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.     

TiOx Films Deposited by Plasma Enhanced Chemical Vapour Deposition Method in Atmospheric Dielectric Barrier Discharge Plasma

The plasma enhanced chemical vapour deposition method applying atmospheric dielectric barrier discharge (ADBD) plasma was used for TiO_x thin films deposition employing titanium (IV) isopropoxide and oxygen as reactants, and argon as a working gas. ADBD was operated in the filamentary mode. The films were deposited on glass. The films?? chemical composition, surface topography, wettability and aging were analysed, particularly the dependence between precursor and reactant concentration in the discharge atmosphere and its impact on TiO_x films properties. Titanium in films near the surface area was oxidized, the dominating species being TiO₂ and substoichiometric titanium oxides. The films exhibited contamination with carbon, as a result of atmospheric oxygen and carbon dioxide reactions with radicals in films. No relevant difference of the film surface due to oxygen concentration inside the reactor was determined. The films were hydrophilic immediately after deposition, afterwards their wettability diminished, due to chemical reactions of the film surface and chemical groups involved in the atmosphere.     

结晶和去润湿竞争条件下分子结构对超薄膜表面形貌的影响

将星形支化结构的聚己内酯, 包括六臂星形聚己内酯(HPCL)和树枝状星形聚己内酯(DPCL), 以及线形聚己内酯(LPCL)室温旋涂于云母片上,通过原子力显微镜(AFM)观察分子结构对星形支化聚己内酯超薄膜的润湿-去润湿性质的影响. 在旋涂过程中, 薄膜的形成受去润湿和结晶竞争的控制. 差示扫描量热(DSC)测试结果表明, 当相对分子质量相同时, 结晶性的顺序是: DPCL最弱, HPCL次弱, LPCL最强. 依据分子结构和相对分子质量的影响, 即去润湿和结晶竞争的结果, LPCL、HPCL和DPCL的超薄膜表现出不同的表面形态, 包括尺寸不同的完整的球晶、开口的球晶、树枝状片、分散的颗粒.     

衬底温度对强流脉冲离子束烧蚀沉积类金刚石薄膜化学结构的影响

采用强流脉冲离子束(High-intensitypulsedionbeam,HIPIB)烧蚀技术在Si(100)基体上沉积类金刚石(Diamond-likecarbon,DLC)薄膜,衬底温度的变化范围为298～673K.利用Raman光谱和X射线光电子谱(XPS)对DLC薄膜的化学结合状态与衬底温度之间关系进行研究.薄膜XPS的C1s谱的解谱分析得出薄膜中含有sp³C(结合能为285.5eV)和sp²C(结合能为284.7eV)成分,根据解谱结果评价薄膜中sp³C含量.根据XPS分析可知,衬底温度低于473K时,sp³C的含量大约为40%左右;随着沉积薄膜时衬底温度的提高,sp³C的含量降低,由298K时的42.5%降到673K时的8.1%,从573K开始发生sp³C向sp²C转变.Raman光谱表明,随着衬底温度的提高,Raman谱中G峰的峰位靠近石墨峰位,G峰的半峰宽降低,D峰与G峰的强度比I_D/I_G增大,说明薄膜中的sp³C的含量随衬底温度增加而减少.     

Ultra-Shallow Chemical Characterization of Organic Thin Films Deposited by Plasma and Vacuum-Ultraviolet, Using Angle- and Excitation Energy-Resolved XPS

Nitrogen (N)-rich organic thin films were deposited using both low-pressure plasma- and vacuum-ultraviolet-based techniques, from mixtures of ammonia (NH₃) and ethylene (C₂H₄). These films were investigated using angle-resolved and excitation energy resolved X-ray photoelectron spectroscopy (ARXPS and ERXPS, respectively) in order to determine their sub-surface chemical profiles. These two techniques enable one to tune the ??XPS 95%?? information depth, z _95%, by varying either the angle or the excitation energy. Using a combination of both techniques, z _95% can be varied continuously from 0.7 to 11 nm. The surface-near chemistry is investigated using both high-resolution C 1s spectra and elemental concentrations derived from elemental peak intensities. Results show that while laboratory XPS, and even ARXPS, suggest homogenous surface chemistries, the novel combination of ARXPS and ERXPS points to the existence of a compositional profile in the extreme outer surface layer. Our conclusions are supported by simulations using SESSA software.     

Structure–Property Relationship of Thin Plasma Deposited Poly(allyl alcohol) Films

Poly(allyl alcohol) films with a thickness of about 150 nm were deposited by pulse plasma polymerization onto different substrates (inorganic and organic). The structure/property relationships of these samples were studied in dependence on the duty cycle (DC) of the plasma by a broad combination of different techniques and probes. For the first time volume sensitive methods (FTIR and dielectric spectroscopy) are combined with surface analytics by employing XPS for that system. FTIR spectroscopy gives qualitatively the same dependence of the concentration of the OH groups on DC like XPS. The observed differences are discussed considering the different analytical depths of both the methods. The dielectric measurements show that the plasma deposited films are not thermally stable but undergo a post plasma chemical reaction during heating. The results obtained by dielectric spectroscopy are discussed in detail with the data from FTIR and XPS measurements.     

Influence of Chemical Modification of the Surface on the Electret Properties of Polytetrafluoroethylene

Thermal stability of the electret state of polytetrafluoroethylene films with element oxide structures on the surface was studied. The frequency factor and the activation energies of the newly formed groups of deep centers that capture the electret charge were determined.     

埃洛石-聚醚砜复合膜的形态结构及性能

通过非溶剂致相分离法成功制备了多孔性埃洛石一聚醚砜复合膜。通过扫描电镜观察了膜的微观结构，并对膜的水通量、截留率、亲水性和力学性能等进行了研究。结果表明：埃洛石的加入使得非对称性膜由海绵状结构转变为大指状孔结构。当凝固浴温度为40℃时，复合膜的水通量均比原膜的低。当埃洛石的质量分数为2％时，复合膜的水通量随着凝固浴温度的升高而升高。当埃洛石的质量分数从2％增加到8％时，复合膜的截留率和亲水性随之增加，力学性能随之降低。     

Influence of the Plasma Chemistry on the Composition of ZrOx and NbOx Thin Films Deposited by Reactive Magnetron Sputtering

The plasma chemistry of magnetron sputtered Zr and Nb in an Ar/O₂ atmosphere has been measured as a function of the O₂ partial pressure. The previously reported composition of films deposited onto grounded non-intentionally heated substrates was correlated with the dominant positive and negative ion populations in the plasma. While the oxygen deficient films were grown in the Ar⁺ dominant mode, the close-to-stoichiometric films were grown in the O⁺/O⁻ dominant mode. The formation of close-to-stoichiometric ZrO_2.1 is observed in the compound mode (CM), while the formation of close-to-stoichiometric Nb₂O_4.7 thin films was reported in addition to the CM also in the transition mode (TM). This may be understood based on the 1.5–1.9 times higher power dissipated in the Nb–Ar–O₂ plasma as compared to the Zr–Ar–O₂ plasma. We suggest that at larger power O₂ dissociation may be more efficient and lead to the presence of sufficient atomic oxygen to fully oxidize the films. This finding may provide a pathway towards a deposition rate enhancement, since compound formation at the substrate is enabled in the TM of the higher power Nb–Ar–O₂ plasma and not only in the CM, as in the case of the lower power Zr–Ar–O₂ plasma.     

气相燃烧合成纳米复合粒子的形态与结构

在气相燃烧反应器中成功地合成了TiO₂-SiO₂、TiO₂-SnO₂复合粒子。TiO₂-SiO₂复合粒子中TiO₂以金红石型和锐钛型存在，SiO₂以无定型的形式存在。复合结构为SiO₂附着于TiO₂的外部，在Ti∶Si的进料比较大时SiO₂附着于TiO₂的表面，Ti∶Si比值减小到1∶4时，SiO₂包覆全部TiO₂表面。包覆层的厚度大约为6～7nm。TiO₂-SnO₂的复合粒子中同时存在着三种晶体结构SnO₂、金红石型和锐钛型的TiO₂。在复合粒子的表面，TiO₂和SnO₂两种组分分布均匀。通过改变进料方式可以调整复合粒子的结构。     

Structure of Conducting Polymer Films Prepared on the Surface and in the Pores of Poly(ethylene terephthalate) Track Membranes by Template Synthesis

The results of a structural study of conducting polymer coatings deposited onto poly(ethylene terephthalate) (PET) track membranes by template synthesis are reported. The following aspects of the quality of polymer coatings were studied: the ratio between film and granular polymers, the polymer distribution over the surface of track membranes, and the thickness of polymer layers on the opposite sides of track membranes. The fraction of granular polypyrrole (PPy) on the surface and in the pores of a film increased with pore diameter. A decrease in the polymerization temperature decreased the amount of granular PPy on the surface of membranes, whereas the effect of granular PPy on the water permeability of track membranes remained unchanged. A more homogeneous distribution of PPy over the surface of track membranes can be obtained by density equalization of reacting solutions; however, the fraction of granular PPy on the membrane surface increased in this case. It was found that polymer coatings on the two sides of the surface of a membrane template had different thicknesses. Poly(N-methylpyrrole) completely covered only one side of a track membrane facing a monomer solution.     

等离子化学气相沉积硅-硼-氮复合薄膜的组成和结构

利用X射线衍射（XRD）和X光电子能谱（XPS）等技术对射频－直流－等离子化学气相沉积（RF－DC－PVCD）在钢基本上Si-B-N复合薄膜的组成和结构进行分析和研究；结果表明，通过给试样基体加一适当的直流负偏压，得到含有显著六方氮化硼（h-BN)，立方氮化硼（c-BN)结晶相的Si-B-N薄膜。     

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.     

Experimental Study of the Effect of a Nonthermal Plasma Jet on the Wettability of Polytetrafluoroethylene Surface

High Energy Chemistry - A change in the surface properties of polytetrafluoroethylene films by treatment in nonthermal nonequilibrium plasma generated by atmospheric-pressure plasma jets has been...     

Surface Properties of Polydimethylsiloxane-Based Inorganic/Organic Hybrid Films Deposited on Polyimide Sheets by the Sol-Gel Method

Polydimethylsiloxane (PDMS)-based inorganic/organic hybrids films were prepared on polyimide sheets by the sol-gel method using silanol-terminated PDMS and titanium tetraisopropoxide as starting materials. The effect of heat-treatment temperature on the surface property of the hybrid films was examined in terms of contact angle of water and Tapping-Mode Atomic Force Microscopy (AFM). AFM phase images showed the presence of domains, 200–500 nm in size, on the surface of these films after heat-treatment below 300°C. These regions were more hydrophilic than the rest of the area. The domains disappeared at 300°C and the surface became homogeneous surface of the peak to valley value, about 10 nm. It is also uniformly hydrophobic and a maximum contact angle (about 115°C) was obtained.     

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.     

溶胶-凝胶法制备的纳米PrOy-ZrO2固溶体的表层和体相结构

用改进的柠檬酸溶胶-凝胶法制备了纳米PrOy-ZrO2固溶体. 采用XRD, Raman和TEM等技术对纳米PrOy-ZrO2进行了表征. 结果表明, 改进的柠檬酸溶胶-凝胶法制备的PrOy-ZrO2固溶体于650 ℃焙烧后晶粒大小在5~10 nm之间; 于950 ℃焙烧(Pr>16%)后晶粒大小在20 nm左右. Pr能有效地使ZrO2稳定在四方或立方晶相. 随Pr含量的增加, PrOy-ZrO2固溶体的物相结构从单斜相逐步向四方和立方相转变. XRD和Raman得到的物相结构的差别表明, PrOy-ZrO2固溶体表层和体相结构存在不一致性, 随Pr含量增加, 体相逐步按照m→t→c的物相转变, 表层按照m→t→t"的物相转变. 表层更易生成低对称性和无序结构.     

等离子体增强磁控溅射沉积碳化硅薄膜的化学结构与成膜机理

以CH4和Ar为工作气体,单晶硅为溅射靶,通过微波电子回旋共振(MW-ECR)等离子体增强非平衡磁控溅射方法在不同的CH4流量和沉积温度下制备了a-Si1-xCx∶H薄膜.利用傅里叶变换红外(FT-IR)光谱,X光电子能谱(XPS)和纳米硬度仪等表征方法研究不同沉积参数下薄膜的化学结构、化学配比和硬度的变化.结果表明:室温(25℃)下随CH4流量由5cm·3min-1增加到45cm3·min-1(标准状态)时,薄膜中Si—CH2键,C—H键含量逐渐增加,Si—H键变化不明显;膜中C原子百分比由28%增至76%,Si原子百分比由62%降至19%.当CH4流量为15cm3·min-1时,随沉积温度的升高,薄膜中Si和C原子百分比含量分别为52%和43%,且基本保持不变;膜中Si—H键和C—H键转化为Si—C键,薄膜的显微硬度显著提高,在沉积温度为600℃时达到29.7GPa.根据分析结果,提出了室温和高温下a-Si1-xCx:H薄膜生长模型.     

退火对MgxZn1-xO薄膜特性的影响

采用MOCVD法在c面蓝宝石衬底上生长出了高质量的MgxZn1-xO薄膜. 研究了退火对MgxZn1-xO薄膜各种特性的影响. 将样品分别在真空和氧气中退火1 h. X射线衍射研究发现, 在真空中, 尤其是在氧气中退火的样品的(002)峰均增强. 由原子力显微镜观察发现, 在真空中退火样品的表面与未退火样品的表面几乎相同, 而在氧气中退火后样品的表面变得光滑了很多. 从光致发光光谱中发现, 真空退火后的样品的紫外光谱峰显著增强, 而深能级发射峰几乎消失. 在氧气中退火后样品的紫外光谱峰减弱而深能级发射峰显著增强. 所以退火对MgxZn1-xO薄膜的各种性质具有重要的影响, 通过退火可调节MgxZn1-xO的晶体质量与光学质量.