In situ STM of pulsed laser nanostructured deposits: First stages of film formation

In the synthesis of nanostructured thin films the characterization of the growth processes plays a fundamental role for the control of the film and surface properties. Moreover when the deposition technique is based on the production and the assembling of nanoparticles/clusters the characterization of the precursor size distribution is of fundamental importance.We have designed a pulsed laser deposition (PLD) apparatus for the production of nanostructured thin films and surfaces, connected to a UHV variable temperature scanning tunneling microscope (STM). The whole system is devoted to the synthesis and in situ study of nanostructured and nanoporous functional metal and metal oxide films and surfaces. We have deposited W nanoparticles produced by a few hundreds laser pulses in order to investigate the initial mechanisms of the film growth. Different deposition conditions have been explored by controlling the laser generated plasma expansion through a background gas in the PLD chamber. STM measurements have been performed on W thin films deposited on different substrates to study both the size distribution and the aggregation of the precursors on the surface. Although substrate effects must be taken into account, the control of the background gas pressure and of the target-to-substrate distance allows to produce surfaces with different morphologies. This opens the possibility to tailor the material properties through the control of the size and deposition energy of the building nano-units.     

Amine-containing film deposited in pulsed dielectric barrier discharge at a high pressure and its cell adsorption behaviours

With monomer allylamine, amine-containing functional films were prepared in alternative current pulsed dielectric barrier discharge (DBD) at a high pressure. This paper analyses in detail the film properties and structures, such as hydrophilicity, compounds and microstructures as well as amine density by the water contact angle, Fourier transform infrared spectroscopy, atomic force microscopy, and ultraviolet--visible measurement. The influence of discharge parameters, in particular applied power, on amine density was investigated. As an application the cell adsorption behaviours on plasma polymerization films was performed in-vitro. The results show that at a high pressure pulsed DBD plasma can polymerize films with sufficient amine group on surface, through which the very efficient cell adsorption behaviours was demonstrated, and the high rate of cell proliferation was visualized.     

Interfacial morphology and friction properties of thin PEO and PEO/PAA blend films

The scanning force microscope (SFM) was used to investigate morphology of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blend. The effect of solvent and dewetting in surface structure of PEO film was reported. The results manifested that the crystallization of PEO could be suppressed completely in ultrathin region via using chloroform as a solvent, and the branched-like crystallization was recovered after dewetting. Also, the effect of thickness, the ratio of PEO/PAA and dewetting in surface morphology of PEO-PAA blend films were investigated. These results showed that the crystallization was highly dependent on the ratio of PEO/PAA and the thickness of blend film. Furthermore, we assembled the PEO/PAA layer-by-layer film by spin-casting method for the first time, which exhibited highly efficiency. As a complementary tool, we also used lateral force microscopy (LFM) to explore surface information of these films. The result was indicative of interfacial constraints in ultrathin region, and also was supported by the results showing the spin-casting PEO/PAA blends rather than heterogeneous mixture.     

Growth characteristics of plasma electrolytic oxidation ceramic coatings on Ti-6Al-4V alloy

The aim of this work is to discuss the growth characteristics of the ceramic coatings on Ti alloy by plasma electrolytic oxidation (PEO) technique. Ceramic coatings were prepared on Ti alloy by plasma electrolytic oxidation in different electrolyte solutions under different pulse modes. The composition and the structure of the coatings were investigated by X-ray diffraction and scanning electron microscopy (SEM), respectively. The amount of the dissolved titanium into the electrolytes during PEO process was measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The structure and the composition of the coatings were related to the mode of the spark discharge during PEO process. (a) Under the pulsed single-polar mode: In Na₃PO₄ solution, the spark discharge was mainly due to the breakdown of the oxide film, and the coatings prepared were porous and mainly structured by the Ti from the substrate. In K₄ZrF₆-H₃PO₄ and NaAlO₂-Na₃PO₄ solutions, the main mode of the spark discharge was the breakdown of the oxide film at the initial stage, and then changed into the breakdown of the vapor envelope, and the coatings were rough and thick, and mainly structured by the elements from the electrolyte. (b) Under the pulsed bi-polar mode in NaAlO₂-Na₃PO₄ solution, the spark discharge may be mainly due to the breakdown of the oxide film, the coatings prepared were dense in inner layer and loose in outer layer, and structured by the elements from both the substrate and the electrolyte. Besides, the ICP-AES analyses showed that the amount of the dissolved titanium in the electrolyte during PEO process was more under the breakdown of the oxide film than under the breakdown of the vapor envelope, which was consistent with the changes of the structure of the coatings. Cathode pulse in the pulsed bi-polar mode increased the amount of the dissolved titanium in the electrolyte, compared with the pulsed single-polar one.     

Ti/Ti-类金刚石多层膜的制备与表征

采用电子回旋共振-化学气相沉积结合中频磁控溅射的真空镀膜技术, 以99.99%Ti为靶材, 乙炔为碳源制备了Ti/Ti-类金刚石(DLC)多层膜. 利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱仪 对Ti/Ti-DLC多层膜进行了相结构、组织、成分及形态分析. 采用显微硬度仪、摩擦磨损仪、表面粗糙度仪对Ti/Ti-DLC多层膜进行了力学性能考察. 结果表明: Ti/Ti-DLC多层膜中主要含有TiC晶相; Ti层和Ti-DLC层中未出现柱状晶体生长模式, 分层中均以岛状模式生长; 当调制周期Λ≤ 50 nm时, 分层结构变模糊; 调制周期Λ对Ti/Ti-DLC多层膜的复合硬度、摩擦系数、表面形貌、表面粗糙度都有影响, 当调制周期Λ较小时表现出纳米增硬效应, 表面出现大颗粒, 表面粗糙度和摩擦系数均变大.     

Tribological Behavior of Multiply-Alkylated Cyclopentanes (MACs)-Cu Nanoparticles Composite Thin Film

Multiply-alkylated cyclopentanes (MACs) composite thin films containing Cu nanoparticles are fabricated on the octadecyltrichlorosilane (OTS)-modified substrate by a spin-coating technique. The thickness, wetting behavior, and nanoscale morphologies of the films are characterized by means of ellipsometry, contact angle measurement, and atomic force microscope (AFM). The friction and wear behaviors of the thin films sliding against Si₃N₄ ball are examined on a UMT-2MT tribometer in a ball-on-disk contact mode. The worn surfaces of the OTS-MAC-Cu composite film and the counterpart Si₃N₄ balls are investigated with a scanning electron microscope. Water contact angle on OTS-MAC-Cu composite film is higher than that of OTS-MAC film. OTS-MAC-Cu composite film exhibits higher load-carrying capacity and better friction reduction and antiwear behavior as compared with OTS-MAC film. This may be attributed to the load-carrying and self-repairing property of the Cu nanoparticles in the composite film and the formation of a transfer layer composed of OTS, MAC, and Cu on the rubbing surface of the counterpart ball.     

Crystallization of Poly(Ethylene Oxide) in Thin Films

Crystallization of poly(ethylene oxide) (PEO) in thin films was studied using hot-stage polarized optical microscopy. Isothermal linear crystal growth rates were measured for various film thicknesses at various degrees of undercooling. At a given crystallization temperature, the linear crystal growth rate decreased exponentially with decreasing film thickness below a film thickness of 80 nm. Films showed similar spherulitic morphology down to a film thickness of 30 nm. Control experiments on hydrophilic and hydrophobic surfaces showed that surface chemistry affects stability of the polymer films and causes a competition between crystallization and dewetting.     

AFM studies on Langmuir-Blodgett films of cholesterol

The Langmuir monolayer of cholesterol at the air-water interface exhibits a condensed phase in which the cholesterol molecules are aligned normal to the water surface. We have transferred the monolayer from water surface to different substrates by Langmuir-Blodgett (LB) technique and have studied their assembly by atomic force microscope (AFM). Our studies reveal that the aggregation of cholesterol molecules on hydrophobic surfaces leads to interesting structures. The cholesterol molecules assemble into a uniform film, elongated domains and uniformly distributed torus-shaped domains (doughnuts) for one, two and four cycles of deposition, respectively. Beyond four cycles, the molecules adsorb and desorb by an equal amount resulting in no further deposition. The formation of uniformly distributed doughnuts can be attributed to the hydrophobic interaction and reorganization of the molecules due to successive adsorption and desorption during deposition cycles. Our studies on hydrophilic surfaces show that cholesterol cannot form more than one layer of deposition.PACS: 68.47.Pe Langmuir-Blodgett films on solids; polymers on surfaces; biological molecules on surfaces - 68.37.Ps Atomic force microscopy (AFM) - 68.43.Mn Adsorption/desorption kinetics     

SUPERCONDUCTING FILM INJECTED BY IONS FROM PULSED ENERGETIC DENSE PLASMA SOURCE

The oxygen and silicon ions have been obtained respectively from pulsed energetic dense oxygen plasma and silane plasma generated by electrodeless discharge. The oxygen ions have been injected into superconducting Nb films, and the Si ions into superconducting YBCO films in order to investigate the variation of their superconductivity with the ions injected into them. Auger profile data show that the injection depths range from 20 to 40nm in the films, depending on the injection condition and film material. The resistance－temperature relations (R-T curves) indicate that the superconductivity remains unchanged in the photoresist-masked part of the film, but is significantly changed in the exposed part. The evenness of the film surface remains unchanged after injection. This technique may serve as an alternative to the planar inhibiting fabrication technique in the fabrication of the multi-layer structure of superconducting films, and also possibly to the conventional plasma source ion implantation technique in material surface processing.     

Modification of surface properties of polypropylene (PP) film using DC glow discharge air plasma

The industrial use of polypropylene (PP) films is limited because of undesirable properties such as poor adhesion and printability. In the present study, a DC glow discharge plasma has been used to improve the surface properties of PP films and make it useful for technical applications. The change in hydrophilicity of modified PP film surface was investigated by contact angle (CA) and surface energy measurements as a function of exposure time. In addition, plasma-treated PP films have been subjected to an ageing process to determine the durability of the plasma treatment. Changes in morphological and chemical composition of PP films were analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The improvement in adhesion was studied by measuring T-peel and lap shear strength. The results show that the surface hydrophilicity has been improved due to the increase in the roughness and the introduction of oxygen-containing polar groups. The AFM observation on PP film shows that the roughness of the surface increased due to plasma treatment. Analysis of chemical binding states and surface chemical composition by XPS showed an increase in the formation of polar functional groups and the concentration of oxygen content on the plasma-processed PP film surfaces. T-peel and lap shear test for adhesion strength measurement showed that the adhesion strength of the plasma-modified PP films increased compared with untreated films surface.     

脉冲偏压电弧离子镀TiO2薄膜的力学与光学性能

用脉冲偏压电弧离子镀技术在玻璃基片上制备均匀透明的TiO₂薄膜.利用X射线衍射仪、原子力显微镜、扫描电子显微镜、紫外-可见透射光谱仪和纳米压痕仪等手段,对不同脉冲负偏压下合成薄膜的相结构、微观结构、表面形貌、力学和光学性能进行表征.结果表明，沉积态薄膜为非晶态.脉冲负偏压对薄膜性能有明显的影响.随偏压的增加，薄膜厚度、硬度和弹性模量均先增大后减小，前者峰值出现在100—200 V负偏压范围，后两者则在250—350V范围.300 V负偏压时薄膜硬度最高，薄膜达到原子级表面光滑度，均方 关键词： 2薄膜')" href="#">TiO₂薄膜 脉冲偏压电弧离子镀 硬度 折射率     

Two-dimensional hydrogen behaviors on solid surfaces studied by hydrogen microscope

Recently, much work has been done to study hydrogen behavior on solid surfaces for applications in fuel cells, semiconductor devices, and diamond-like carbon films. We have developed a hydrogen microscope making use of electron stimulated desorption (ESD) spectroscopy. A thermal-field emission type electron gun set to a low-energy range (<1 keV) is used to obtain a beam size less than 100 nm in diameter. A pulsed beam has been used to measure the time-of-flight (TOF) to detect desorbed ions from specimen surfaces. Scanning the pulsed beams across solid surfaces, a two-dimensional distribution image of hydrogen atoms can be obtained. This paper reviews some capabilities of the hydrogen microscope and a chemical state analysis for H and O adsorbed by different elements on a surface.     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

Simultaneous iso-electric focusing of proteins in a micro-fabricated capillary coated with hydrophobic and hydrophilic plasma polymerized films

The ability to modify and reduce the electroosmotic flow (EOF) is one of the most influential parameters which affects iso-electric focusing (IEF) of proteins. Therefore capillaries are usually coated with polymers or gels to prevent non-specific adsorption and suppress the EOF in capillary iso-electric focusing (cIEF) of proteins. In this research hexamethyldisiloxane (HMDS) and 2,3-epoxy-1-propanol (glycidol) plasma polymerized films were deposited onto both surfaces of the capillary separation channel. Cathode solution pH 3, anode solution pH 10 and a carrier ampholyte, pharmalyte provided the necessary stable pH gradient. Simultaneous IEF of proteins in capillaries coated with hydrophobic and hydrophilic plasma polymerized films occurred within minutes. The electroosmotic force of uncoated glass capillaries was suppressed by 50% after deposition of 200 nm 2,3-epoxy-1-propanol compared with a 30% reduction of EOF when the capillary was coated with 200 nm HMDS. The hydrophilic 2,3-epoxy-1-propanol plasma polymerized film was more resistant with a stronger attachment to the glass surface than previously prepared acetonitrile plasma polymerized films.     

Surface-induced breakout crystallization in cylinder-forming P(I-b-EO) diblock copolymer thin films

We have found very slow crystallization in thin films of cylinder-forming poly(isoprene-b -ethyleneoxide) (P(I-b -EO)) diblock copolymers with PEO being the minority block. The film was crystallized at room temperature after melting at 62 ^°C . Imaging methods were combined with X-ray reflectometry and grazing-incidence small-angle X-ray scattering and diffraction. Initially, hexagonally packed, amorphous PEO cylinders lie in the film plane. After 148 days, crystallized, finger-like terraces were observed over the entire film surface. The terrace height is 20% higher than the repeat distance in the as-prepared film. Thus, at the film surface, the cylinders have been destroyed by crystalline lamellae lying in the film plane. The PEO chain stems are perpendicular to the substrate surface and are once-folded and fully interdigitated. The substrate-near layers still consist of the hexagonally packed, amorphous PEO cylinders within the PI matrix.     

Deposition of latex particles encapsulated in polyelectrolyte shells at heterogeneous metal surfaces modified by multilayer films

We used an oblique impinging jet (OIJ) cell to determine the initial deposition rate for the microcapsules deposited on the heterogeneous metal surfaces bare or modified by polyelectrolyte (PE) films. The dependence of reduced particle flux on the Reynolds number of the flow in the OIJ cell was determined by direct counting of particles deposited on the studied surfaces. We used fluorescently labelled latex particles and microcapsules built on these fluorescent cores and the use of fluorescent microscope allowed us to observe “in situ” the deposition processes of particles on rough, highly reflective surfaces. We demonstrated that modification of metallic surfaces of various materials and heterogeneity by the multilayer PE films result in the formation of uniformly charged film of nanometers thickness. The formation of such a film leads to the increase of deposition efficiency and its initial rate is governed by the charge of the film covered surface and the outermost layer of the capsule shell being in agreement with the prediction of the convective-diffusion theory.     

Mechanism of plasma polymerization: The effect of substrate and substrate topography

Surface properties of metals and plastic substrates and properties of plasma polymerized films on these substrates are reported. The surface and film properties were measured with ellipsometry, surface potential difference, photoelectron-emission and fluid contact angles. Light scattering, profilometry and scanning electron microscopy were used to characterize surface roughness and topography. The modification of the adhesive properties of low energy surfaces (such as Teflon) by plasma polymerization is shown. Adhesive properties of plasma films on metals is also shown. It is shown that photoelectron-emission may be a valuable tool for detecting the presence and decay of excited molecules and radicals formed during plasma polymerization.     

Surface modification of a polyamide 6 film by He/CF4 plasma using atmospheric pressure plasma jet

Polyamide 6 (PA 6) films are treated with helium(He)/CF₄ plasma at atmospheric pressure. The samples are treated at different treatment times. The surface modification of the PA 6 films is evaluated by water contact angle, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The etching rate is used to study the etching effect of He/CF₄ plasma on the PA 6 films. The T-peel strengths of the control and plasma treated films are measured to show the surface adhesion properties of the films. As the treatment time increases, the etching rate decreases steadily, the contact angle decreases initially and then increases, while the T-peel strength increases first and then decreases. AFM analyses show that the surface roughness increases after the plasma treatment. XPS analyses reveal substantial incorporation of fluorine and/or oxygen atoms to the polymer chains on the film surfaces.     

Self-organized transformation to polyaniline nanowires by pulsed energetic electron irradiation in a plasma focus device

An ingenious method for fabricating network of polyaniline nanowires at room temperature in microsecond timescale is demonstrated by using the pulsed electron beam of a plasma focus device. The electron beam of the plasma focus device having a wide range of energies (10-200 keV) was irradiated on to the freestanding polyaniline film. The growth of polyaniline nanowires on the surface of film sample is confirmed by field emission scanning electron microscope images showing nanowires of about 50-80 nm in diameter and up to few tens of micrometers in length.     

Synthesis,structure, and electrochemical properties of epitaxial perovskite La0.8Sr0.2CoO3 film on YSZ substrate

Epitaxial films of the perovskite, La_0.8Sr_0.2CoO₃ (LSC), for SOFCs cathode were deposited on yttria-stabilized zirconia (YSZ) single crystals by pulsed laser deposition method. The films were characterized by thin-film X-ray diffraction measurement, atomic force microscopy (AFM), transmission electron microscope (TEM), and ac impedance spectroscopy. The film orientations depend on the substrate planes. The LSC films on the YSZ (100) and (111) substrates showed the (110) orientation with different twin structures, while those on the YSZ (110) had (100) and (112) orientations. Surface morphology of the films also depends on the substrate orientations. These films showed different electrode properties depending on the orientations. The relationships between the properties, the film orientations, surface morphology, and lattice misfit are discussed.