Surface morphology, growth rate and quality of diamond films synthesized in hot filament CVD system under various methane concentrations

Hot filament chemical vapor deposition (CVD) technique has been used to deposit diamond films on silicon substrate. In the present study, diamond films were grown at various vol.% CH₄ in H₂ from 0.5% to 3.5%, at substrate temperature and pressure of 850 °C and 80 torr, respectively. Scanning electron microscopy, X-ray diffraction and Raman spectroscopy were employed to analyze the properties of deposited films. The formation of methyl radicals as a function of vol.% CH₄ not only changes film morphology but also increase film growth rate. At low, intermediate and high vol.% CH₄, cluster, faceted cubes and pyramidal features growth, were dominant. By increasing vol.% CH₄ from 0.5% to 3.5%, as the growth rate improved from ∼0.25 μm/h to ∼2.0 μm/h. Raman studies features revealed high purity diamond films at intermediate range of vol.% CH₄ and grain density increased by increasing CH₄ concentration. The present study represents experimentally surface morphology, growth rate and quality of diamond films grown in hot filament CVD system at various CH₄ concentrations.     

Enhanced field emission characteristics of boron doped diamond films grown by microwave plasma assisted chemical vapor deposition

Boron doped diamond films were synthesized on silicon substrates by microwave plasma chemical vapor deposition (MPCVD) technique. The effect of B₂O₃ concentration varied from 1000 to 5000 ppm on the field emission characteristics was examined. The surface morphology and quality of films were characterized by scanning electron microscope (SEM) and Raman spectroscopy. The surface morphology obtained by SEM showed variation from facetted microcrystal covered with nanometric grains to cauliflower of nanocrystalline diamond (NCD) particles with increasing B₂O₃ concentration. The Raman spectra confirm the formation of NCD films. The field emission properties of NCD films were observed to improve upon increasing boron concentration. The values of the onset field and threshold field are observed to be as low as 0.36 and 0.08 V/μm, respectively. The field emission current stability investigated at the preset value of ∼1 μA is observed to be good, in each case. The enhanced field emission properties are attributed to the better electrical conductivity coupled with the nanometric features of the diamond films.     

Magnetic properties of Co/Pd multilayered films on porous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> templates with developed cell substructure

We studied the structure and magnetic properties of porous multilayered Co/Pd films deposited on the templates of anodized Al₂O₃ with a specific surface morphology that is characterized by a cellular–porous structure with several pores inside each cell. X-ray diffraction analysis and reflectometry are used to study the peculiarities of the formation of phases in deposited films. The effect of morphological features of porous Co/Pd films on their magnetoanisotropic properties and magnetization reversal processes (magnetization reversal mechanisms, domain structure of films, and coercive field H _c ) is revealed by SQUID magnetometry and magnetic force microscopy.     

Nanostructured high valence silver oxide produced by pulsed laser deposition

Among silver oxides, Ag₄O₄, i.e. high valence Ag(I)Ag(III) oxide, is interesting for applications in high energy batteries and for the development of antimicrobial coatings. We here show that ns UV pulsed laser deposition (PLD) in an oxygen containing atmosphere allows the synthesis of pure Ag₄O₄ nanocrystalline thin films, permitting at the same time to control the morphology of the material at the sub-micrometer scale. Ag₄O₄ films with a crystalline domain size of the order of tens of nm can be deposited provided the deposition pressure is above a threshold (roughly 4 Pa pure O₂ or 20 Pa synthetic air). The formation of this particular high valence silver oxide is explained in terms of the reactions occurring during the expansion of the ablated species in the reactive atmosphere. In particular, expansion of the PLD plasma plume is accompanied by formation of low stability Ag-O dimers and atomic oxygen, providing reactive species at the substrate where the film grows. Evidence of reactive collisions in the expanding ablation plume is obtained by analysis of the plume visible shape in inert and reactive atmospheres. In addition, we show how the dimensionless deposition parameter L, relating the target-to-substrate distance to the ablation plume maximum expansion length, can be used to classify different growth regimes. It is thus possible to vary the stoichiometry and the morphology of the films, from compact and columnar to foam-like, by controlling both the gas pressure and the target-to-substrate distance.     

Structural investigations of Ge nanoparticles embedded in an amorphous SiO2 matrix

Transmission electron microscopy and X-ray photoelectron spectroscopy analyses are performed to investigate Ge nanoparticles embedded in an amorphous SiO₂ matrix. GeSiO thin films are prepared by two methods, sol?Cgel and radio frequency magnetron sputtering. After the deposition, the sol?Cgel films are annealed in either N₂ (at 1 atm and 800 °C) or H₂ (at 2 atm and 500 °C), and the sputtered films in H₂ (at 2 atm and 500 °C), to allow Ge segregation. Amorphous Ge-rich nanoparticles (3?C7 nm size) are observed in sol?Cgel films. Crystalline Ge nanoparticles in the high pressure tetragonal phase (10?C50 nm size) are identified in the sputtered films. The size of the nanoparticles increases with Ge concentration in the volume of the film. At the film surface, the Ge concentration is much larger that in the volume for both sol?Cgel and sputtered films. At the same time, at the film surface, only oxidized Ge is observed.     

Surface morphology and surface chemical states of epitaxial Pb(Zr0.95Ti0.05)O3 thin films grown on SrTiO3(100) by sputter deposition

0.95 Ti_0.05)O₃ thin films of an orthorhombic perovskite structure were obtained on SrTiO₃(100) substrates by radio frequency sputter deposition. The surface morphology of the films was investigated with atomic force microscopy, scanning electron microscopy, and reflection electron microscopy. It is shown that the film surfaces are rather bumpy. There are undulations of about 400 nm in length in an in-plane direction. The mean roughness perpendicular to the surface is 39.6 nm, for the film thickness of 0.45 μm. The surface roughening was probably caused by island-shaped nucleation and growth during the film growth. It has also been found that some gorges and a number of small pits remain at the film surfaces. The surface chemical states of the films were characterized by using X-ray photoelectron spectroscopy. A Pb enrichment layer and a large amount of adsorbed oxygen have been found at the surfaces of the films. Near the film surface Pb and Zr exist mainly in the forms of, besides Pb(Zr,Ti)0₃, metal Pb, metal Zr, oxygen-chemisorbed Pb, and various lead oxides. In addition, a small amount of lead, whose binding energy of Pb 4f_7/2 is much lower than that of metal Pb, was observed at the film surfaces, but its chemical state is unknown up to now. Received: 2 June 1997/Accepted: 22 September 1997     

Electrostatic spray deposition of Gd0.1Ce0.9O1.95 and La0.9Sr0.1Ga0.8Mg0.2O2.87 thin films

The deposition of gadolinia-doped ceria (CGO, Gd_0.1Ce_0.9O_1.95) and LaGaO₃-based perovskite oxides (LSGM, La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.87) thin films on a stainless steel substrate was studied using the electrostatic spray deposition (EDS) technique. The effect of process conditions, such as deposition temperature, deposition time and liquid flow rate, on the surface morphology and microstructure of thin films was examined with scanning electron microscopy (SEM) and powder X-ray diffraction (XRD). The deposited CGO films with a highly porous and three-dimensional interconnected structure were obtained at a liquid flow rate of 0.5 ml/h, a deposition temperature of 503 K and a deposition time ranging from 0.5 to 1 h. On the other hand, the deposited LSGM thin films with porous microstructure were also obtained at the deposition time of 1 h, the deposition temperature of 533 K and the liquid flow rate of 0.5 ml/h. The deposited CGO and LSGM thin films were amorphous at the used deposition temperature. Subsequently, the samples were annealed at 1173 K for 2 h and the desired crystal structures were obtained. The chemical analysis of the thin films was investigated by energy dispersive X-ray (EDX) analysis. The observed chemical compositions of the samples were in a fair agreement with those of the starting solutions.     

Deposition of hydrogenated amorphous carbon nitride films by dielectric barrier discharge plasmas

Hydrogenated amorphous carbon nitride (a-C:N:H) films were synthesized from CH₄/N₂, C₂H₄/N₂ and C₂H₂/N₂ mixtures using dielectric barrier discharge (DBD) plasmas. Atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) were used to characterize the surface morphology, bonding structure, and composition of the a-C:N:H films. The influences of plasma parameters (discharge pressure in the range of 25-1000 Pa) and feed gases used on the composition and the structure of deposited films were systematically studied. The a-C:N:H films with the uniform surface structure were deposited by low-pressure DBD plasmas with various systems. Compared to the films deposited in C₂H₄/N₂ and C₂H₂/N₂ systems, the films deposited in the CH₄/N₂ system exhibit the relatively lower surface roughness and deposition rate. For all the films prepared in these three systems, increasing the discharge pressure leads to an increase in film surface roughness and deposition rate. Significant differences among the FTIR spectra of all deposited a-C:N:H films were also observed. Both FTIR and XPS spectra show that for all the films deposited in three different systems, increasing the N₂ fraction leads to a decrease in the H content of deposited a-C:N:H films and an increase in the N content. The properties of deposited films may change from those of polymerlike to diamond-like when the discharge pressure is increased. Correlations between the film properties and growth processes are discussed in this study.     

Deposition of Na2WO4 films by ultrasonic spray pyrolysis: effect of thickness on the crystallographic and sensing properties

Na₂WO₄ films have been grown on Si (1 0 0) and glass substrate using ultrasonic spray pyrolysis. The films are prepared from aqueous solution containing Na₂WO₄·2H₂O at 475 °C temperature and characterized by XRD and SEM techniques and the chemical composition of the films have been verified by EDX and PIXE and its formula Na₂WO₄ is confirmed by XRD. The evolution of the crystallinity was studied as a function of film thickness ranging from 2500 to 4200 nm, which corresponds to a deposition time from 10 to 30 min, respectively. The crystalline quality was found to improve, where the grain size values increased with increasing thickness. Atomic Force Microscopy (AFM) was used to study the morphology evolution with the deposition time, where porous films were found due to the synthesis parameters, and a better sensing response to gases was developed with increasing thickness. Thus, this study demonstrates the possibility of utilizing Na₂WO₄ thick films as a sensor element for the detection of ethanol vapor at room temperature, where thicker films exhibit excellent ethanol vapor sensing properties with a maximum sensitivity at 25 °C in air atmosphere with fast response time.     

掺Ag纳米颗粒的BaTiO3复合薄膜的非线性光学特性

通过准分子激光(XeCl, 308 nm, 20 ns)在MgO(100)单晶衬底上制备了不同掺杂浓度的Ag:BaTiO₃纳米复合薄膜,通过X射线衍射和X射线光电子能谱对薄膜的结构和组分进行了表征.在430 nm和470 nm附近观测到了不同浓度Ag纳米颗粒引起的等离子体吸收峰,通过z扫描技术对复合薄膜的三阶非线性光学特性进行了测量,并对其光学非线性的增强机制进行了讨论. 关键词： 金属纳米复合薄膜 激光沉积 非线性光学     

Columnar-grown porous films of lithium manganese oxide spinel (LiMn2O4) prepared by ultrasonic spray deposition

Using LiNO₃ and Mn(Ac)₂ as raw materials, ultrasonic spray deposition (USD) technique was used to fabricate LiMn₂O₄ films on platinum substrate at different substrate temperatures from 310 to 390 °C. The prepared thick films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrochemical performance of the USD-derived films was also evaluated with LiMn₂O₄/Li cells. It is found that all of the LiMn₂O₄ films are porous and composed of orderly oriented columnar particles. The substrate temperature affects the fine microstructure of the columnar particles. The film prepared at 360 °C substrate temperature give rise to best electrochemical behavior.     

Influence of oxygen on the growth of cubic boron nitride thin films by plasma-enhanced chemical vapour deposition

Cubic boron nitride thin films were deposited on silicon substrates by low-pressure inductively coupled plasma-enhanced chemical vapour deposition. It was found that the introduction of O₂ into the deposition system suppresses both nucleation and growth of cubic boron nitride. At a B₂H₆ concentration of 2.5\% during film deposition, the critical O₂ concentration allowed for the nucleation of cubic boron nitride was found to be less than 1.4\%, while that for the growth of cubic boron nitride was higher than 2.1\%. Moreover, the infrared absorption peak observed at around 1230--1280~cm^-1, frequently detected for cubic boron nitride films prepared using non-ultrahigh vacuum systems, appears to be due to the absorption of boron oxide, a contaminant formed as a result of the oxygen impurity. Therefore, the existence of trace oxygen contamination in boron nitride films can be evaluated qualitatively by this infrared absorption peak.     

金属纳米团簇复合薄膜Au/BaTiO3与Fe/BaTiO3的PLD制备及其光吸收特征

用脉冲激光沉积技术制备了掺杂纳米金属颗粒Au或Fe的BaTiO₃复合薄膜.用透射电子显微镜和x射线光电子能谱表征了金属颗粒的形态和化学态.330—800nm范围的吸收谱研究表明，掺Au颗粒的BaTiO₃薄膜在580nm附近有一个明显的共振吸收峰，而掺Fe颗粒的BaTiO₃薄膜没有这样的吸收峰.用Mie散射理论对结果进行了分析. 关键词： 复合薄膜 金属颗粒 脉冲激光沉积 吸收谱     

Magnetic properties of CoFeP films prepared by electroless deposition

Structure and magnetization of CoFeP films prepared by the electroless deposition were systematically investigated by varying the bath composition and deposition parameters to optimize soft magnetic properties. The cobalt content in the CoFeP films varies from 40.4 to 94.9 wt% by controlling the bath composition. Increase of the metallic ratio FeSO₄·7H₂O/(CoSO₄·7H₂O+FeSO₄·7H₂O) affects the films’ microstructure, which switches from amorphous to crystalline structure. The magnetic properties of CoFeP films reveal that the coercivity (H_c) values range from 80 up to 185 A/m and the saturation magnetization (M_s) from 82 to 580 eum/g depending on the bath composition, deposition parameters and heat-treatment conditions. Increase of M_s and remanent magnetization (M_r) as well as decrease of H_c are observed for the CoFeP films with bath pH, temperature and the metallic molar ratio increasing. It is also found that the H_c is enhanced with the increase of NaH₂PO₂·H₂O concentration. CoFeP films showing good soft magnetic properties with coercivities less than 140 A/m and M_s close to 600 emu/g can be obtained in high pH bath and thereafter heat treatment. The deposit is found to be suitable as soft magnetic materials for core materials.     

Gas sensing properties of nanostructured MoO3 thin films prepared by spray pyrolysis

Thin films of molybdenum trioxide (MoO₃) were deposited on common glass using the chemical spray pyrolysis technique. A (NH₄)₆Mo₇O₂₄4H₂0 solution 0.1 M was used as the precursor one. The influence of substrate temperature on the crystallographic structure, surface morphology and electrical behavior of MoO₃ thin films was studied. MoO₃ can exist in two crystalline forms, the thermodynamically stable orthorhombic α-MoO₃ and the metastable monoclinic β-MoO₃ phase. XRD-spectra showed a growth of α-MoO₃ phase percentage as substrate temperature increases from 420 K up to 670 K. Films deposited in the 500–600 K range have a clearly porous surface structure of nanometer order as can be seen in SEM images. Changes up to six magnitude orders were observed in MoO₃ thin films electrical resistance when films temperature varied from 100 K up to 500 K. The sensing property of these MoO₃ films was also studied. The sensitivity was investigated in the temperature range 160 and 360 K for H₂O and CO gases, respectively. Both of them are of reducing nature. In all studied cases sensitivity decreases slowly as film temperature is raised. At room temperature the sensitivity changes from 12 up to 75% depending on substrate temperature. The sensitivity for CO gas was found to be lower than that of H₂O.     

Effects of deposition temperature and hydrogen flow rate on the properties of the Al-doped ZnO thin films and amorphous silicon thin-film solar cells

A compound of 98 mol% ZnO and 1 mol% Al₂O₃ (AZO, Al:Zn = 98:2) was sintered at 1350 °C as a target and the AZO thin films were deposited on glass using a radio frequency magnetron sputtering system. The effects of deposition temperature (from room temperature to ～300 °C) on the optical transmission spectrum of the AZO thin films were studied. The Burstein–Moss shift was observed and used to prove that defects in the AZO thin films decreased with increasing deposition temperature. The variations in the optical band gap (E _g) values of the AZO thin films were evaluated from plots of (αhv)²=c(hν?E _g), revealing that the measured E _g values increased with increasing deposition temperature. The effects of the H₂ flow rate during deposition (0 %～11.76 %, deposition temperature of 200 °C) on the crystallization, morphology, resistivity, carrier concentration, carrier mobility, and optical transmission spectrum of the AZO thin films were measured. The chemical structures of the Ar-deposited and 2 % H₂-flow rate-deposited AZO thin films (both were deposited at 200 °C) were investigated by XPS to clarify the mechanism of improvement in resistivity. The prepared AZO thin films were also used as transparent electrodes to fabricate amorphous silicon thin-film solar cells, and their properties were also measured.     

Optical properties of organic-inorganic hybrid films prepared by the two-step growth process

Thin films of microcrystalline (C₈H₁₇NH₃)₂PbBr₄ have been prepared by the two-step growth process as follows: (1) precipitation of nanometer-sized PbBr₂ particles on substrates by vapor deposition and then (2) growth of (C₈H₁₇NH₃)₂PbBr₄ films by exposing PbBr₂ particles to C₈H₁₇NH₃Br vapor. Atomic force microscope observations reveal that the substrate is fully covered with nanometer-sized rodlike precipitates. X-ray diffraction studies suggest that (C₈H₁₇NH₃)₂PbBr₄ films are found to be microcrystalline form, single phase and highly oriented with the c-axis perpendicular to the substrate surface. (C₈H₁₇NH₃)₂PbBr₄ films show a clear exciton absorption and free-exciton emission even at room temperature. At low temperatures below 40 K, the emission band separates into three bands at 3.07 (A-band), 3.14 (B-band) and 3.20 (C-band) eV, respectively. Both A- and C-bands correspond to the free-exciton emission with large binding energies. On the contrary, time-resolved PL spectra indicate that the B-band is attributed to phosphorescence formed by the intersystem crossing.     

Lead-free ferroelectric thin films obtained by pulsed laser deposition

Na_0.5Bi_0.5TiO₃-BaTiO₃ (NBT-BT) thin films grown by pulsed laser deposition have been investigated by X-ray diffraction, scanning electron microscopy, and dielectric spectroscopy in order to clarify the role of substrate temperature on crystalline structure, grain morphology, and dielectric properties. We have shown that the structural and dielectric properties of NBT-BT thin films with composition at morphotropic phase boundary (6% BT) critically depend on the substrate temperature: small variations of this parameter induce structural changes, shifting the morphotropic phase boundary toward tetragonal or rhombohedral side. Higher deposition temperature (1000 K) favor the formation of rhombohedral phase, films deposited at 923 K and 973 K have tetragonal symmetry at room temperature. Grains morphology depends also on the deposition temperature. Atomic force micrographs show grains with square or rectangular shape in a compact structure for films grown at lower temperatures, while grains with triangular shape in a porous structure are observed for films grown at 1000 K. Dielectric spectroscopy measurements evidenced the phase transition between ferroelectric and antiferroelectric phase at 370 K. Films grown at 1000 K shown low electrical resistivity due to their porous structure. High dielectric constant values (about 800 at room temperature and 2700 at 570 K) have been obtained for films grown at temperatures up to 973 K.     

Novel fabrication of net-like and flake-like Fe doped TiO2 thin films

New morphologies of net-like and flake-like TiO₂ thin films with different concentrations of Fe dopant were successfully fabricated by micro-arc oxidation (MAO) process of Ti plates and a subsequent chemical treatment of the as-prepared MAO-TiO₂ thin films. It was found that Fe ions can be easily introduced into the MAO-TiO₂ samples with the increase concentration of K₄(FeCN)₆·3H₂O precursor, and the amount of Fe determined the morphologies of TiO₂ thin films after chemical treatment; net-like morphology was observed with low Fe dopant, while it transformed to a flake-like one when Fe exceeds 1.7 at.%. UV-vis spectroscopy test showed that the absorption edge of the Fe ions doped TiO₂ thin films with new morphologies has an obvious red shift.     

Realization of controllable etching for ZnO film by NH4Cl aqueous solution and its influence on optical and electrical properties

ZnO films were deposited on c-plane Al₂O₃ substrates by pulsed laser deposition. The etching treatments for as-grown ZnO films were performed in NH₄Cl aqueous solution as a function of NH₄Cl concentration and etching time. It was found that NH₄Cl solution is an appropriate candidate for ZnO wet etching because of its controllable and moderate etching rate. The influence of etching treatment on the morphology, optical and electrical properties of the ZnO films has been investigated systematically by means of X-ray diffraction, atomic force microscope, photoluminescence and Hall effect. The results indicated that the surface morphology and optical properties of the films were highly influenced by etching treatment.