Segregation of silicone acrylate from acrylate mixture at resin-mold interface and its effect on UV embossing

When silicone diacrylate was added in small amount (<5 wt.%) to ultraviolet (UV) curable formulations containing other oligomeric diacrylates, there was segregation of the silicone additive at the solid substrate-formulation interface. The amount was quantified by X-ray photoelectron spectroscopy measurement of the UV cured film surface composition. The effect of silicone diacrylate concentration, resin formulation and substrate polarity on silicone surface excess was systematically studied. Young's-Gibbs adsorption theory was applied to the prediction of the silicone surface excess at the solid substrate interface for these oligomeric mixtures. Further, we proposed a simplified Young's-Gibbs adsorption theory equation to predict the variation of surface excess from only formulation surface tension and substrate critical surface tension. The selective segregation is beneficial to demolding in UV embossing since only small amount of release added can result in large decrease of the mold-resin interfacial energy difference leading to easy demolding and high replication fidelity.     

Patterning of indium-tin oxide on glass with picosecond lasers

The results of patterning of the indium-tin oxide (ITO) film on the glass substrate with high repetition rate picosecond lasers at various wavelengths are presented. Laser radiation initiated the ablation of the material, forming grooves in ITO. Profile of the grooves was analyzed with a phase contrast optical microscope, a stylus type profiler, scanning electron microscope (SEM) and atomic force microscope (AFM). Clean removal of the ITO film was achieved with the 266 nm radiation when laser fluence was above the threshold at 0.20 J/cm², while for the 355 nm radiation, the threshold was higher, above 0.46 J/cm². The glass substrate was damaged in the area where the fluence was higher than 1.55 J/cm². The 532 nm radiation allowed getting well defined grooves, but a lot of residues in the form of dust were generated on the surface. UV radiation with the 266 nm wavelength provided the widest working window for ITO ablation without damage of the substrate. Use of UV laser radiation with fluences close to the ablation threshold made it possible to minimize surface contamination and the recast ridge formation during the process.     

Growth of thin Fe(0 0 1) films for terahertz emission experiments

The electrical and magnetic properties of thin iron (Fe) films have sparked significant scientific interest. Our interest, however, is in the fundamental interactions between light and matter. We have discovered a novel application for thin Fe films. These films are sources of terahertz (THz) radiation when stimulated by an incident laser pulse. After intense femtosecond pulse excitation by a Ti:sapphire laser, these films emit picosecond, broadband THz frequencies. The terahertz emission provides a direct measure of the induced ultrafast change in magnetization within the Fe film. The THz generation experiments and the growth of appropriate thin Fe films for these experiments are discussed. Several criteria are used to select the substrate and film growth conditions, including that the substrate must permit the epitaxial growth of a continuous, monocrystalline or single crystal film, yet must also be transparent to the emitted THz radiation. An Fe(0 0 1) film grown on the (0 0 1) surface of a magnesium oxide (MgO) substrate makes an ideal sample. The Fe films are grown by physical vapor deposition (PVD) in an ultrahigh vacuum (UHV) system. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) are used to characterize the Fe(0 0 1) films. Two substrate surface preparation methods are investigated. Fe(0 0 1) films grown on MgO(0 0 1) substrates that are used as-received and films grown on MgO(0 0 1) substrates that have been UV/ozone-cleaned ex vacuo and annealed in vacuo produce the same results in the THz generation experiments. Either substrate preparation method permits the growth of samples suitable for the THz emission experiments.     

Effect of substrate temperature on the surface and interface oxidation of NiTi thin films

NiTi shape memory alloy thin films are deposited on pure Cu substrate at substrate ambient temperatures of 300 °C and 450 °C. The surface and interface oxidation of NiTi thin films are characterized by X-ray photoelectron spectroscopy (XPS). After a subsequent annealing treatment the crystallization behavior of the films deposited on substrate at different temperatures is studied by X-ray diffraction (XRD). The effects of substrate temperature on the surface and interface oxidation of NiTi thin films are investigated. In the film surface this is an oxide layer composed of TiO₂. The Ni atom has not been detected on surface. In the film/substrate interface there is an oxide layer with a mixture Ti₂O₃ and NiO in the films deposited at substrate temperatures 300 °C and 450 °C. In the films deposited at ambient temperature, the interface layer contains Ti suboxides (TiO) and metallic Ni.     

Grafting onto poly(ethylene terephthalate) driven by 172 nm UV light

The reactivity of the surface of poly(ethylene terephthalate) (PET) film under 172 nm UV irradiation (xenon excimer lamp) towards nitrogen-borne 1-octene, n-nonane and heptafluorodecene vapor was investigated. Materials receiving from 0 to 24 J/cm² of UV were examined by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF/SIMS), water and mineral oil contact angle measurement and atomic force microscopy (AFM). A uniform nanoscale layer developed on PET surface attributed to the grafting reaction between photolytically-produced polymer radicals and vapor phase molecules.     

Formation of interface and surface oxides on supported Pd nanoparticles

We have quantitatively studied the interaction between oxygen and an Fe₃O₄-supported Pd model catalyst by molecular beam (MB) methods, time resolved IR reflection absorption spectroscopy (TR-IRAS) and photoelectron spectroscopy (PES) using synchrotron radiation. The well-shaped Pd particles were prepared in situ by metal evaporation and growth under ultrahigh vacuum (UHV) conditions on a well-ordered Fe₃O₄ film on Pt(1 1 1).It is found that for oxidation temperatures up to 450 K oxygen predominantly chemisorbs on metallic Pd whereas at 500 K and above (∼10⁻⁶ mbar effective oxygen pressure) large amounts of Pd oxide are formed. These Pd oxide species preferentially form a thin layer at the particle/support interface, stabilized by the iron-oxide support. Their formation and reduction is fully reversible. Upon decomposition, oxygen is released which migrates back onto the metallic part of the Pd surface. In consequence, the Pd interface oxide layer acts as an oxygen reservoir, the capacity of which by far exceeds the amount of chemisorbed oxygen on the metallic surface.Additionally, Pd surface oxides can also be formed at temperatures above 500 K. The extent of surface oxide formation critically depends on the oxidation temperature. This effect is addressed to different onset temperatures for oxidation of the particle facets and sites. It is shown that the presence of Pd surface oxides sensitively modifies the adsorption and reaction properties of the model catalyst, i.e. by lowering the CO adsorption energy and CO oxidation probability. Still, a complete reduction of the Pd surface oxides can be obtained by extended CO exposure, fully reestablishing the metallic Pd surface.     

Combined AFM and Brewster-angle analysis of gradually etched ultrathin SiO2 - Comparison with SRPES results

Two surface sensitive techniques are employed to assess both structural and optical properties of an inhomogeneous Si(1 1 1)/silicon oxide multilayer system. Upon gradual etch-back of the native silicon oxide layer, structural changes of the respective interfaces were determined by contact-mode atomic force microscopy (CM-AFM); optical data were obtained by Brewster-angle analysis (BAA) at a single wavelength. It is shown, that the sensitivity of BAA leads to the identification of an additional strained sub-surface layer that was investigated by subsequent etching experiments and following optical analysis. Inclusion of this layer and its interfaces into a multilayer model allowed precise numerical evaluation of the respective oxide thicknesses in the range between 12 Å and 2 Å. These values, obtained by combination of BAA and AFM, are in excellent agreement with results obtained by synchrotron radiation photoelectron spectroscopy (SRPES). It is furthermore shown, that the thickness resolution limit of BAA (at constant nanotopographic roughness) is well below 1 Å. A limitation of BAA single-wavelength analysis is reached when the roughness variation, in terms of an effective layer and its thickness, exceeds the oxide thickness variation.     

The effect of cerium and lanthanum surface treatments on early stages of oxidation of A361 aluminium alloy at high temperature

X-ray photoelectron spectroscopy analysis has been used to study the surface of A361 aluminium alloy after electrodeposition of cerium and lanthanum compounds followed by oxidation tests in air at 100-500 °C for 2 h. Cerium and lanthanum oxide deposits are found on the β-AlFeSi second phase particles and to a lesser extent on the eutectic Al-Si areas, while the α-Al phase is covered with a thin aluminium oxide film. This uneven deposition may be related either to a preferential nucleation and growth process on active interfaces or to the differing electrical conductivity of the phases and intermetallic compounds of the alloy. Initial stages of oxidation of A361 alloy disclosed thickening of the aluminium oxide layer and Mg enrichment at the surface, especially above 400 °C. Rare earth deposits revealed two different effects: reduced Mg diffusion and enhanced thickening of the aluminium oxide film. A distinctive behaviour of Ce oxide appears at 300-500 °C related with Ce(III) to Ce(IV) transition.     

Growth and oxidation of a Ni3Al alloy on Ni(1 0 0)

The growth and oxidation of a thin film of Ni₃Al grown on Ni(1 0 0) were studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and high resolution electron energy loss spectroscopy (EELS). At 300 K, a 12 Å thick layer of aluminium was deposited on a Ni(1 0 0) surface and subsequently annealed to 1150 K resulting in a thin film of Ni₃Al which grows with the (1 0 0) plane parallel to the (1 0 0) surface of the substrate. Oxidation at 300 K of Ni₃Al/Ni(1 0 0) until saturation leads to the growth of an aluminium oxide layer consisting of different alumina phases. By annealing up to 1000 K, a well ordered film of the Al₂O₃ film is formed which exhibits in the EEL spectra Fuchs-Kliewer phonons at 420, 640 and 880 cm⁻¹. The LEED pattern of the oxide shows a twelvefold ring structure. This LEED pattern is explained by two domains with hexagonal structure which are rotated by 90° with respect to each other. The lattice constant of the hexagonal structure amounts to ∼2.87 Å. The EELS data and the LEED pattern suggest that the γ^′-Al₂O₃ phase is formed which grows with the (1 1 1) plane parallel to the Ni(1 0 0) surface.     

The influence of UV irradiation on the surface of chitosan films

The surface properties of chitosan films before and after UV-irradiation (λ = 254 nm and 248 nm, respectively) were investigated using the technique of scanning electron microscopy (SEM) and by means of contact angle measurements allowing the calculation of surface free energy. Moreover, in order to determine the film mass changes, quartz crystal microbalance (QCM) measurements were performed. Measurements of the contact angle for diiodomethane (D), formamide (F) and glycerol (G) on the surface of chitosan films were made. The chemical and structural changes during UV irradiation were studied by FTIR-ATR spectroscopy.The contact angle and the surface free energy were altered by UV irradiation of chitosan films. The microscopy images have shown that the KrF excimer laser irradiation caused visible damages on the surface in comparison with the surface exposed to the mercury UV lamp. The surface modification of chitosan films can be achieved using both, the low intensity UV lamp and the excimer laser.     

The growth of Au/Pd/alumina/Cu-Al system studied by SRPES

An ultra-thin alumina layer grown on Cu-9at.%Al (1 1 1) surface was studied using synchrotron radiation photoelectron spectroscopy (SRPES), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). By deconvolving SRPES spectra of the Al 2p doublet, four components belonging to metallic as well as oxide phases were recognized. Pd-Au alloy formation was confirmed by SRPES measurement during Pd and Au deposition. The study of the system's thermal stability reveals diffusion of Pd and Au atoms through the alumina layer. While Au atoms start to diffuse under the alumina layer at 670 K, Pd atoms are forming Pd-Al surface alloy at this temperature. The diffusion of Pd atoms through alumina occurs when sample was heated over 770 K. Alumina layer was stable even after heating the sample at 870 K, but its structure was corrupted probably due to the diffusion of metal atoms.     

Composition depth profiles of Bi3.15Nd0.85Ti3O12 thin films studied by X-ray photoelectron spectroscopy

In the present work, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition depth profiles of Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin film, which was prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD). It is shown that there are three distinct regions formed in BNT film, which are surface layer, bulk film and interface layer. The surface of film is found to consist of one outermost Bi-rich region. High resolution spectra of the O 1s peak in the surface can be decomposed into two components of metallic oxide oxygen and surface adsorbed oxygen. The distribution of component elements is nearly uniform within the bulk film. In the bulk film, high resolution XPS spectra of O 1s, Bi 4f, Nd 3d, Ti 2p are in agreement with the element chemical states of the BNT system. The interfacial layer is formed through the interdiffusion between the BNT film and Pt electrode. In addition, the Ar⁺-ion sputtering changes lots of Bi³⁺ ions into Bi⁰ due to weak Bi-O bond and high etching energy.     

Morphology and composition of nanoscale surface oxides on Fe–20Cr–18Ni{1 1 1} austenitic stainless steel

Surface oxidation ranging from initial stages to the onset of passive oxide layer formation have been investigated on Fe–20Cr–18Ni{1 1 1} single crystal surface by X-ray photoelectron spectroscopy (XPS). Surface segregation of the alloying elements and the morphology of the surface oxide nanostructure were characterized quantitatively by inelastic electron background analysis. Our results demonstrate that by increasing the oxidation temperature the relative concentrations of Fe²⁺ and Fe³⁺ cations increase due to their enhanced mobility. Higher temperature also improves the mobility of chromium, thus enhancing its segregation to the oxygen-rich surface and thereby reinforcing the passive layer on the alloy. This is in agreement with the results showing the sudden decrease in oxide film thickness at the oxidation temperatures exceeding 600 K. Additionally, a pronounced segregation of metallic nickel is found in the interface between the surface oxide layer and the bulk alloy.     

Effect of the chemistry and structure of the native oxide surface film on the corrosion properties of commercial AZ31 and AZ61 alloys

The purpose of this study has been to advance in knowledge of the chemical composition, structure and thickness of the thin native oxide film formed spontaneously in contact with the laboratory atmosphere on the surface of freshly polished commercial AZ31 and AZ61 alloys with a view to furthering the understanding of protection mechanisms. For comparative purposes, and to more fully describe the behaviour of the native oxide film, the external oxide films formed as a result of the manufacturing process (as-received condition) have been characterised. The technique applied in this research to study the thin oxide films (thickness of just a few nanometres) present on the surface of the alloys has basically been XPS (X-ray photoelectron spectroscopy) in combination with ion sputtering. Corrosion properties of the alloys were studied in 0.6 M NaCl by measuring charge transfer resistance values, which are deduced from EIS (electrochemical impedance spectroscopy) measurements after 1 h of exposure. Alloy AZ61 generally showed better corrosion resistance than AZ31, and the freshly polished alloys showed better corrosion resistance than the alloys in as-received condition. This is attributed to a combination of (1) higher thickness of the native oxide film on the AZ61 alloy and (2) greater uniformity of the oxide film in the polished condition. The formation of an additional oxide layer composed by a mixture of spinel (MgAl₂O₄) and MgO seems to diminish the protective properties of the passive layer on the surface of the alloys in as-received condition.     

Epitaxial growth of Al on Si(1 1 1) with Cu buffer layers

The structure of thin Al films grown on Si(1 1 1) with thin Cu buffer layers has been investigated using synchrotron radiation photoemission spectroscopy. A thin Cu(1 1 1) layer between the Si(1 1 1) substrate and an Al film may enhance quantum well effects in the Al film significantly. The strength of quantum well effects has been investigated qualitatively with respect to the thickness of the Cu buffer layer and to the Al film thickness. Deposition of Cu on Si(1 1 1)7 × 7 leads to formation of a disordered silicide layer in an initial regime before a well-ordered Cu(1 1 1) film is formed after deposition of the equivalent of 6 layers of Cu. In the regime below 6 layers of Cu the disorder is transferred to Al layers subsequently grown on top. The initial growth of up to 8 layers of Al on a well-ordered Si/Cu(1 1 1) layer leads to a disordered film due to the lattice mismatch between the two metals. When the Cu buffer layer and the Al over-layer are above 6 and 8 layers, respectively the Al film shows sharp low energy electron diffraction patterns and very sharp quantum well peaks in the valence band spectra signalling good epitaxial growth.     

A green synthetic approach to graphene nanosheets for hydrogen adsorption

A green and facile strategy of preparing graphene by reducing exfoliated graphite oxide (GO) with glucose was developed in this study. The as-prepared samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Atomic force microscopy (AFM). The characterization results indicated that the graphene sheets (GS) were of high quality with smooth surface, rich pore structure and few layer graphene. The samples have a BET specific surface area of 1205.8 m² g⁻¹ measured by N₂ adsorption at 77 K. The hydrogen storage capacity of 2.7 wt.% at 298 K and 25 bar demonstrated that the as-prepared graphene employing glucose as reductant is supposed to be a promising material with outstanding property for hydrogen storage.     

紫外辐照对聚醚酰亚胺薄膜介电性能的影响

研究了不同紫外辐照时间对聚醚酰亚胺(PEI)薄膜介电性能的影响。采用FT-IR和SEM表征了PEI薄膜的分子结构和微观形貌。结果表明,紫外辐照后PEI薄膜在1742 cm-1处的吸收峰比原薄膜增大,说明PEI分子链中的C=O基团随辐照时间的增加而增加,并在薄膜表面产生了微裂纹。对PEI薄膜的介电性能进行的研究结果表明,随着紫外辐照时间的增加,PEI薄膜的介电常数和介电损耗增大,而表面电阻率下降,体积电阻率基本不变。并随紫外辐照时间的增加,直流击穿强度呈先增加后降低的趋势,一定辐照剂量可使薄膜发生交联反应,使击穿场强较原薄膜提高20%以上。     

Morphological and compositional analysis of passive film on austenitic stainless steel in nitric acid medium

Passive film properties of type 304L stainless steel in nitric acid medium are investigated in both ex situ and in situ conditions. Ex situ results revealed that variation in passive film morphology occurs depending upon the concentration and time of immersion. In situ surface morphological investigation showed formation of platelet like structures at lower concentrations (0.1 M, 0.5 M), and towards higher concentration (0.6 M, 1 M) the platelet like structures got agglomerated, homogenized and started depleting from the surface leading to opening up of oxide boundaries. Compositional analysis of the passive film revealed duplex nature at lower concentration consisting of hydroxide and oxide layer, and with increasing concentration oxide layer predominates over the surface.     

紫外辐照对聚醚酰亚胺薄膜介电性能的影响北大核心CSCD

研究了不同紫外辐照时间对聚醚酰亚胺(PEI)薄膜介电性能的影响。采用FT-IR和SEM表征了PEI薄膜的分子结构和微观形貌。结果表明,紫外辐照后PEI薄膜在1742cm^(-1)处的吸收峰比原薄膜增大,说明PEI分子链中的C=O基团随辐照时间的增加而增加,并在薄膜表面产生了微裂纹。对PEI薄膜的介电性能进行的研究结果表明,随着紫外辐照时间的增加,PEI薄膜的介电常数和介电损耗增大,而表面电阻率下降,体积电阻率基本不变。并随紫外辐照时间的增加,直流击穿强度呈先增加后降低的趋势,一定辐照剂量可使薄膜发生交联反应,使击穿场强较原薄膜提高20%以上。     

Thermal decomposition of Mo(CO)6 on thin Al2O3 film: A combinatorial investigation by XPS and UPS

A thin and homogeneous alumina film was prepared by deposition and oxidation of aluminum on a refractory Re(0 0 0 1) substrate under ultrahigh vacuum conditions. X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and high-resolution electron-energy-loss spectroscopy (HREELS) demonstrate that the oxide film is long-range ordered, essentially stoichiometric and free from surface hydroxyl groups. The chemisorption and thermal decomposition of Mo(CO)₆ on the Al₂O₃ film were investigated by means of XPS and UPS. Mo(CO)₆ adsorbs molecularly on the oxide film at 100 K; however, thermal decomposition of the adsorbate occurs upon annealing at high temperatures. Consequently the metallic molybdenum clusters are deposited on the thin alumina film via complete decarbonylation of Mo(CO)₆.