Dip-coating conditions and modifications of lead titanate and lead zirconate titanate films

The modifications of dip-coated lead titanate (PT) and lead zirconate titanate (PZT) films strongly depend on the film thickness and the substrate in addition to the heat-treatment temperature. At 500 to 600 ° C, metastable paraelectric pyrochlore grew on glass plates (amorphous plates) when the thickness of the coated films produced by one coating cycle was below 100 nm, while ferroelectric perovskite formed on crystalline substrates or when thick films were coated on amorphous plates. This tendency is discussed in terms of an inhomogeneous reaction and the epitaxial effect. The perovskite PT films coated on single-crystal SrTiO₃ plate at 700 ° C were strongly oriented to thec-axis.     

N-type crystalline silicon films free of amorphous silicon deposited on glass by HCl addition using hot wire chemical vapour deposition

Since n-type crystalline silicon films have the electric property much better than those of hydrogenated amorphous and microcrystalline silicon films, they can enhance the performance of advanced electronic devices such as solar cells and thin film transistors (TFTs). Since the formation of amorphous silicon is unavoidable in the low temperature deposition of microcrystalline silicon on a glass substrate at temperatures less than 550 degrees C in the plasma-enhanced chemical vapour deposition and hot wire chemical vapour deposition (HWCVD), crystalline silicon films have not been deposited directly on a glass substrate but fabricated by the post treatment of amorphous silicon films. In this work, by adding the HCl gas, amorphous silicon-free n-type crystalline silicon films could be deposited directly on a glass substrate by HWCVD. The resistivity of the n-type crystalline silicon film for the flow rate ratio of [HCl]/[SiH4] = 7.5 and [PH3]/[SiH4] = 0.042 was 5.31 x 10(-4) ohms cm, which is comparable to the resistivity 1.23 x 10(-3) ohms cm of films prepared by thermal annealing of amorphous silicon films. The absence of amorphous silicon in the film could be confirmed by high resolution transmission electron microscopy.     

Preparation of lead zirconate titanate thin films with a combination of self-assembly and spin-coating techniques

A low-temperature synthetic method for preparing lead zirconate titanate (PZT) perovskite film on a Pt substrate is proposed. The method consists of the self-assembly of PZT particles on a substrate and successive spin coating with a precursor of PZT. The PZT particles that had sub-micron sizes and perovskite structures were prepared by annealing amorphous PZT particles formed from a complex alkoxide precursor. The PZT particles were deposited on a Pt substrate that was surface-modified with (3-mercaptopropyl) trimethoxysilane to chemically fix the particles on the substrate. Another PZT precursor solution was used for the spin-coating on the PZT-deposited substrate, and then the spin-coated film was annealed at 350 °C to remove organic residues left in the film. The spin-coated PZT film prepared at 350 °C had a dielectric constant of 118 at a frequency of 1000 Hz.     

Preparation of nanocrystalline TiN coated cubic boron nitride powders by a sol-gel process

Cubic boron nitride (cBN) particles coated with 20 wt% nanocrystalline TiN were prepared by coating the surface of cBN particles with TiO2, followed by nitridation with NH3 gas at 900 degrees C. Coating of TiO2 on cBN powders was accomplished by a sol-gel process from a solution of titanium (IV) isopropoxide and anhydrous ethanol. An amorphous TiO(x) layer of 50 nm thickness was homogenously formed on the surface of the cBN particles by the sol-gel process. The amorphous layer was then crystallized to an anatase TiO2 phase through calcination in air at 400 degrees C. The crystallized TiO2 layer was 50 nm in thickness, and the size of TiO2 particles comprising the layer was nearly 10 nm. The TiO2 on cBN surfaces was completely converted into nanocrystalline TiN of uniform particles 20 nm in size on cBN particles by nitridation under flowing NH3 gas.     

Evaluation of the oxidation of TiO2 films during reactive evaporation of Ti3O5 and during exposure of the films to the atmosphere

A surplus amount of oxygen is needed to produce titanium dioxide film by reactive electron-beam evaporation of Ti3O5. We investigated the ratio of the rates at which oxygen molecules and TiO(x) molecules impinge upon substrates at 25 degrees and 250 degrees C to produce TiO2 filmsthat show no optical absorption in the visible spectral region. On unheated substrates the ratio was 49, and at 250 degrees C it was 26, provided that the substrates had been exposed to air after being coated at the given substrate temperature. Higher ratios were required if the TiOs film was covered with a SiO2 film, which impeded further oxidation. Furthermore, the postdeposition oxidation behavior of these films was studied.     

Soft solution synthesis of ZnO films with developed superstructures

A novel and simple two-step solution approach to prepare ZnO thin film consisted of 3D flower-like superstructure was demonstrated. The uniform, nano-dimensional scale and sphere-like ZnO crystals were first prepared on the borosilicate glass substrate in mild solution at 95 degrees C for 3 h, then introduced into 0.02 mol L(-1) hexamethylenetetramine (HMT, C6H12N4) aqueous solution and heated at the same temperature for 3 d. The obtained ZnO thin films were characterized by XRD, SEM and photoluminescence. The results indicated that the thin film with 3D flower-like superstructure possessed high crystallinity, high surface-volume ratio microstructure and excellent photoluminescence property. It is a potential way to prepare nano-structured materials by the mentioned simple and novel two-step solution synthesis process.     

The effects of substrate and annealing on structural and electrochemical properties in LiCoO2 thin films prepared by DC magnetron sputtering

LiCoO2 thin films were fabricated by direct current magnetron sputtering method on STS304 and Ti substrates. The effects of substrate and annealing on their structural and electrochemical properties of LiCoO2 thin film cathode were studied. Crystal structures and surface morphologies of the deposited films were investigated by X-ray diffraction and field emission scanning electron microscopy. The as-deposited films on both substrates have amorphous structure. The (104) oriented perfect crystallization was obtained by annealing over 600 degrees C in STS304 substrate. The LiCoO2 thin film deposited on Ti substrate shows the (003) texture after annealing at 700 degrees C. The electrochemical properties were investigated by the cyclic voltammetry and charge-discharge measurement. The 600 degrees C-annealed LiCoO2 film deposited on STS304 substrate exhibits the inithial discharge capacity of 22 uAh/cm2 and the 96% capacity retention rate at 50th cycles. The electrochemical measurement on annealed films over 600 degrees C was impossible due to the formed TiO2 insulator layer using Ti substrate. As a result, it was found that the STS304 substrate seems to be more suitable material than the Ti substrate in fabricating LiCoO2 thin film cathode.     

Synthesis and characterization of titania-coated silver nanoparticles

Silver particles of 70 +/- 10 nm mean diameter were coated with uniform layers of amorphous titania by the hydrolysis and polycondensation process using titanium(IV) n-butoxide in aqueous solution. Because of the large dielectric function of titania, a shift to the longer wavelengths was observed for the plasmon resonance maximum of coated silver nanoparticles. By changing the alkoxide to particles ratio in the reaction mixture, thickness ranging from 5 to 20 nm was obtained. Hydrothermal treatment performed on coated particles at 350 degrees C for 4 h converted amorphous titania to the anatase crystalline form. The anatase form was confirmed by X-ray powder diffraction. More red shift of the plasmon resonance was observed for the hydrothermally treated samples compared with the particles coated with amorphous titania.     

Nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition

Nano-polycrystalline vanadium oxide thin films have been successfully produced by pulsed laser deposition on Si(100) substrates using a pure vanadium target in an oxygen atmosphere. The vanadium oxide thin film is amorphous when deposited at relatively low substrate temperature (500 degrees C) and enhancing substrate temperature (600-800 degrees C) appears to be efficient in crystallizing VOx thin films. Nano-polycrystalline V3O7 thin film has been achieved when deposited at oxygen pressure of 8 Pa and substrate temperature of 600 degrees C. Nano-polycrystalline VO2 thin films with a preferred (011) orientation have been obtained when deposited at oxygen pressure of 0.8 Pa and substrate temperatures of 600-800 degrees C. The vanadium oxide thin films deposited at high oxygen pressure (8 Pa) reveal a mix-valence of V5+ and V4+, while the VOx thin films deposited at low oxygen pressure (0.8 Pa) display a valence of V4+. The nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition have smooth surface with high qualities of mean crystallite size ranging from 30 to 230 nm and Ra ranging from 1.5 to 22.2 nm. Relative low substrate temperature and oxygen pressure are benifit to aquire nano-polycrystalline VOx thin films with small grain size and low surface roughness.     

Effects of temperature on columnar microstructure and recrystallization of TiO2 film produced by ion-assisted deposition

Titanium oxide thin films were deposited by electron-beam evaporation with ion-beam-assisted deposition. The effect of the substrate temperature and annealing temperature on the columnar microstructure and recrystallization of titanium oxide was studied. The values of the refractive index varied from 2.26 to 2.4, indicating that the different substrate temperatures affected the film density. X-ray diffraction revealed that all films were amorphous as deposited. At annealing temperatures from 100 degrees C to 300 degrees C, only the anatase phase was formed. As the substrate temperature increased from 150 degrees C to 200 degrees C to 250 degrees C, the recrystallization temperature fell from 300 degrees C through 250 degrees C to 200 degrees C. Changing the substrate temperature resulted in the formation of various types of columnar microstructure, as determined by scanning-electron microscopy. Different columnar structures resulted in different surface morphologies, as measured by atomic-force microscopy.     

Optimization of PECVD silicon oxynitride films for anti-reflection coating

In this work, amorphous silicon oxynitride films were deposited on silicon substrates by plasma-enhanced chemical vapor deposition (PECVD). The main purpose was to use silicon oxynitride film as a single-layer anti-reflection coating for Si-based optoelectronic devices. The chemical information was measured by infrared spectroscopy. Surface and cross-section morphology was determined by a scanning electron microscope. Spectroscopic ellipsometry (SE) was applied to measure the refractive index, extinction coefficient and thickness. The results of SE presented the refractive indices varied in the range of 1.83-1.92 by altering SiH₄/NH₃ ratio. One-side polished silicon substrate coated with silicon oxynitride film exhibited low reflectance, and two-side polished silicon substrate coated with silicon oxynitride film exhibited high transmittance. The results suggested that silicon oxynitride film was a very attractive single-layer anti-reflection coating.     

Polycrystalline silicon films on glass grown by amorphous-liquid-crystalline transition at temperatures below 330 °C

An approach to deposit polycrystalline silicon layers on amorphous substrates is presented. It is shown that metastable amorphous silicon can be transformed into its more stable microcrystalline structure at a temperature below 330 °C via an intermediate liquid solution stage. In particular, the interaction of liquid indium nanodroplets in contact with amorphous silicon is shown to lead to the formation of circular polycrystalline domains. Crystallinity of these domains is analyzed by micro-Raman spectroscopy. The droplet size necessary for the onset of crystallization is related to the temperature of the film. Full coverage of the substrate with microcrystalline silicon has been obtained at 320 °C within less than one hour. These films might act as seeding layers for further enlargement by steady-state liquid phase epitaxy.     

Amorphous alumina coatings: processing, structure and remarkable barrier properties

Amorphous aluminium oxide coatings were processed by metalorganic chemical vapour deposition (MOCVD); their structural characteristics were determined as a function of the processing conditions, the process was modelled considering appropriate chemical kinetic schemes, and the properties of the obtained material were investigated and were correlated with the nanostructure of the coatings. With increasing processing temperature in the range 350 degrees C-700 degrees C, subatmospheric MOCVD of alumina from aluminium tri-isopropoxide (ATI) sequentially yields partially hydroxylated amorphous aluminium oxides, amorphous Al2O3 (415 degrees C-650 degrees C) and nanostructured gamma-Al2O3 films. A numerical model for the process allowed reproducing the non uniformity of deposition rate along the substrate zone due to the depletion of ATI. The hardness of the coatings prepared at 350 degrees C, 480 degrees C and 700 degrees C is 6 GPa, 11 GPa and 1 GPa, respectively. Scratch tests on films grown on TA6V titanium alloy reveal adhesive and cohesive failures for the amorphous and nanocrystalline ones, respectively. Alumina coating processed at 480 degrees C on TA6V yielded zero weight gain after oxidation at 600 degrees C in lab air. The surface of such low temperature processed amorphous films is hydrophobic (water contact angle 106 degrees), while the high temperature processed nanocrystalline films are hydrophilic (48 degrees at a deposition temperature of 700 degrees C). It is concluded that amorphous Al2O3 coatings can be used as oxidation and corrosion barriers at ambient or moderate temperature. Nanostructured with Pt or Ag nanoparticles, they can also provide anti-fouling or catalytic surfaces.     

Fabrication of a polyurethane acrylate/polyimide-based polymer mold for a hot embossing process

A high-thermal-resistance polymer-based flexible imprint mold was developed to be used in a hot embossing process. This mold was readily replicated in a UV curing imprint process and can be used as a mold for hot embossing and thermally curing imprint processes. The nano-sized pattern of this mold was not degraded by soaking at 350 degrees C for 10 min and the pattern fidelity was maintained after 10 separate cyclic heating tests between 0 degrees C and 350 degrees C. The substrate of this flexible mold was PI film, and a UV-cured polyurethane acrylate (PUA) layer was used to form the nano-scale patterns. The durability of this polymeric mold was tested by repetitive hot embossing processes. Nano-scale patterns of the mold were readily transferred to a PMMA layer coated onto a Si substrate by hot embossing lithography at 180 degrees C. After 10 cycles of hot embossing processes, no damage or degradation was observed in the flexible polymer mold. Using this polymer mold, patterns as small as 50 nm were successfully transferred to a Si substrate. Due to the flexibility of the polymer mold, nano-scale patterns were successfully transferred to a non-flat acryl substrate by hot embossing lithography.     

Influence of substrate temperature and film thickness on the structure of reactively evaporated In2O3 films

Indium oxide films 25–550 Å thick were reactively evaporated at an oxygen pressure of about 0.27 Pa and at a substrate temperature between room temperature and 400°C. The dependence of the structure of the films on the substrate temperature and on the film thickness was studied using transmission electron microscopy and electron diffraction. It was found that thick films (about 550 Å) were amorphous at room temperature, partially crystallized at 50–125°C and crystalline at 150–400°C. The crystallinity of the films deposited at 150–250°C also depended markedly on the film thickness. Very thin films about 25 Å thick were quasi-amorphous, but with increasing film thickness the amorphous phase transformed into a crystalline phase.The thermal transformation of the amorphous films after deposition was also studied. Amorphous films about 550 Å thick deposited at room temperature and 100°C crystallized at 230°C and 210°C respectively.     

Fabrication of La<Subscript>3</Subscript>TaO<Subscript>7</Subscript> using a new precursor solution route by chemical solution method

La₃TaO₇ (LTO) has been fabricated using a new precursor solution route by chemical solution method. The newly developed LTO precursor solution was obtained in ambient atmosphere. A serious of studies on the properties of LTO precursor gel and its powder annealed at different temperatures were presented in order to understand the decomposition of LTO precursor gel and the growth behavior of LTO. The single phase LTO powder and LTO film on textured Ni–W substrate were obtained after annealed at 1,100° in a gas mixture of Ar-4% H₂. But it should be pointed out that LTO film was annealed by adopting a rapid elevated temperature processing (RETP) method. X-ray diffraction shows that the LTO film on Ni–W tape was highly oriented, and its out-of-plane texture is very close to that of the underlying Ni–W substrate. The SEM investigation of LTO film reveals a dense, smooth, pinhole-free and crack-free microstructure for coated buffer. These results offer the potential to use the LTO film prepared by the new precursor solution route as a buffer layer for further manufacturing other buffer layer in coated conductors.     

Interfacial reactions between Sn-3.5 Ag solder and Ni–W alloy films

Nickel based alloys are currently being investigated in an effort to develop stable barrier films between lead free solder and copper substrate. In this study, interfacial reactions between Ni–W alloy films and Sn-3.5 Ag solder have been investigated. Ni–W alloys films with tungsten content in the range of 5.0–18.0 at.% were prepared on copper substrate by electrodeposition in ammonia citrate bath. Solder joints were prepared on the Ni–W coated substrate at a reflow temperature of 250 °C. The solder joint interface was investigated by Cross-sectional scanning electron microscopy, energy dispersive X-ray spectroscopy and electron back scatter diffraction. It has been observed that a Ni₃Sn₄ layer with faceted morphology formed on the Ni–W alloy film after reflow. The thickness of the bright layer was found to decrease with the increase of tungsten content in the Ni–W film. An additional layer with a bright appearance was also found to form below the Ni₃Sn₄ layer. The bright layer was identified to be a ternary phase containing Sn, W and Ni. The bright layer is found to be amorphous and is suggested to have formed through solid state amorphization caused by anomalously fast diffusion of Sn into Ni–W film.     

BaTiO3 thin film prepared by coating-pyrolysis process on Nb-doped SrTiO3 substrate

Epitaxial BaTiO3 thin film was prepared on Nb-doped SrTiO3 substrate by coating-pyrolysis process using a mixed solution of barium and titanium naphthenates. The amorphous film pyrolyzed at 470 °C was crystallized with high orientation after heat-treatment at 850 °C under low oxygen partial pressure. X-ray diffraction /2 and scans indicated that the BaTiO3 film was epitaxial relationship with Nb-doped SrTiO3 substrate. The dielectric constant was approximately 230 at 103 Hz and was monotonically decreased with increasing of frequency at room temperature.     

Crystallization of Au-Si/glass thin film: a real-time synchrotron X-ray scattering study

The crystallization of amorphous, Si-rich, Au28Si72/glass thin film was studied in real-time synchrotron X-ray scattering experiments. The amorphous film crystallizes first into Au and Si phases at a low temperature of 206 degrees C. At annealing temperatures above eutectic temperature (T(E) = 360 degrees C), the Au phase melts while the Si phase rapidly grows further. The crystallized Au28Si72 thin film has nanowire-type grains with 1000-nm-length and 10-nm-diameter. We confirm that the Au liquid phase contributes to the low-temperature crystallization of the Si solid phase for Si-nanowire growth.