Synthesis of CuInS2 Nanocubes by a Wet Chemical Process

Cube‐shaped CuInS₂ nanoparticles were successfully prepared through a simple low‐temperature solution route. Mercaptoacetic acid was used as capping agent. The product was characterized by means of X‐ray diffraction (XRD), energy dispersive analysis of X‐rays (EDAX), transmission electron microscopy (TEM), and photoluminescence spectroscopy (PL). The CuInS₂ nanocubes obtained were of a chalcopyrite structure. The EDAX analysis shows that as‐synthesized CuInS₂ nanocubes were slightly Cu‐rich and nearly stoichiometric.     

Thermal Plasma Chemical Vapor Deposition of Si-Based Ceramic Coatings from Liquid Precursors

In this paper a process based on the use of rf inductively coupled plasma is applied for the synthesis and deposition of Si-base ceramic materials (i.e., SiC, Si₃N₄, SiO₂). The starting materials are low-cost liquid disilanes. The atomization process is first investigated and the structure of the resulting coatings is characterized by means of X-ray diffraction, scanning electron microscopy as well as with transmission electron microscopy. Results of the influence of some processing parameters (i.e., chamber pressure, spray distance, substrate cooling, plasma gas nature and composition, precursor composition and atomization parameters) on the phase and microstructure of the coating is reported. Control of the microstructure (or nanostructure) as well as the phase content, namely the / ratio of the phases for SiC and Si3N4, can be achieved with such a synthesis and deposition technique.     

Plasma Enhanced Chemical Vapor Deposition of Fluorinated Amorphous Carbon Thin Films from Tetrafluoroethylene and Tetraisocyanatesilane

Fluorinated amorphous carbon films were prepared from tetrafluoroethylene (TFE; C₂F₄) and tetraisocyanatesilane (TICS; Si(NCO)₄) using an RF plasma enhanced chemical vapor deposition method for the purpose of application to inter layer low permittivity films used in large scale integrated circuits. Structure of the deposited films was investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Adhesion characteristics were examined by a tape-peel method. Permittivity of the films was investigated from capacitance measurement on metal-insulator-semiconductor structure. The structural analysis revealed that the deposited films contained imide-like group in spite of the fact that TICS molecules contained isocyanate group . The films deposited under the flow ratio TICS/(TFE + TICS) = 70% showed permittivity of 2.3, good adhesion on silicon substrates, and higher thermal stability than the films deposited without TICS.     

Structure,Composition, Mechanical,and Tribological Properties of BCN Films Deposited by Plasma Enhanced Chemical Vapor Deposition

In this work thin BCN films were deposited by plasma enhanced chemical vapor deposition (PECVD) using chloridic precursors. Through adjusting the BCl₃ content in the inlet gas mixture the chemical composition of the deposited films was changed from carbon rich to boron rich. Based on optical emission spectroscopy (OES) measurements, a correlation between film composition and precursor species concentration in the plasma was established. The films were amorphous as detected by grazing incidence X-ray diffraction (GIXRD). The hardness and the elastic modulus have maximal values of 25.5±1.2 and 191±6 GPa, respectively, for the films with a boron concentration of 45.2 at.%. GIXRD data suggest that a depletion in boron content may initiate the formation of graphitic domains in the amorphous matrix. The observed degradation of the mechanical properties is associated with the graphitization. The tribological behavior was studied with a tribometer operated in pin-on-plate configuration at the temperatures 25 and 400°C. The wear mechanisms were discussed with respect to the formation of a boric acid surface layer which was detected by reflection electron energy loss spectroscopy (REELS) analysis.     

Deposition of Gallium Nitride Thin Films by MOCVD in Microwave Plasma

The deposition of GaN thin films in a nitrogen–hydrogen microwave plasma using Ga(CH ₃ ) ₃ as a gallium precursor was investigated. The deposit was identified as stoichiometric GaN by XPS and XRD. The substrate was dielectrically heated in the microwave discharge and the substrate temperature was lower than that in usual thermal MOCVD. The NH radicals, which were the primary N-atoms precursors, and fragments of Ga(CH ₃ ) ₃ were identified in the plasma by OES. The NH radical formation and the decomposition of Ga(CH ₃ ) ₃ in the plasma may be one of the reasons for the lower deposition temperature of GaN. The position dependence of the substrate temperature showed similar tendency as the position dependence of the electron temperature. The plasma state contributes to the deposition of GaN thin films. The deposited GaN exhibited a wide optical band gap of 3.4eV. Material highly oriented along the c axis was detected in the deposit, and a PL spectrum which has the band head at about 450 mm was obtained.     

Preparation and Characterization of CuInS2 Thin Films for Solar Cells by Chemical Bath Deposition

Introduction Recent years, chalcopyrite semiconductors have been successfully applied as absorber layers for polycrystalline thin-film solar cells. Among the ternary compound semiconductors, CuInS2 thin films with a direct bandgap of about 1.50 eV and a large absorption coefficient in the range of 104-105cm-1[1] are one kind of the most promising optical absorbers for high efficiency thin film solar cells.To date, CuInS2-based solar cells have shown conversion efficiency of about 12. 5%[2]. They exhibit long-term stability without any signs of degradation.     

Formation of Rod-Like CuInS2 Nanocrystals on the Glass Substrate

Rod-like CuInS₂ nanocrystals on the glass substrate were prepared by annealing the coat of CuInS₂ nanoparticles. The products were characterized by means of energy dispersive analysis of x-ray (EDAX), x-ray diffraction (XRD) and scanning electron microscopy (SEM). The results of XRD and EDAX show that the rod-like CuInS₂ nanocrystals obtained are of a chalcopyrite structure and are nearly stoichiometric. The aggregation mechanism of “oriented attachment” of nanocrystals is believed to be operative and compatible in this study.     

Molecular Design of Fluorocarbon Film Architecture by Pulsed Plasma Enhanced and Pyrolytic Chemical Vapor Deposition

Pulsed plasma enhanced chemical vapor deposition (pulsed PECVD) and pyrolytic chemical vapor deposition (pyrolyric CVD) of fluorocarbon films from hexafluoropropylene oxide (HFPO) have demonstrated the ability to molecularly design film architecture. Film structures ranging from highly amorphous crosslinked matrices to linear perfluoroalkyl chain crystallites can be established by reducing the modulation frequency of plasma discharge in plasma activated deposition and by eventually shifting mechanistically from an electrically activated to a thermally activated process. X-ray photoelectron spectroscopy (XPS) showed CF₂ content increasing from 39–65 mol%. Fourier transform infrared spectroscopy (FTIR) showed an increasing resolution between the symmetric and asymmetric CF₂ stretches, and a reduction in the intensity of the amorphous PTFE and CF₃ bands. High-resolution solid-state ¹⁹F nuclear magnetic resonance spectroscopy (NMR) revealed an increasing CF₂CF₂CF₂ character, with the pyrolytic CVD film much like bulk poly(tetrafluoroethylene) (PTFE). X-ray diffraction (XRD) patterns evidenced an increase in crystallinity, with the pyrolytic CVD film showing a characteristic peak at 2 = 18° representing the (100) plane of the hexagonal structure of crystalline PTFE above 19°C.     

Growth Modes of SiO x Films Deposited by Evaporation and Plasma-Enhanced Chemical Vapor Deposition on Polymeric Substrates

In order to study the very first stages of plasma-enhanced chemical vapor deposition (PECVD) of SiO₂ on polymer substrates, we used a distributed electron cyclotron resonance (DECR) reactor, with the substrate placed (I) in the active glow zone, (II) downstream therefrom, and (III) downstream, but shielded from photon emission (e.g., VUV) from the plasma. For comparison, we also study films deposited by physical vapor ddposition (PVD, thermal evaporation). To characterize the ultra-thin deposits, we used oxygen plasma etching combined with scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Rutherford backscattering spectroscopy (RBS). We elucidate the roles of various energetic species (VUV photons, ions, atomic oxygen, and other radicals) in the plasma during the earliest growth phase, and the origin of the interphase which is present between the deposited SiO₂ and the polymer substrate.     

Growth of CuInS2 Nanotubes from Cu2S-CuInS2 Heterostructures as a Potential Photovoltaic Material

Chemically synthesized nanostructures possess well-defined domains with an interconnected network, which helps the carriers to bypass the other material in the solar cell while moving to their respective electrodes. In this work, CuInS₂ films constituting CuInS₂ nanotubes and nanoparticles were fabricated using a hot-injection chemical technique, followed by sulfurization. Structural and microstructural investigations reveal Cu₂S nanoparticle formation at an early stage of growth of nanotubes, serving as possible catalyst sites for the subsequent anisotropic growth of the heterostructured hexagons. The crossover takes place over a number of intermediate stages. This sharing of the heterostructure by the hexagonal Cu₂S and chalcopyrite CuInS₂ minimizes the lattice distortion. The Cu₂S- CuInS₂ interface in the heterostructure acts as the nucleation center for CuInS₂ nanotubes. Optical absorption and Raman spectroscopy studies reveal better optical properties for CuInS₂ nanoparticles as compared to CuInS₂ nanotubes. Compared to all other nanostructures, nanowires or nanotubes tend to provide single-crystalline nanograins for direct characterization. These nanoparticles, especially the nanotubes, can be used to form an interconnected network structure of p- and n-type materials in bulk heterojunctions providing the key to improve solar cell efficiencies.     

SILAR法制备化学计量CuInS2薄膜

在室温下，以不同c_Cu/c_In的CuCl₂和InCl₃混合溶液作为阳离子前驱体，Na₂S水溶液为硫源，利用连续离子层吸附反应法(SILAR)在玻璃基底上制备了CuInS₂薄膜。XRD结果表明，当c_Cu²⁺/c_In³⁺在1～1.5范围内均可形成具有黄铜矿结构的CuInS₂薄膜。SEM观察到随c_Cu²⁺/c_In³⁺的升高，薄膜表面颗粒长大并出现团簇聚集。通过XPS测定薄膜表面的化学组成证明当c_Cu²⁺/c_In³⁺=1.25时，CuInS₂薄膜接近其标准的化学计量组成。此时薄膜的吸收系数大于>10⁴ cm^-1，禁带宽度E_g为1.45 eV。     

离子层气相反应法(ILGAR)制备CuInS2薄膜的研究

CuInS₂ thin films have been prepared by ion layer gas reaction (ILGAR) using C₂H₅OH as solvent, CuCl and InCl₃ as reagents and H₂S gas as sulfuration source. The effects of cationic concentrations and numbers of cycle on the properties of CuInS₂ film were investigated. The chemical composition, crystalline structure, surface topography, deposited rate, optical and electronic properties of the films were characterized by X-ray diffractrometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), ultraviolet-visible spectrometry (UV-Vis) and Hall System. The results show that the crystalline of CuInS₂ thin films and the deposition rate have been improved with the increase of cationic concentration, while CuxS segregation phases appear with further increasing cationic concentration. The deposition rate is close to constant as cationic concentration is fixed. CuInS₂ thin film derived form lower cationic concentration is uniform, compact and good in adhesion to the substrates. The absorption coefficient of CuInS₂ thin films is larger than 10⁴ cm^-1, and the band gap E_g is in the range of 1.30～1.40 eV. The dark resisitivity of the thin film decreases from 50 to 10 Ω·cm and the carrier concentration ranges are over 10¹⁶ cm^-3.     

Microstructure and Chemical Bonding in Silicon Carbonitride Films Synthesized by Plasma Enhanced Chemical Vapor Deposition

Silicon carbonitride films were synthesized by plasma enhanced chemical vapor deposition using silyl derivatives of asymmetric dimethylhydrazine, (CH₃)₂HSiNHN(CH₃)₂ and (CH₃)₂Si[NHN(CH₃)₂]₂, as molecular precursors. The film material consists of an amorphous matrix with nanocrystalline inclusions. Indexing of synchrotron radiation Xray diffraction patterns suggests that the structure of the nanocrystals is tetragonal with lattice parameters a = 9.6 and c = 6.4. Xray photoelectron spectra indicate that Si—N and C—N sp ³ hybrid bonds are predominant. The absence of G or Dmodes in Raman spectra, which are otherwise typical of structures possessing sp ² bonding, provides further support for the tetragonal structure of the nanocrystals.     

以光辅助MOCVD法在有取向Ni衬底及LAO单晶衬底上制备YBCO外延膜的比较研究

采用光辅助金属有机物化学气相沉积(MOCVD)法,在生长有CeO2/YSZ/Y2O3(YSZ为Y稳定的ZrO2)缓冲层的双轴取向Ni衬底上进行了YBa2Cu3O7-x(YBCO)外延膜生长,并与LaAlO3(100)[LAO(100)]单晶衬底上的YBCO外延膜生长进行了对比.发现在Ni衬底上c轴取向YBCO外延膜的生长温度比LAO衬底上的生长温度低约30℃,但生长速度更快.经分析认为,这种差别主要是由于Ni衬底的热导率比LAO衬底高造成的.Ni衬底及LAO衬底上生长的c轴取向YBCO外延膜的超导极限电流密度(Jc)分别约为0.5 MA/cm2及1.8 MA/cm2.     

UV Absorptance of Titanium Dioxide Thin Films by Plasma Enhanced Deposition from Mixtures of Oxygen and Titanium-Tetrakis-Isopropoxide

A low pressure radio frequency discharge was used to deposit films by mixtures of oxygen and titanium (IV) isopropoxide (TTIP) at powers of 200 W on films of polyethylene-terephthalat and samples of quartz glass. In the non-thermal plasma, films of rather pure TiO₂ could be deposited as revealed by X-ray photo-electron spectroscopy. Besides the film growth rate and the chemical composition, the spectral behaviour of the spectral transmittance of visually transparent films was determined in the range from 200 to 500 nm. Furthermore, the absorptance of films has been derived at characteristic spectral positions of the transmission spectra of the films. Accordingly, cut-off wavelength was found to increase with deposition time from 5 to 10 min as well as with the concentration of TTIP in a range below 1.7%. At 310 nm, the spectral absorption coefficient (extinction coefficient × concentration) was 12 μm⁻¹. While keeping other parameters constant, this coefficient decreased by 4 μm⁻¹ due to an increase of the concentration of TTIP from 1.7% to 8%. Simultaneously, the surface roughness increased as revealed by profilometry. Thus, since the chemical structure of films was found to change only marginally, a decrease of the film density is likely to cause the observed dependence of the absorption coefficient with increasing precursor concentration.     

Chemical Composition and Structure of Thin Films Produced by Chemical Vapor Deposition

This paper reports results from studies of the chemical composition and structure of semiconducting, dielectric, and metallic films produced from molecular precursors by the chemical vapor deposition method. A study was made of films of zinc sulfides, mixed copper, cadmium, and zinc sulfides, boron nitride, carbonitride, silicon carbonitride, and iridium films. It is shown that the use of metal compounds with different ligands (zinc and manganese) enables production of zinc sulfide films in which manganese ions are uniformly incorporated into the zinc sulfide crystal lattice to substitute zinc at the lattice sites. For the films of simple and mixed cadmium, copper, and zinc sulfides, the film structure depends on the type of substrate. The thin layers of mixed cadmium and zinc sulfides are asubstitution solution with a hexagonal structure. The thin layers of boron nitride produced from borazine exhibit a nanocrystalline structure and are a mixture of cubic and hexagonal phases. Composite layers were produced from alkylamine boranes and their mixtures with ammonia. Depending on synthesis conditions, the layers are mixtures of hexagonal boron nitride, carbide, and carbonitride or pure boron nitride. Using silyl derivatives of asymmetric dimethylhydrazine containing Si—N and C—N bonds in the starting molecule, we produced silicon carbonitride films whose crystal habit belongs to a tetragonal structure with lattice parameters a = 9.6 and c = 6.4 . The iridium films obtained by thermal decomposition of iridium trisacetylacetonate(III) on quartz substrates in the presence of hydrogen have a polycrystalline structure with crystallite sizes of 50 to 500 . A method for determining grainsize composition was proposed, and grain shapes for the iridium films were analyzed. The influence of substrate temperature on the internal microstructure and growth of the iridium films is demonstrated. At the iridium–substrate interface, a transition layer forms, whose composition depends on the substrate material and deposition conditions.     

The Role of Oxygen Dissociation in Plasma Enhanced Chemical Vapor Deposition of Zinc Oxide from Oxygen and Diethyl Zinc

The influence of electron impact dissociation of oxygen on neutral chemistry was studied for plasma-enhanced chemical vapor deposition (PECVD) of zinc oxide using oxygen and diethyl zinc. Electron conditions in the reactor were estimated based on simulations of well-known Ar-O₂ plasmas, while the majority of the thermal chemistry was abstracted from the combustion literature. A rudimentary model of film growth was developed using the rate of oxygen dissociation as the lone adjustable parameter.n Model results were compared directly with experimental measurements of deposition rates and neutral species densities for a wide range of conditions. Good quantitative agreement between experiments and model were observed as a function of composition and rf power. The system is highly sensitive to the electron impact dissociation of oxygen, which creates the radical pool that drives the majority of the chemistry. The approach detailed here provides a framework for the development of models of oxide PECVD derived from other metalorganic precursors.     

大气压射频等离子体化学气相沉积TiO2体系的发射光谱诊断

开展了大气压射频(RF)等离子体化学气相沉积(PCVD)TiO₂放电体系的发射光谱诊断研究, 分别考察了氧气分压、钛酸四异丙酯(TTIP)分压和输入功率对氧原子谱线相对强度、氩原子激发温度、OH振动温度以及转动温度的影响. 结果表明: 随着氧气分压的增加, 氧原子谱线相对强度先迅速增加至峰值后缓慢下降, OH振动温度缓慢增加, 而氩原子激发温度和OH转动温度基本不变. 随着TTIP 分压的增加, 氧原子谱线相对强度下降, 氩原子激发温度没有明显变化, 而OH振动温度和转动温度增加. 随着输入功率的增加, 氧原子谱线相对强度下降, 氩原子激发温度、OH振动温度和转动温度升高.     

电化学沉积技术制备LiNiO2薄膜及表征

Well-crystallized LiNiO₂ thin films were prepared directly on nickel substrates in LiOH solution by constant current electrochemical deposition technique at 95 ℃. The as-prepared LiNiO₂ thin films were characterized by using XRD, SEM and XPS, and the results reveal that the as-prepared LiNiO₂ thin films are dense and uniform in surface and show hexagonal structure. The influence of processing parameters such as reaction temperature, duration, electrical current density as well as the concentration of LiOH solution on the structure and morphologies of as-prepared LiNiO₂ thin films were studied，and the preferable electrochemical processing conditions for preparing LiNiO₂ thin films were suggested.     

Inclined Substrate Deposition of Nanostructured TiO2 Thin Films for DSSC Application

Nanostructured TiO₂ films were deposited onto Indium Tin Oxide (ITO) and glass substrates by dc reactive magnetron sputtering at different substrate inclination angles. The structural and optical properties of the deposited films were studied by X-ray diffraction, scanning electron microscopy and UV–Vis spectrophotometer, respectively. Dye-sensitized solar cells (DSSC) were assembled using these TiO₂ films as photoelectrodes and the effect of the substrate inclination angle in the preparing process of TiO₂ films on the DSSC conversion efficiency was studied.