) as a carbon source. In the low 10¹⁹ cm⁻³ range, almost all carbon atoms are electrically activated and at 9×10¹⁹ cm⁻³, 91% are activated. The carbon incorporation efficiency in GaAs layers grown by metalorganic molecular beam epitaxy (MBE) and chemical beam epitaxy (CBE) is lower than that by MBE due to the site-blocking effect of the triethylgallium molecules. In addition, in CBE of GaAs using tris-dimethylaminoarsenic (TDMAAs), the carbon incorporation is further reduced, but it can be increased by cracking TDMAAs. Annealing studies indicate no hydrogenation effect.     

As2S3 and AgI thin layers as ion sensitive membranes

The possibilities of using thin layers of As₂S₃ and AgI as ion sensitive membranes for ion selective field-effect transistors (ISFETs) are investigated. The thin films have been prepared by vacuum deposition on static and rotating substrates. The As₂S₃ layers were additionally doped with silver. The influence of the type of substrates and preparation conditions on electrochemical properties of the layers was studied. Electrochemical measurements revealed a reasonable sensitivity of chalcogenide and halide layers to silver and iodide ions, respectively. The near Nernstian behavior of sensitivity of As₂S₃ layers to Ag⁺ ions and of AgI layers to I⁻ ions is observed. The results obtained are promising for the development of ISFETs.     

基于碳化硅衬底的宽禁带半导体外延

宽禁带半导体具备禁带宽度大、电子饱和飘移速度高、击穿场强大等优势,是制备高功率密度、高频率、低损耗电子器件的理想材料。碳化硅(SiC)材料具有热导率高、化学稳定性好、耐高温等优点,在SiC衬底上外延宽禁带半导体材料,对充分发挥宽禁带半导体材料的优势,并提升宽禁带半导体电子器件的性能具有重要意义。得益于SiC衬底质量持续提升及成本不断降低,基于SiC衬底的宽禁带半导体电子市场占比呈现逐年增加的态势。在SiC衬底上外延生长高质量的宽禁带半导体材料是提高宽禁带半导体电子器件性能及可靠性的关键瓶颈。本文综述了近年来国内外研究者们在SiC衬底上外延SiC、氮化镓(GaN)、氧化镓(Ga₂O₃)所取得的研究进展,并展望了SiC衬底上宽禁带半导体外延的发展及应用前景。     

Kinetics and mechanisms of surface reactions in epitaxial growth of Si from SiH4 and Si2H6

Surface science and kinetic modelling studies of the surface chemical mechanisms active during low pressure chemical vapor deposition (CVD) and chemical beam epitaxy (CBE) growth of Si from mono- and disilane are summarized. Time-of-flight direct recoiling (DR) is discussed as an in situ method to analyze the composition of the growth interface. Steady state measurements of surface hydrogen coverage (θ_H) are made by DR in situ during CBE Si growth from Si₂H₆ and SiH₄, and are illustrated here. Key results using other experimental methods are briefly discussed.     

Epitaxial growth of the CoFe2O4 film on SrTiO3 and its characterization

Cobalt ferrite (CoFe₂O₄) thin film is epitaxially grown on (0 0 1) SrTiO₃ (STO) by laser molecular beam epitaxy (LMBE). The growth modes of CoFe₂O₄ (CFO) film are found to be sensitive to laser repetition, the transitions from layer-by-layer mode to Stranski–Krastanov (SK) mode and then to island mode occur at the laser repetition of 3 and 5 Hz at 700 °C, respectively. The X-ray diffraction (XRD) results show that the CFO film on (0 0 1) SrTiO₃ is compressively strained by the underlying substrate and exhibits high crystallinity with a full-width at half-maximum of 0.86°. Microstructural studies indicate that the as-deposited CFO film is c-oriented island structure with rough surface morphology and the magnetic measurements reveal that the compressive strained CoFe₂O₄ film exhibits an enhanced out-of-plane magnetization (190 emu/cm³) with a large coercivity (3.8 kOe).     

Multilayer SiO2 and TiO2 coatings on glasses by the sol-gel process

Glass films of pure SiO₂ and TiO₂ have been prepared on sodalime silica flat slide glasses by the sol-gel process using the dip-coating technique from TEOS and Ti(OC₃H₇)₄ solutions. The various parameters such as chemicals concentrations, viscosity, type of catalyst, withdrawal speed and temperature of densification leading to the obtention of good and adherent coatings with definite film thicknesses are reported. The same technique has been used for the depositon of layers of colored films SiO₂---M_xO_y (M = Co, Mn, Nd and Cr). Brilliant yellow coatings have been obtained with TiO₂---CeO₂.     

The growth kinetics of (SmY)3(FeGa)5O12 epitaxial layers in the 920–980°C range

The growth kinetics of (SmY)₃(FeGa)₅O₁₂ garnets obtained by liquid phase epitaxy on Gd₃Ga₅O₁₂ substrates are discussed in the 920 to 980°C. range. The experiments have been carried out with the substrates in a horizontal plane and with unidirectional rotation ranging from 30 to 300 rotations per minute (rpm). A sharp increase in the growth velocity at temperatures higher than 960°C is interpreted on the basis of a diffusion-reaction theory. It is found that the diffusion constant increases steeper at higher temperatures and that the linear law of the growth rate as a function of the square root of the rotation rate holds to much higher rotation rates at these temperatures. The influence of the surface incorporation is too small to be detectable. The results are compared with published data concerning other compositions.     

Selective area epitaxy of InP/GaInAsP heterostructures by MOMBE

This study reports on the selective area growth of InP/GaInAsP layers and heterostructures by metaloganic molecular beam epitaxy (MOMBE). It was found that neither the growth rate nor the material composition for GaInAsP depends on the area where material growth takes place. This enables a flexible SiO₂ mask to be designed independent of the aspect ratio. The use of slightly misoriented substrates allows the selective growth of planar structures having nearly perfectly vertical side walls even for 2 μm thick layers or narrow stripes to take place.     

Crystal growth of NdAl3(BO3)4 from K2O/MoO3/Nd2O3/B2O3/KF flux

NdAl₃(BO₃)₄ single crystals were grown by the flux method and the TSSG technique using a K₂O/3MoO₃/B₂O₃/0.5Nd₂O₃/KF flux system. Light-violet clear crystals could be obtained. The effects of fluoride on the growth of NAB crystals were investigated. As the content of KF was gradually increased, the growth form of NAB was changed from the equant to the columnar and the primary crystalline region of NAB was shrinked. At the ratio of KF/K₂O = 0.75, NAB crystals could not be grown.