A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.     

射频磁控反应溅射氮氧化硅薄膜的研究

利用SiOxNy薄膜光学常数随化学计量比连续变化的特性,给出了制备折射率连续可调的SiOxNy薄膜的实验条件。用磁控反应溅射法制备了不同氮氧比的SiOxNy薄膜。研究了不同气流比率条件下薄膜光学常数、化学成分及溅射速率等的变化。用UV-VIS光谱仪测试了透射率曲线,利用改进的单纯型法拟合透射率曲线计算得到了折射率和消光系数。测试了红外傅立叶光谱(FTIR)曲线和X光光电子能谱(XPS)分析了薄膜成分的变化。实验表明薄膜特性与N2／O2流量比率密切相关,通过控制总压和改变气体流量比可控制SiOxNy薄膜的折射率n从1．92到1．46连续变化,应用Wemple-DiDomenico模型计算出光子带隙在6．5eV到5eV之间单调变化。     

The influence of gas flow rate on the structural,mechanical, optical and wettability of diamond-like carbon thin films

In this research, diamond-like carbon (DLC) thin films were deposited on silicon substrates by radio-frequency plasma enhanced chemical vapor deposition method using gas mixture of CH₄ and Ar. The effect of different CH₄/Ar gas ratio on the structure, refractive index, transmission and hardness of the DLC thin films were investigated by means of Raman spectroscopy, ellipsometry, Fourier transform Infrared Spectroscopy and nano-indentation methods, respectively. Nuclear resonant reaction analysis was used to measure the amount of hydrogen and carbon in the thin films. Furthermore, wettability of the thin films was achieved by measuring of water contact angle (WCA). The results indicated that the structural properties of the diamond-like carbon thin films are strongly dependent on the composition of gas mixture. Based on ellipsometry results, refractive index of the thin films varied in the range of 1.89–2.06 at 550 nm. FTIR results determined that deposition of DLC thin films on silicon substrate led to an increase of the light transmission in IR region and these films have the potential to be used in silicon optics as the antireflective coatings in this region. Nano-indentation analysis showed that the thin films hardness changed in the range of 7.5–11 GPa. On the other hand hydrogen content and fraction of C?H bonds in the samples increased by an increase in the gas ratio of CH₄/Ar. Also, WCA measurements indicated that WCA for thin films with gas ratio of 3/7 is the most and equal to 79°.     

射频等离子体增强化学气相沉积SiNx薄膜的研究

采用射频等离子体增强化学气相沉积技术,以N2和SiH4作为反应气体,在P型硅基片上进行SiNx薄膜的沉积.使用椭偏仪对薄膜厚度和光学常量进行了测量, 用傅里叶变换红外光谱仪对SiNx薄膜的化学键合结构进行了分析.研究了基片温度、射频功率以及N2和SiH4的气体流量比率等实验工艺参量对薄膜沉积速率和光学常量的影响.结果表明,射频等离子体增强化学气相沉积技术沉积的SiNx薄膜是低含氢量的SiNx薄膜,折射率在1.65~2.15之间,消光系数k在0.2~0.007之间,当SiNx薄膜为富氮时k≤0.01,最高沉积速率高达6.0 nm/min,N2和SiH4气体流量比率等于10是富硅和富氮SiNx薄膜的分界点.     

The influence of the substrate nature on the iron repartition in the titania matrix

Fe-doped titania films were deposited by RF sputtering onto different substrates (glass and ITO/glass) in the same deposition run. The rutile nanocrystalline structure of Fe-doped thin films deposited on glass substrates and anatase nanocrystalline structure of Fe-doped thin films deposited on ITO/glass substrates were evidenced by XRD. SEM investigations showed a smooth surface with a dense nanostructure. XPS study evidenced an almost stoichiometric composition with different iron contents. EPR and XPS studies evidenced that iron entered into TiO₂ lattice by substitution, as isolated and dimer species. In Fe-doped thin films deposited on ITO/glass substrates the iron content is ten times higher than in Fe-doped thin films deposited on glass substrates and that a part of them entered as Fe²⁺.     

靶压对磁控溅射GeC薄膜折射率的影响

采用磁控溅射技术,以碳氢气体和氩气为工作气体,在Ge基底上制备了GeC薄膜。研究了靶压对薄膜折射率的影响,发现在较高的靶压下制备的GeC薄膜具有较低的折射率,而在较低的靶压下则得到了高折射率的薄膜。通过控制溅射靶压,制备了折射率在2．5～3．8之间可变的GeC薄膜。利用拉曼光谱研究了GeC薄膜的结构。薄膜样品的硬度测试表明,较低折射率的GeC薄膜具有较高的硬度。     

氮化硼薄膜的红外光谱研究

用磁控溅射法制备六角氮化硼薄膜,在衬底温度、衬底偏压、工作气压等条件一定的情况下改变工作气体(氮气+氩气)中氮气的比例,以制备高质量的六角氮化硼薄膜,薄膜以红外吸收光谱标识。实验结果表明,工作气体中氮气的比例对制得的六角氮化硼薄膜有很大影响,在氮气比例为20%时得到理想的六角氮化硼薄膜。     

Effect of argon ion activity on the properties of Y2O3 thin films deposited by low pressure PACVD

Yttrium oxide thin films are deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition process using an indegeneously developed Y(thd)₃ {(2,2,6,6-tetramethyl-3,5-heptanedionate)yttrium} precursor. Depositions were carried out at two different argon gas flow rates keeping precursor and oxygen gas flow rate constant. The deposited coatings are characterized by X-ray photoelectron spectroscopy (XPS), glancing angle X-ray diffraction (GIXRD) and infrared spectroscopy. Optical properties of the films are studied by spectroscopic ellipsometry. Hardness and elastic modulus of the films are measured by load depth sensing nanoindentation technique. Stability of the film and its adhesion with the substrate is inferred from the nanoscratch test.It is shown here that, the change in the argon gas flow rates changes the ionization of the gas in the microwave ECR plasma and imposes a drastic change in the characteristics like composition, structure as well as mechanical properties of the deposited film.     

Study of elemental and phase composition of PZT thin films by auger depth profiling

The composition of PZT thin films deposited by diode HF sputtering of a ceramic target on Pt/Ti/SiO₂/Si substrates was studied. The remanent polarization of grown films was to 22 μC/cm². A technique for verifying the adequacy of elemental and phase composition of thin films to the ferroelectric phase composition was proposed. The problems of reliable contact of Pt electrodes with the PZT layer were considered.     

Optimization of Gas Sensing Performance of Nanocrystalline SnO_2 Thin Films Synthesized by Magnetron Sputtering

Tin oxide(SnO_2) is one of the most promising transparent conducting oxide materials,which is widely used in thin film gas sensors.We investigate the dependence of the deposition time on structural,morphological and hydrogen gas sensing properties of SnO_2 thin films synthesized by dc magnetron sputtering.The deposited samples are characterized by XRD,SEM,AFM,surface area measurements and surface profiler.Also the H_2 gas sensing properties of SnO_2 deposited samples are performed against a wide range of operating temperature.The XRD analysis demonstrates that the degree of crystallinity of the deposited SnO_2 films strongly depends on the deposition time.SEM and AFM analyses reveal that the size of nanoparticles or agglomerates,and both average and rms surface roughness is enhanced with the increasing deposition time.Also gas sensors based on these SnO_2 nanolayers show an acceptable response to hydrogen at various operating temperatures.     

Comparison and semiconductor properties of nitrogen doped carbon thin films grown by different techniques

Amorphous carbon nitride (a-CN_x) thin films have been synthesised by three different deposition techniques in an Ar/N₂ gas mixture and have been deposited by varying the percentage of nitrogen gas in the mixture (i.e. the N₂/Ar + N₂ ratio) from 0 to 10%. The variation of the electrical conductivity and the gap values of the deposited films versus the N₂/Ar + N₂ ratio were investigated in relation with their local microstructure. Film composition was analysed using Raman spectroscopy and optical transmission experiments. The observed variation of electrical conductivity and optical properties are attributed to the changes in the atomic bonding structures, which were induced by N incorporation, increasing both the sp² carbon content and their relative disorder. The low N content samples seem to be an interesting material to produce films with interesting properties for optoelectronic applications considering the facility to control the gas composition as a key parameter.     

Unusual elastic behavior of nanocrystalline diamond thin films

This Letter studies the relationship between the elastic constants and the microstructure of nanocrystalline diamond thin films deposited by the chemical vapor deposition method doping various concentration of N2 gas. The elastic constants were measured by resonant ultrasound spectroscopy and picosecond laser ultrasounds. The increase of N2 gas decreases the diagonal elastic constants, but increases the off-diagonal elastic constants. The micromechanics calculation can explain this unusual elastic behavior, and it predicts thin graphitic phases at grain boundaries.     

On the phase formation of titanium oxide thin films deposited by reactive DC magnetron sputtering: influence of oxygen partial pressure and nitrogen doping

This work describes about the control on phase formation in titanium oxide thin films deposited by reactive dc magnetron sputtering. Various phases of titanium oxide thin films were deposited by controlling the oxygen partial pressure during the sputtering process. By adding nitrogen gas to sputter gas mixture of oxygen and argon, the oxygen partial pressure was decreased further below the usual critical value, below and above which the sputtering yields metallic and oxide films, respectively. Furthermore, nitrogen addition eliminated the typical hysteretic behaviour between the flow rate and oxygen partial pressure, and significantly influenced the sputter rate. On increasing the oxygen partial pressure, the ratio between anatase and rutile fraction and grain size increases. The fracture cross-sectional scanning electron microscopy together with the complementary information from X-ray diffraction and micro-Raman investigations revealed the evolution and spatial distribution of the anatase and rutile phases. Both the energy delivered to the growing film and oxygen vacancy concentrations are correlated with the formation of various phases upon varying the oxygen partial pressure.     

Electrical behaviour of SiOxNy thin films and correlation with structural defects

Silicon oxynitride thin films were deposited by reactive r.f. sputtering from a silicon target. Different Ar:O₂:N₂ gas atmospheres were used at fixed power density (3.18 W cm⁻²) and pressure (0.4 Pa) to obtain various film composition. Pt-SiO_xN_y-Pt sandwich type structure was realised for electrical property investigations. The C-V measurements showed the absence of a Schottky barrier and thus confirmed that Pt electrode provides an ohmic contact. The evolution of the current density showed a decrease of the film conductivity when the oxygen concentration in the films increases. The various layer composition leads to two different conduction mechanisms which were identified as space charge limited current (SCLC) and Poole-Frenkel effect. Finally, the structural defects of the films were studied by EPR analysis and the spin densities were correlated to both the composition and the electrical behaviour of the films.     

Synthesis of YBa2Cu3O7−x superconducting thin films on LaAlO3 by means of PAMOCVD

High-T_c superconducting thin films have been deposited in situ by means of a plasma assisted metal-organic chemical vapour deposition (PAMOCVD) process on LaAlO₃. An EMCORE high-speed rotating disc reactor was used to deposit the films at a substrate temperature of 600°C to 800°C. The system is equipped with a (remote) 120 W microwave plasma generator. The oxidising plasma gas is N₂O and/or O₂ while Ar was used as the inert carrier gas for the different metal-organics. The influence of different process parameters (such as the temperatures of the metal-organics, substrate temperature, and plasma gas composition) on the superconductive properties and on the morphology of the films was investigated. Surface morphology and composition were studied by SEM/EDX or EPMA, and AC susceptibility measurements were used to investigate the superconductive properties (T_c and J_c). X-ray diffraction measurements indicated that single-phase YBa₂Cu₃O_7−x films were epitaxially grown with the 00l orientation perpendicular to the substrate surface. The critical temperature (T_c) of the films is about 90 K and the critical current density (J_c) is higher than 10⁶ A/cm² at 77 K and zero field.     

Growth mechanism and characterisation of chemically grown Sb doped Bi2Se3 thin films

The synthesis of combinatorial Bi_2−xSb_xSe₃ thin films by arrested precipitation technique (APT) using triethanolamine-bismuth, triethanolamine-antimony and sodium selenosulphite as sources of Bi³⁺, Sb³⁺ and Se²⁻, respectively is investigated on commercial glass substrates. The growth mechanism of film formation, composition and surface morphology of the as deposited films were studied as a function of preparative parameters and bath composition. The films were monophasic, polycrystalline and covered the surface of the substrate completely. Energy dispersive X-ray analysis gave coherent elemental composition indicating single phase BiSbSe₃ was made. The good results obtained for Bi_2−xSb_xSe₃ thin films revealed that arrested precipitation technique is best suited for the deposition of large area thin films on conducting/nonconducting substrates to produce materials for device applications.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

Nanoporous gold thin films synthesised via de-alloying of Au-based nanoglass for highly active SERS substrates

Nanoporous gold thin films have been fabricated through chemical de-alloying of Au-based nanoglass with a nanocolumnar structure, with composition Au₄₀Cu₂₈Ag₇Pd₅Si₂₀ (at.%), that had previously been deposited by magnetron sputtering. By varying the de-alloying conditions, gold ligaments ranging from 20 to 100?nm were obtained. The microstructure and chemical composition of the as-prepared films were characterised by various techniques. Surface-enhanced Raman scattering (SERS) of thin films was investigated using rhodamine 6G. The results indicate that the main microstructural features with interconnected ligaments and defects of nanoporous gold result in significant SERS enhancement.     

Selective deposition of Au films on GaAs by projection-patterned excimer laser doping combined with electroless plating

Resistless microfabrication of Au thin films on n-type GaAs by projection-patterned laser doping using a KrF excimer laser and a 10% SiH₄-He gas is described. Gold thin films with a linewidth as narrow as 1.57 m are deposited selectively on the doped regions by electroless plating in a commercial Au-24s aqueous solution. The isotropic growth of the deposited films is discussed by comparing the linewidth of the deposited films with that of the doped regions. Furthermore, the dependence of the deposition characteristics of Au thin films on the laser irradiation conditions is investigated.Presented at LASERION '91, June 12–14, 1991, München (Germany)     

Structural characterization and magnetoresistance of manganates thin films and Fe-doped manganates thin films

Perovskites thin films with the composition La_0.6Ca_0.4MnO₃ doped with 20% Fe, were prepared by pulsed reactive crossed beam laser ablation, where a synchronized reaction gas pulse interacts with the ablation plume. The films were grown on various substrates and the highest colossal magnetoresistance ratio (CMR) was detected by Hall measurements for films grown on LaAlO₃ (1 0 0), which was selected as substrate for further investigations.Several growth parameters, such as substrate temperature and target to substrate distance were varied to analyze their influence on the film properties.The structure of the deposited thin films was characterized by X-ray diffraction and atomic force microscope, while Rutherford backscattering (RBS) was used to determine the film stoichiometry. The electrical properties were determined by Hall effect measurements in a magnetic field of 0.51 T.These measurements reveal that the amplitude of the CMR ratio depends strongly on the substrate and that the oxygen content influences the temperature where the transition from semiconductor to metal is observed.