Correlation between interfacial structure and c-axis-orientation of LiNbO3 films grown on Si and SiO2 by electron cyclotron resonance plasma sputtering

Thin films of crystalline lithium niobate (LN) grown on Si(1 0 0) and SiO₂ substrates by electron cyclotron resonance plasma sputtering exhibit distinct interfacial structures that strongly affect the orientation of respective films. Growth at 460–600 °C on the Si(1 0 0) surface produced columnar domains of LiNbO₃ with well-oriented c-axes, i.e., normal to the surface. When the SiO₂ substrate was similarly exposed to plasma at temperatures above 500 °C, however, increased diffusion of Li and Nb atoms into the SiO₂ film was seen and this led to an LN–SiO₂ alloy interface in which crystal-axis orientations were randomized. This problem was solved by solid-phase crystallization of the deposited film of amorphous LN; the degree of c-axis orientation was then immune to the choice of substrate material.     

Agglomeration control during the selective epitaxial growth of Si raised sources and drains on ultra-thin silicon-on-insulator substrates

We have studied the impact of several Si selective epitaxial growth (SEG) process on the agglomeration of ultra-thin, patterned silicon-on-insulator (SOI) layers. Through a careful analysis of the effects of the in situ H₂ bake temperature (that followed an ex situ “HF-last” wet cleaning) and of the silicon growth temperature on the SOI film quality, we have been able to develop a low-temperature SEG process that allows the growth of Si on patterned SOI layers as thin as 3.4 nm without any agglomeration or Si moat recess at the Si window/shallow trench isolation edges. This process consists of an in situ H₂ bake at 650 °C for 2 min, followed by a ramping-up of the temperature to 750 °C, then some SEG of Si at 750 °C using a chlorinated chemistry (i.e. SiH₂Cl₂+HCl).     

Formation of LiNbO3 films by hydrolysis of metal alkoxides

Homogeneous, crack-free, thin films of crystalline LiNbO₃ were synthesized above 250°C on Si(100) substrates by the dip-coating method using a double alkoxide solution. The coating solution, which was prepared by the controlled partial hydrolysis of the double alkoxide, gave stoichiometric LiNbO₃ crystalline films at temperatures as low as 250°C. The concentration of the alkoxide solution influenced both of thickness and quality of films. Crystallinity of thin film top-coated directly on the substrate affected the crystallization state of films coated on the film remarkably. Films crystallized on -Al₂O₃(0001) showed preferred orientation along the c-axis, while the preferred orientation could not be observed on Si(100) substrates.     

A new method for fabricating water repellent silica films having high heat-resistance using the sol–gel method

There has been a great demand in the field of kitchen appliances to develop transparent water repellent films which have high heat-resistance around 300°C. However, those films have not been obtained by conventional sol–gel methods. In this paper, we propose a new method for fabricating transparent water repellent films with high heat-resistance using the sol–gel method, in which silicon or germanium substrates were coated with a solution including tetraethoxysilane (Si(OC₂H₅)₄) and (2-perfluorooctyl)ethyltrimethoxysilane (CF₃(CF₂)₇C₂H₄Si(OCH₃)₃), followed by ‘ammonia-treatment' and annealed at 300°C. The contact angles of water on the ammonia-treated film maintained its initial value, 110° after the heat treatment at 300°C for 250 h while those on the untreated film decreased to 70°, indicating that the ammonia-treatment improves heat-resistance on the film. The mechanism of ammonia-treatment was inferred from FT-IR results; the ammonia-treatment should accelerate hydrolysis and polymerization of FAS and TEOS molecules, resulting in high density of siloxane bonds between FAS and silica glass. These bonds suppress the evaporation of FAS molecules from the film during the heat treatment at 300°C, thus the film has high heat-resistance.     

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).     

Structure and thermal stability of MOCVD ZrO2 films on Si (1 0 0)

The structure and thermal stability of ZrO₂ films grown on Si (1 0 0) substrates by metalorganic chemical vapor deposition have been studied by high-resolution transmission electron microscopy, selected area electron diffraction and X-ray energy dispersive spectroscopy. As-deposited films consist of tetragonal ZrO₂ nanocrystallites and an amorphous Zr silicate interfacial layer. After annealing at 850°C, some monoclinic phase is formed, and the grain size is increased. Annealing a 6 nm thick film at 850°C in O₂ revealed that the growth of the interfacial layer is at the expense of the ZrO₂ layer. In a 3.0 nm thick Zr silicate interfacial layer, there is a 0.9 nm Zr-free SiO₂ region right above the Si substrate. These observations suggest that oxygen reacted with the Si substrate to grow SiO₂, and SiO₂ reacted with ZrO₂ to form a Zr silicate interfacial layer during the deposition and annealing. Oxygen diffusion through the tetragonal ZrO₂ phase was found to be relatively easier than through the monoclinic phase.     

Effect of NH3 on the growth characterization of TiN films at low temperature

Titanium nitride (TiN) films were obtained by the atmospheric pressure chemical vapor deposition method of the TiCl₄–N₂–H₂ system with various flow rates of NH₃ at 600°C. The growth characteristics, morphology and microstructure of the TiN films deposited were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Without NH₃ addition, no TiN was deposited at 600°C as shown in the X-ray diffraction curve. However, by adding NH₃ into the TiCl₄–N₂–H₂ system, the crystalline TiN was obtained. The growth rate of TiN films increased with the increase of the NH₃ flow rate. The lattice constant of TiN films decreased with the increase of the NH₃ flow rate. At a low NH₃ flow rate, the TiN (2 2 0) with the highest texture coefficient was found. At a high NH₃ flow rate, the texture coefficient of TiN (2 0 0) increased with the increase of the NH₃ flow rate. In morphology observation, thicker plate-like TiN was obtained when the NH₃ flow rate was increased. When the flow rate of NH₃ was 15 sccm, Moiré fringes were observed in the TiN film as determined by TEM analysis. The intrinsic strain was found in the TiN film as deposited with 60 sccm NH₃.     

Analysis of the formation of BaTiO3 island deposited on (111) InSb by metalorganic chemical vapor deposition at low temperature

Islands of BaTiO₃ in a thin film deposited on a (111) InSb substrate by metalorganic chemical vapor deposition at a temperature of 300°C were investigated. Refractive index measured by ellipsometer using a He-Ne laser was 1.95, which is nearly the same value as that of amorphous BaTiO₃ with microcrystals. X-ray diffraction peaks showed the deposit to be mostly amorphous and partly crystalline having the 110BaTiO₃ direction normal to the (111) InSb. Transmission electron microscopy results showed that partially epitaxial BaTiO₃ islands with periodic misfit dislocations had been formed at the interface between amorphous BaTiO₃ thin layer and the (111) InSb substrate. These BaTiO₃ islands on the (111) InSb substrate formed at a low growth temperature were three-dimensional nuclei which were closely associated with surface irregularities of the (111) InSb substrate.     

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.     

Anomalous effect of temperature on atomic layer deposition of titanium dioxide

A strong influence of growth temperature on the deposition rate and refractive index of TiO₂ thin films, grown by atomic layer deposition from TiCl₄ and H₂O, was observed. The growth rate increased from 0.05 to 0.09 nm per cycle while the refractive index decreased from 2.63 to 2.00 with the increase of growth temperature from 150°C to 225°C. The effect was due to crystallization processes starting at these temperatures. The substrate temperature range, in which the growth rate most significantly changed, depended on the TiCl₄ pulse time.     

Low-pressure chemical vapor deposition of TaCN films by pyrolysis of ethylamido-tantalum

Thin films of Tantalum nitride (TaN) were deposited from tetra-ethylamido-tantalum (Ta (NEt₂)₄) by low-pressure chemical vapor deposition. Good-quality step coverage is achieved below 400°C, because the deposition rate is determined by the reaction rates on the surface. The film resistivity increases, however, as the substrate temperature decreases. In order to obtain the low resistivity of films deposited at lower temperatures, we have increased the amount of injected H₂ gas during the deposition. The resistivity decreases by the increase in the H₂ gas flow rate, and it is shown that a large amount of H₂ gas injection during the deposition is an effective method for obtaining both low resistivity and high-quality step coverage. The residual carbon concentration in the film is measured to be >10%, on the other hand, the concentration of N less than 1%. The microstructural investigation using transmission electron microscopy (TEM) reveals that crystalline structure of the deposited film has an amorphous phase.     

Homoepitaxial growth of 6H–SiC thin films by metal-organic chemical vapor deposition using bis-trimethylsilylmethane precursor

Homoepitaxial silicon carbide (SiC) films were grown on 3.5° off-oriented (0 0 0 1) 6H–SiC by metal-organic chemical vapor deposition (MOCVD) using bis-trimethylsilylmethane (BTMSM, C₇H₂₀Si₂). A pronounced effect of the growth conditions such as source flow rate and growth temperature on the polytype formation and structural imperfection of the epilayer was observed. The growth behavior was explained by a step controlled epitaxy model. It was demonstrated by high-resolution X-ray diffractometry and transmission electron microscopy that high-quality 6H–SiC thin films were successfully grown at the optimized growth condition of substrate temperature 1440°C with the carrier gas flow rate of 10 sccm.     

Effect of heat treatment on phase transformation of aluminum nitride ultrafine powder prepared by chemical vapor deposition

Ultrafine aluminum nitride (AlN) powders were obtained by chemical vapor deposition via AlCl₃–NH₃–N₂ system operated at various temperatures and at a same 200 cm³/min flow rate of NH₃ and N₂, respectively. It has been shown that when the reaction temperature of AlCl₃ and NH₃ was above 600°C, then crystalline AlN powder can be formed; whereas, amorphous AlN was obtained with NH₄Cl if reacted in a lower-temperature zone of the reaction chamber. The amorphous AlN powder was heat treated at 1400°C under NH₃ and N₂ atmosphere for 2 h, then the crystalline phases of the obtained powder belong to a single phase of AlN; a mixture of AlN and Al₂O₃ and only AlON, respectively. On the other hand, if crystalline AlN powder is heat treated at 1400°C under N₂ atmosphere for 2 h, the crystalline phases were composed of the major phase of AlN and a minor phase of Al₂O₃. The morphology, particle size and agglomerate size of the AlN powder were strongly dependent on the heat-treatment temperature. The particle size of AlN powder increases from 28.1 to 45.0 nm, as the heat treatment temperature increases from 800 to 1400°C.     

Annealing effects of highly homogeneous a-Si1−xCx:H

We report the effect of annealing on the properties of amorphous hydrogenated silicon carbide thin films. The samples were deposited onto different substrates by plasma enhanced chemical vapor deposition at temperatures between 300 and 350 °C. The gaseous mixture was formed by silane and methane, at the ‘silane starving plasma regime’, and diluted with hydrogen. Rutherford backscattering and Fourier transform infrared spectrometry were used, respectively, to determine the atomic composition and chemical bonds of the samples. The film’s structure was analyzed by means of X-ray absorption fine structure and X-ray diffraction. For temperatures higher than 600 °C, amorphous silicon carbide films annealed under inert atmosphere (Ar or N₂) clearly changed their structural and compositional properties due to carbon loss and oxidation, caused by the presence of some oxygen in the annealing system. At 1000 °C, crystallization of the films becomes evident but only stoichiometric films deposited on single crystalline Si[1 0 0] substrates presented epitaxial formation of SiC crystals, showing that the crystallization process is substrate dependent. Films annealed in high-vacuum also changed their structural properties for annealing temperatures higher than 600 °C, but no traces of oxidation were observed or variations in their silicon or carbon content. At 1200 °C the stoichiometric films are fully polycrystalline, showing the existence of only a SiC phase. The XANES signal of samples deposited onto different substrates and annealed under high-vacuum also show that crystallization is highly substrate dependent.     

Properties of ZnO films grown on (0 0 0 1) sapphire substrate using H2O and N2O as O precursors by atmospheric pressure MOCVD

In this paper, we compare the properties of ZnO thin films (0 0 0 1) sapphire substrate using diethylzinc (DEZn) as the Zn precursor and deionized water (H₂O) and nitrous oxide (N₂O) as the O precursors, respectively in the main ZnO layer growth by atmospheric pressure metal–organic chemical vapor deposition (AP-MOCVD) technique. Surface morphology studied by atomic force microscopy (AFM) showed that the N₂O-grown ZnO film had a hexagonal columnar structure with about 8 μm grain diameter and the relatively rougher surface compared to that of H₂O-grown ZnO film. The full-widths at half-maximum (FWHMs) of the (0 0 0 2) and () ω-rocking curves of the N₂O-grown ZnO film by double-crystal X-ray diffractometry (DCXRD) measurement were 260 and 350 arcsec, respectively, indicating the smaller mosaicity and lower dislocation density of the film compared to H₂O-grown ZnO film. Compared to H₂O-grown ZnO film, the free exciton A (FX_A) and its three phonon replicas could be clearly observed, the donor-bound exciton A⁰X (I₁₀):3.353 eV dominated the 10 K photoluminescence (PL) spectrum of N₂O-grown ZnO film and the hydrogen-related donor-bound exciton D⁰X (I₄):3.363 eV was disappeared. The electron mobility (80 cm²/V s) of N₂O-grown ZnO film has been significantly improved by room temperature Hall measurement compared to that of H₂O-grown ZnO film.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.     

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.     

HREM investigations of intermediate ZnO and ZnO/Y–ZrO2 layers in Y–ZrO2 bicrystals and ZnO films grown on Y–ZrO2 bicrystal substrates

The structure of yttrium-stabilized ZrO₂ (YSZ) bicrystals with ZnO and ZnO/YSZ/ZnO/YSZ/ZnO intermediate layers, as well as ZnO films grown on YSZ bicrystal (1 1 0)/90° substrates, has been investigated by means of high-resolution electron microscopy (HREM) and microanalysis. All bicrystals were produced by the solid-phase intergrowth (SPI) method. The internal ZnO film in the bicrystal formed at the SPI temperature of 1400°C consisted of domains with two symmetrical orientations: , and , . A bicrystal with a ZnO/YSZ/ZnO/YSZ/ZnO internal film was formed at the temperature of 1200°C. There was no mixing of ZnO and YSZ films and no traces of any solid-phase reactions were observed. Grains in all internal ZnO films and ZnO films grown on the bicrystal substrates had numerous stacking faults. It was found that SPI does not influence the density and structure of these defects. Orientational relationships between YSZ and ZnO in all samples were determined. The ZnO films grown on (1 1 0)/90° bicrystal substrates inherited the grain boundary (GB) from the substrate. Its structure and geometry is determined by four variants of ZnO grain growth.     

The photoluminescence of ZnO thin films grown on Si (1 0 0) substrate by plasma-enhanced chemical vapor deposition

High-quality ZnO thin films have been grown on a Si(1 0 0) substrate by plasma-enhanced chemical vapor deposition (PECVD) using a zinc organic source (Zn(C₂H₅)₂) and carbon dioxide (CO₂) gas mixtures at a temperature of 180°C. A strong free exciton emission with a weak defect-band emission in the visible region is observed. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption peak in the absorption spectra, are closely related to the gas flow rate ratio of Zn(C₂H₅)₂ to CO₂. Full-widths at half-maximum of the free exciton emission as narrow as 93.4 meV have been achieved. Based on the temperature dependence of the PL spectra from 83 to 383 K, the exciton binding energy and the transition energy of free excitons at 0 K were estimated to be 59.4 meV and 3.36 eV, respectively.     

Enhanced two-dimensional growth of MOVPE InN films on sapphire (0 0 0 1) substrates

MOVPE growth of InN on sapphire substrates is compared using two different designs of horizontal reactor. The major difference between the two designs is a variation in the reactant-gas flow-spacing between the substrate and the ceiling of the quartz chamber: 33 mm for the Type A reactor and 14 mm for Type B. Compared with the Type A reactor, the Type B reactor brings about InN films with a larger grain size. This is especially true when InN is grown at 600°C using the Type B reactor, in which case the two-dimensional (2D) growth of InN is found to be extremely enhanced. An investigation of the NH₃/TMIn molar ratio dependence of the surface morphology of grown InN films using the two reactors suggests that the enhanced 2D growth is attributed to the decrease in the effective NH₃/TMIn ratio in the growth atmosphere. Even using the Type A reactor, a film with enhanced 2D growth can be obtained when the NH₃/TMIn ratio is considerably low (1.8×10⁴). The enhanced 2D growth results in a smaller XRC-FWHM (full-width at half maximum of the X-ray rocking curve) (1500 arcsec), than that for a 3D-grown film (5000 arcsec).