Study of surface and interface roughnesses in porous silicon by high-resolution X-ray methods

The methods of triple-crystal X-ray diffractometry and the total external X-ray reflection are used to study porous silicon films on a p-type single crystal Si(111) substrate. For the first time, an increase of the pseudopeak intensity was experimentally observed for thick porous films. The following film characteristics are determined: thickness (1.8 μm), strain (3.8 × 10^?3), porosity (70%), pore size (～5 nm), roughness height of the surface (～3 nm) and the film—substrate interface (～7 nm), and correlation length (～7–10 nm). It is shown that the main contribution to the pseudopeak intensity for thin films on single crystal substrates comes from angular broadening of the incident beam formed by the exit slit of a monochromator of a finite width. It is shown that the method is very sensitive to density inhomogeneity in subsurface crystal layers.     

Liquid-phase epitaxy of ZnSe from Zn-Ga solution

Undoped or Ga doped ZnSe single crystal layers with thicknesses between 3 and 13 μm were grown on ZnS_xSe_1?x (0 ? x ? 1) single crystal substrates by liquid phase epitaxy in a sealed tube system from a Zn or Zn-Ga alloy solution. Smooth and uniform epitaxial layers with high crystal perfection were obtained on the (111)- and (100)-oriented substrates. All the epitaxial layers were n-type and highly conductive (0.1 < ? < 10 Ω cm). A remarkable enhancement of the blue part of the photoluminescence spectra at room temperature was observed for the epitaxial layers grown from the Zn-Ga alloy solution.     

Substituted rare earth garnet substrate crystals and LPE films for magnetooptic applications

Novel substituted transparent rare earth garnet substrates with lattice parameters as large as 12.569 Å were grown from the direct melt by the Czochralski technique. These single crystals were fabricated, polished and used as substrates in the LPE deposition of magnetic garnet thin films. The use of these large unit cell parameters has resulted in obtaining magnetooptic iron garnet films containing the light (larger radii) rare earths and bismuth. Faraday rotation measurements made on representative samples at 0.6337 μm showed Faraday rotations as high as -25.2 × 10³ deg/cm.     

Zur Realstruktur von Ga1–xInxAs LPE-Schichten

Ga_1–xIn_xAs epitaxial layers (0.02 ≦ × ≦ 0.12) are grown on (111)-oriented GaAs substrates from nonstoichiometric melts. The etch pit densities – determined by chemical etching – yield values between 2 · 10⁵ cm⁻² and 3 · 10⁷ cm⁻² and were found to be dependent on composition, layer thickness and cooling rate. X-ray topography of cleaved {110}-planes gives information on layer quality and indicates the existence of stress in the substrate lattice near the heterojunction. The validity of Vegard's law in the investigated concentration range was confirmed by X-ray determination of the lattice constants. The half width of double crystal spectrometer rocking-curves, the epd and the relative intensity of photoluminescence show similar dependence on the composition of the mixed crystal layers.     

Growth of epitaxial TmFeCuO4 thin films by pulsed laser deposition

Epitaxial thin films of TmFeCuO₄ with a two-dimensional triangular lattice structure were successfully grown on yttria-stabilized-zirconia substrates by pulsed laser deposition and ex situ annealing in air. The films as-deposited below 500 °C showed no TmFeCuO₄ phase and the subsequent annealing resulted in the decomposition of film components. On the other hand, as-grown films deposited at 800 °C showed an amorphous nature. Thermal annealing converted the amorphous films into highly (0 0 1)-oriented epitaxial films. The results of scanning electron microscopic analysis suggest that the crystal growth process during thermal annealing is dominated by the regrowth of non-uniformly shaped islands to the distinct uniform islands of hexagonal base.     

Germanium films with strong in-plane and out-of-plane texture on flexible,randomly textured metal substrates

High efficiencies have been achieved in photovoltaic cells based on III–V compounds grown on single crystal germanium substrates. Since the size of these substrates is limited and their cost is very high, such III–V photovoltaics have not found widespread terrestrial use. The objective of this work is to develop highly textured, epitaxial germanium thin films on inexpensive substrates suitable for roll-to-roll continuous processing to serve as templates for III–V compounds. Germanium films with a high degree of in-plane and out-of plane texture have been demonstrated on randomly textured, flexible nickel alloy substrates by epitaxial growth on template films made by ion beam-assisted deposition (IBAD). In order to achieve epitaxial growth, an intermediate layer of CeO₂ was found to be required between the IBAD MgO template and the Ge film. Our study shows that structural match between Ge and the underlying oxide layer is the key to epitaxial growth. Room temperature optical bandgap of the Ge films was identified at 0.67 eV suggesting minimal residual strain in the film. Refraction index and extinction coefficient values of the epitaxial Ge film were found to match well with that measured from a reference Ge single crystal.     

X-ray diffraction characterization of epitaxial CVD diamond films with natural and isotopically modified compositions

Comparative investigations of homoepitaxial diamond films with natural and modified isotopic compositions, grown by chemical vapor deposition (CVD) on type-Ib diamond substrates, are carried out using double-crystal X-ray diffractometry and topography. The lattice mismatch between the substrate and film is precisely measured. A decrease in the lattice constant on the order of (Δa/a)_relax ～ (1.1–1.2) × 10^–4 is recorded in isotopically modified ¹³С (99.96%) films. The critical thicknesses of pseudomorphic diamond films is calculated. A significant increase in the dislocation density due to the elastic stress relaxation is revealed by X-ray topography.     

RbxK1-xTiOPO4 Thin Films Grown on KTiOPO4 Substrates by Liquid Phase Epitaxy

The properties of Rb_xK_1-xTiOPO₄ thin films grown on KTiOPO₄ substrates are reported. High quality films were obtained using the flux liquid phase epitaxy method, and optical waveguiding was observed in these epitaxial films. X-ray analysis shows that the epitaxial films are single crystals films. Their cell constants are different from those of the substrates. The epitaxy growth rate and other film properties were compared for films grown on different faces. Two different surface morphologies were observed for films grown on (100) faces. The morphologies on (201) and (201) faces were also different. The quality of films grown on the (201) face was better. The reason for a structure inversion for films grown on the z⁻ face is discussed.     

Epitaxy of CdTe on sapphire substrates with titanium buffer layers

The formation of a developed electrical relief on the sapphire substrate surface is investigated. A technique is proposed for introducing Ti⁴⁺ impurity atoms into the sapphire crystal lattice by depositing titanium layers with a thickness of about 5 nm and their annealing in air (oxidizing atmosphere) to a temperature of 1400°C. It is shown that this preliminary treatment of the sapphire substrate surface results in epitaxial growth of (111) СdTe films parallel to the sapphire (0001) plane at a temperature of 350°C.     

Modifications of epitaxy in evaporated films by electric charge effects

Modifications of epitaxy in Ge, Si, CdS, β-Sn, and α-Fe films, 100–600 Å in thickness, evaporated onto air-cleaved and vacuum-cleaved (001) NaCl substrates under electron bombardment (∽10¹⁵ electrons/cm² sec, at 200–400 V) or an electric field (dc 100–300 V/cm) applied to the substrate surface were investigated by reflection electron diffraction, transmission electron microscopy and selected-area diffraction. Results indicated that epitaxial temperatures of Ge and Si films were considerably lowered, and a monocrystalline β-Sn film was produced by the application of electron bombardment. The application of electric field resulted in the formation of an epitaxial cubic CdS phase, and a single orientation in an α-Fe film. These results are discussed in terms of current speculation concerning the electric charge effects on alkali halide substrates.     

Epitaxial growth of some II–VI compound films evaporated onto electron-bombarded NaCl substrates

Epitaxial growth of CdS, CdSe, CdTe and ZnSe films, several 10–1000 Å in thickness, evaporated onto (001), (110) and (111)NaCl substrates at 50–400° C, with or without electron bombardment, and almost perpendicularly to the substrate surface, was investigated by RHEED, TEM, TED and XMA. Without electron bombardment, both wurtzite and sphalerite phases generally coexisted in the films. When the substrates were bombarded with electrons (∽10¹² electrons/cm² · sec at 300–500 V) during evaporation at about 150–300° C a single-crystal film of the sphalerite phase was obtained on the (001) and (110)NaCl, and that of the wurtzite phase on the (111)NaCl. Similar effects were observed also when the electron bombardment was applied to the substrate immediately before or in the very early stages of the deposition, or only to the evaporation vapor during the deposition. These results indicate that surface defects and electric charges of the substrate and the vapor play very important roles in the epitaxial process of these compounds.     

Preparation of InN epitaxial layers in InCl3?NH3 system

The epitaxial growth of InN by the open tube flow method using the interaction of InCl₃ and NH₃ is discussed. The influence of various technological parameters on the process and structure perfection of the epitaxial layers, grown on the single crystal (0001)-oriented sapphire substrates is considered. The main kinetic dependences of the process are plotted and discussed. InN epitaxial layers were mosaic and n-type with electron concentration 2 · 10²⁰–8 · 10²¹ cm⁻³ and mobilities 50-35 cm²/V · s, respectively.     

Room temperature epitaxial growth of (001) CeO2 on (001) LaAlO3 by pulsed laser deposition

The room temperature epitaxial growth of CeO₂ on lattice matched (001) LaAlO₃ substrates by using pulsed laser deposition (PLD) method under various oxygen partial pressure (Po₂) is demonstrated. X‐ray diffraction analysis with 2‐Theta/rocking curve/Phi‐scan, cross‐sectional transmission electron microscopy with selected‐area diffractions are used to characterize structural of grown films. The epitaxial (001) CeO₂ can be achieved at room temperature under Po₂ less than 2 × 10⁻³ Torr. The best quality of grown film is obtained under Po₂ = 2 × 10⁻⁵ Torr and degraded under Po₂ = 2 × 10⁻⁶ Torr due to oxygen deficiency in structure. The epitaxial relationship between CeO₂ and LAO is confirmed to be (001)CeO₂ //(001)LAO, [100]_CeO2//[110]_LAO and [010]_CeO2//[10]_LAO. No obvious reduction reaction occurred, from Ce⁺⁴ turned into Ce⁺³ states, as reducing oxygen partial pressure during growth by PLD.     

Annealing-induced relief of compressive misfit strain in liquid phase epitaxial yttrium iron garnet films

Films of yttrium iron garnet were grown on (111) gadolinium gallium garnet by liquid phase epitaxy from a PbO-B₂O₃ flux. Incorporation of Pb as a substitutional impurity produced an increase in film lattice parameter which resulted in initial compressive misfit strains in the films. The initial strains were relieved by annealing in O₂. The relief process was studied by X-ray double-crystal diffractometry and topography supplemented by optical and scanning electron microscopy. Strain relief was found to be associated with the occurrence of defects which were imaged in both film and substrate topographs. When the initial compressive misfit was sufficiently large, annealing eventually resulted in a tensile strain and the development of cracks which propagated through the films and into the substrates.     

利用Al/AlAs中间层调控GaAs在Si(111)上外延生长的研究

为了实现Ⅲ-V器件在硅基平台上单片集成,近年来Ⅲ-V半导体在硅衬底上的异质外延得到了广泛研究。由于Ⅲ-V半导体与Si之间大的晶格失配以及晶格结构不同,在Si上生长的Ⅲ-V半导体中存在较多的失配位错及反相畴,对器件性能造成严重影响。而Si(111)表面的双原子台阶可以避免Ⅲ-V异质外延过程中形成反相畴。本文利用分子束外延技术通过Al/AlAs作为中间层首次在Si(111)衬底上外延生长了GaAs(111)薄膜。通过一系列对比实验验证了Al/AlAs中间层的插入对GaAs薄膜质量的调控作用,并在此基础上通过低温-高温两步法优化了GaAs的生长条件。结果表明Al/AlAs插层可以为GaAs外延生长提供模板,并在一定程度上释放GaAs与Si之间的失配应力,从而使GaAs薄膜的晶体质量得到提高。以上工作为Ⅲ-V半导体在硅上的生长提供了新思路。     

Preparation and Characterization of MBE-grown Si/CaF2 Heterostructures

Growth and fabrication of silicon-on-insulator structures, based on heteroepitaxial growth of insulating films on Si, is an area of research that has rapidly developed in recent years. Thin CaF₂ films and Si/CaF₂ multilayers were prepared on {111}-oriented Si substrates by molecular beam epitaxy (MBE) and were investigated by RHEED and RBS. For epitaxial growth the Si substrates were cleaned using the ultraviolet/ozone surface cleaning method which is an effective tool to remove contaminants from the surface by low-temperature in-vacuo preheating. The growth of CaF₂ on such Si{111} substrates provides epitaxial layers with a high structural perfection. When this layer system, however, is used as a substrate for epitaxial Si growth the Si layers show always twin formation. Si layers without twins could be obtained only after deposition of thin amorphous Si buffer layers at room temperature, immediately followed by Si growth at 700 °C.     

Growth of high quality a-plane GaN epi-layer on r-plane sapphire substrates with optimization of multi-buffer layer

Nonpolar (1 1–2 0) a-plane GaN films have been grown using the multi-buffer layer technique on (1–1 0 2) r-plane sapphire substrates. In order to obtain epitaxial a-plane GaN films, optimized growth condition of the multi-buffer layer was investigated using atomic force microscopy, high resolution X-ray diffraction, and transmission electron microscopy measurements. The experimental results showed that the growth conditions of nucleation layer and three-dimensional growth layer significantly affect the crystal quality of subsequently grown a-plane GaN films. At the optimized growth conditions, omega full-width at half maximum values of (11–20) X-ray rocking curve along c- and m-axes were 430 and 530 arcsec, respectively. From the results of transmission electron microscopy, it was suggested that the high crystal quality of the a-plane GaN film can be obtained from dislocation bending and annihilation by controlling of the island growth mode.     

Epitaxial growth of ferroelectric PLZT [(Pb,La)(Zr,Ti)O3] thin films

Thin films of PLZT were epitaxially grown at around 700°C on sapphire and SrTiO₃ substrates: (111) PLZT  (0001) sapphire and (100) PLZT  (100) SrTiO₃. PLZT films on semiconductor substrates were also grown at around 620°C. The crystal quality of these PLZT films was investigated by X-ray diffraction, reflection electron diffraction, scanning electron microscopy (SEM), and Auger electron spectroscopy (AES). The epitaxy of PLZT films grown on different single crystal substrates is discussed. The refractive index of the film on the sapphire substrate was determined as 2.49₇ by an optical waveguide technique.     

Crystallographic defects in epitaxial layers of cadmium sulphide

Thin epitaxial films of CdS deposited in high vacuum on ionic single crystal substrates have been studied by transmission electron microscopy. The (100), (110) and (111) faces of NaCl and the (111) face of BaF₂ were used as substrate surfaces. Both cubic sphalerite and hexagonal wurtzite structure films have been produced. The orientations of the sphalerite structure films were (100) and (110) and were produced on substrate faces having the same two orientations. The wurtzite structure films were in (0001) orientation and grew on (111) oriented substrate faces. For a fixed rate of deposition both the number and type of defects found in the films appear to be dependent upon the growth temperature and the crystal structure. Annealing the films at a high temperature has been tested as a means for reducing their defect content and the effect is very different for the two crystal structures. A reduction in the defect content of the wurtzite structure films is induced but no change in the crystal structure occurs. In contrast to this, the sphalerite structure films undergo a progressive phase transformation to the wurtzite stucture while at the same time losing a high proportion of their defects.     

Thickness and substrate orientation dependence of ferromagnetism in Mn doped ZnO thin films

The effect of film thickness and substrate orientation on ferromagnetism in Mn doped ZnO thin films have been studied. The Mn doped ZnO films of different thickness (15, 35 and 105 nm) have been grown on both Si (100) and Si (111) substrates. The structural, electrical, optical, elemental and magnetic properties of the films have been investigated by X‐ray diffraction (XRD), Hall Effect measurements, photoluminescence (PL), energy dispersive spectroscopy (EDS) and vibrating sample magnetometer (VSM), respectively. It is found that all the properties are strongly influenced by the film thickness and substrate orientation. The XRD analysis confirmed that the formation of high quality monophasic hexagonal wurtzite structure for all the grown films. The room temperature VSM measurements showed that the films of lower thickness have better ferromagnetism than that of the thicker films grown on both the substrates. Among the lower thickness films, the film grown on Si (111) substrate has higher saturation magnetization (291×10^‐5 emu cm^‐3) due to high density of the defects. The observed ferromagnetism has been well justified by XRD, Hall measurements and PL. The presence of Mn atoms in the film has been confirmed by EDS. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)