Porphyrin effect on the surface morphology of amphiphilic polymers as observed by atomic force microscopy

Complexes of porphyrin photosensitizers (PPS) with triblock copolymers of ethylene- and propylene oxide – Pluronics^® – exhibit markedly increased activity in the generation of singlet oxygen in aqueous media, as compared to pure porphyrins. Pluronics are amphiphilic polymers with surfactant properties suitable for a number of medical applications. PPS–Pluronic systems are considered as promising agents for photodynamic therapy which implies generation of singlet oxygen in the water-based human tissue.Importantly, Pluronics are capable of solubilization of not only water-soluble, but also hydrophobic PPS providing their transfer into the aqueous phase. It has been shown earlier that specific interactions of PPS with Pluronics must play a primary role for the photocatalytic properties of PPS–Pluronic systems. In the process of solubilization of a hydrophobic porphyrin by a Pluronic, both components are dissolved in an organic solvent, which is then removed, and the dry film is re-dissolved in water. Apparently, the initial binding between the porphyrin and the lipophilic part of the polymer takes place already at the stage of the film formation.We applied atomic force microscopy (AFM) to visualize structures formed by Pluronics upon their interactions with meso-tetraphenylporphyrin (TPP). We studied the surface structure of Pluronics^® F87, F108 and F127 crystallized alone or together with TPP on silicon substrates from chloroform solutions. We found Pluronics to form similar dendritic structures independently of their molecular weight and degree of hydrophobicity. In the presence of TPP, though, we observed formation of distinct convex structures on top of the Pluronic dendrites. These structures appeared to consist of multiple flat layers placed on top of each other. Their sizes varied among the three Pluronics. We believe that TPP aggregates interact with the hydrophobic units of Pluronics causing the polymer chains to pack themselves in a distinct manner around those TPP-containing “cores”. These interactions apparently direct formation of complexes between the porphyrin and the polymer upon their dissolution in water, thus resulting in the encapsulation of TPP aggregates inside a Pluronic micelle. A single mechanism for the TPP solubilization by Pluronics is consistent with the same catalytic activity of the three TPP–Pluronic systems observed in the photooxidation of tryptophan.     

Characterization of silanization and antibody immobilization on spin-on glass (SOG) surface

Most embedded optical waveguide biosensors require low dielectric optical material. The prerequisites for such applications include the selection of an appropriate material and effective bio-functionalization. Spin-on glass (SOG) is one of the preferred polymers that can be easily deposited. Further, the chemical properties of the polymer make it amenable for bio-functionalization. This paper reports a detailed study of a protocol for immobilization of antibodies on SOG for possible immunobiosensor applications. The effect of silanization at different pH values on the number of free and usable amine sites was quantified by fluorimetry. Contact angle measurements, ellipsometry, AFM, and fluorescence microscopy was used for assessing the surface properties at various stages of preparation, functionalization and biomolecule immobilization.     

Parameterization of the magnetite coating surfaces on low-carbon steel with the use of atomic force microscopy data

The atomic force microscopy (AFM) technique is used to obtain information on the dynamic behavior of the magnetite coating (MC) formed on a steel 3 (St3) sample by chemical oxidation in a solution of ammonium nitrate. Digitized AFM data are the sets of profiles of chaotic roughness obtained via a sensing probe scanning over the surface fragment under study. The flicker noise spectroscopy (FNS) technique is used to analyze AFM images and to select parameters adapted to MC state characterization at the initial stages of formation. The FNS parameters introduced to characterize coating surfaces are calculated from spatial power spectra and transient structure functions. These parameters are considered to be the correlation lengths for different-type irregularities (jumps and spikes). Additionally, dimensionless parameters are introduced to characterize the loss of correlation in a series of irregularities when spatial intervals are substantially less than the correlation lengths. The performed FNS parameterization enabled us to obtain information on the state of the initial surface of St3 samples and to reveal the structural features intrinsic to the surface of MCs formed after different periods of oxidation. This information determines correlations between the elements of the MC structure and characterizes the properties of its microirregularities arising at different stages of coating formation.     

Porphyrin films — 5: Strong fluorescence

Films of tetra(perfluorophenyl)porphyrin (TFPP) show comparable strong host fluorescence whether deposited on room temperature or heated (135°C) mica substrates. Films of tetraphenylporphyrin (TPP) show only 9% as much fluorescence when deposited on unheated mica but 60% as much fluorescence when deposited on heated mica; moreover, the latter films show enhanced fluorescence from impurity guests. Octaethylporphyrin (OEP) behaves like tetraphenylporphyrin. It is observed that crystallite size is larger for films deposited on heated as compared to unheated mica. Larger crystallites could explain increased host and guest fluorescence in films of TPP and OEP prepared on heated substrates if grain boundaries serve as sites both for quenching and for trapping host excitons. The strong host fluorescence of films of TFPP can be explained either (a) by very slow exciton diffusion rates or (b) very few host quenching sites and very few guest trapping sites.     

Structural and optical properties of amorphous hydrogenated silicon carbonitride films produced by PECVD

Amorphous hydrogenated silicon carbonitride thin films (a-Si:C:N:H), deposited by plasma enhanced chemical vapour deposition (PECVD) using hexamethyldisilazane (HMDSN) as monomer and Ar as feed gas, have been investigated for their structural and optical properties as a function of the deposition RF plasma power, in the range of 100-300 W. The films have been analysed by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), UV-vis-NIR spectrophotometry and atomic force microscopy (AFM). From the analysis of the FT-IR spectra it results that the films become more amorphous and inorganic as RF plasma power increases. The incorporation of oxygen in the deposited layers, mainly due to the atmospheric attack, has been evaluated by XPS and FT-IR spectroscopy. Reflectance/transmittance spectra, acquired in the range of 200-2500 nm, allow to descrive the film absorption edge for interband transitions. A relationship between the optical energy band gap, deduced from the absorption coefficient curve, and the deposition RF plasma power has been investigated. The reduction of the optical energy gap from 3.85 to 3.69 eV and the broadening of the optical absorption tail with RF plasma power increasing from 100 to 300 W are ascribed to the growth of structural disorder, while the increase of the refractive index, evaluated at 630 nm, is attributed to a slight densification of the film. The AFM analysis confirms the amorphous character of the films and shows how the deposited layers become rougher when RF plasma power increases. The wettability of the film has been studied and related to the chemical composition and to the morphology of the deposited layers.     

Surface and interface properties of thin pentacene and parylene layers

To improve Organic Thin Film Transistor (OTFT) properties we study OTFT semiconductor/dielectric interfacial properties via examination of the gate dielectric using thin Parylene C layer. Structural and morphology properties of pentacene layers deposited on parylene layer and SiO₂/Si substrate structure were compared. The surface morphology was investigated using atomic force microscopy (AFM) and scanning electron microscopy (SEM). AFM topography of pentacene layer in non-contact mode confirmed the preferable pentacene grain formation on parylene surface in dependence on layer thickness. The distribution of chemical species on the surfaces and composition depth profiles were measured by secondary ion mass spectroscopy (SIMS) and surface imaging. The depth profiles of the analyzed structures show a homogenous pentacene layer, characterized with C or C₂ ions. Relatively sharp interface between pentacene and parylene layers was estimated by characteristic increased intensity of CCl ions peak. For revealing the pentacene phases in the structures the Micro-Raman spectroscopy was utilized. Conformal coatings of parylene and pentacene layers without pinholes resulted from the deposition process as was confirmed by SIMS surface imaging. For the pentacene layers thicker than 20 nm, both thin and bulk pentacene phases were detected by Micro-Raman spectroscopy, while for the pentacene layer thickness of 5 and 10 nm the preferable thin phase was detected. The complete characterisation of pentacene layers deposited on SiO₂ and parylene surface revealed that the formation of large grains suggests 3D pentacene growth at parylene layer with small voids between grains and more than one monolayer step growth. The results will be utilized for optimization of the deposition process.      

用锌有机源和CO2/H2混合气源PECVD沉积ZnO薄膜

在等离子体作用下,以CO2/H2混合气为氧源,Zn(C2H5)2锌为锌源,在单晶硅上生长出高度择优取向的氧化锌薄膜。X射线衍射分析表明,薄膜为六方结构,c轴高度择优;原子力显微镜观察到晶粒是有规律地按六方排布,薄膜的表面粗糙度较小;从光致发光谱还发现在380 nm处有非常强的紫外峰。     

MAPLE deposition of biomaterial multilayers

Double layers of polyethylene glycol (PEG) and 3-(3,4-dihydroxyphenyl)-2-methyl-l-alanine (m-DOPA) thin films were obtained by matrix assisted pulsed laser evaporation (MAPLE) technique, by depositing a first layer of m-DOPA on Si substrate and a second layer of PEG on top of it. The films were characterized by low angle X-ray diffraction (LAXRD), X-ray reflectivity (XRR), atomic force microscopy (AFM), and micro-Raman spectroscopy. From these analyses it resulted that PEG was deposited without any relevant damage both in terms of chemical structure and molecular weight. Furthermore, PEG chains were mostly in the extended conformation, although PEG micelles appeared.     

Incidence angle dependence on structural and optical properties of UHV deposited copper nano layers

Copper nano-layers with different incident angles as vertical, 20 and 30 degrees, same 73.3 nm thicknesses, and same deposition rate, were deposited on glass substrates, at 373K temperature, under UHV conditions. Their nano-structures were determined by AFM and XRD methods. Their optical properties were measured by spectrophotometry in the spectral range of 300–1100 nm. Kramers–Kronig relations were used for the analysis of the reflectivity curves of Cu films to obtain the optical constants of the nano layers. Different incident angles show important effects on both structural and optical properties. The effective medium approximation was employed to establish the relation between structure zone model (SZM) and EMA predictions. By increasing incidence angle the separation of metallic grains increases, hence the volume fraction of voids increases. That is in agreement with AFM analysis. The predictions of Drude free-electron theory are compared with experimental results for dielectric functions of these nano layers. There is a good agreement between our optical results and Hangman's optical results for a bulk standard Cu sample.     

The role of Laplace pressure in the formation of the structure of thin layers based on silicon dioxide

Formation of the structure of thin layers deposited from the gas phase occurs not only during film deposition but also during the subsequent annealing. In the present work, porous films were deposited using the catalytic chemical vapor deposition (Cat-CVD) procedure. It was shown that the kinetics of a decrease in the film volume during annealing can be explained taking into account the role of Laplace pressure in the formed pores.     

Thermal and fluctuation-induced deformations of chemical bonds in surface and boundary layers of polymers

The deformation of chemical bonds in polymer molecules of surface layers of samples, boundary layers between supramolecular aggregates, and boundary layers between polymers and solids in polymer composites is investigated using IR and Raman spectroscopy. It is found that the chemical bonds are elongated on a free surface and in boundary layers between supramolecular aggregates. By contrast, the chemical bonds are contracted in boundary layers between polymers and solids. The concentration and the strain of excited chemical bonds (strained to approximately a theoretical ultimate elongation) are increased on the free surface and in the boundary layers between supramolecular aggregates, whereas the concentration and the strain of excited chemical bonds in the boundary layers between polymers and solids are decreased. These effects are explained by the changes in the atomic vibrations in the surface and boundary layers.     

Structural, morphology and electrical properties of layered copper selenide thin film

Thin films of copper selenide (CuSe) were physically deposited layer-by-layer up to 5 layers using thermal evaporation technique onto a glass substrate. Various film properties, including the thickness, structure, morphology, surface roughness, average grain size and electrical conductivity are studied and discussed. These properties are characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), ellipsometer and 4 point probe at room temperature. The dependence of electrical conductivity, surface roughness, and average grain size on number of layers deposited is discussed.      

Investigation into the effect of size of local metallization of <Emphasis Type="Italic">N</Emphasis>-GaAs surface on the character of surface potential distribution determined by atomic-force microscopy

The potential of the GaAs surface with locally deposited thin layers of gold is studied by atomic-force microscopy (AFM) using the Kelvin probe method (KPM). The results obtained show that the measured potential in the probe – metal system corresponds, on the whole, to the contact potential difference (CPD) in this system.     

GaN缓冲层对直流反应磁控溅射AlN薄膜的影响(英文)

通过直流磁控反应溅射制备了氮化铝(AlN)薄膜,研究了沉积条件与氮化镓(GaN)缓冲层对薄膜质量的影响。利用X-射线衍射仪(XRD)和扫描电镜(SEM)表征了AlN薄膜的晶体结构和表面形貌。XRD研究结果表明,低工作压强、短靶距和适当的氮气偏压有利于(002)择优取向的AlN薄膜沉积。随着沉积时间的增加,沉积在50 nm厚的GaN缓冲层上的AlN薄膜的(002)面的衍射峰的半高宽急剧减小,而沉积在1μm厚的GaN薄膜上的AlN薄膜的(002)面的衍射峰的半高宽几乎不变。SEM测试结果表明:在沉积的初期,沉积在1μm厚的GaN薄膜上的AlN薄膜的(002)面的晶粒大小分布比沉积在50 nm厚的GaN缓冲层上的AlN薄膜的均匀,而随着沉积时间的增加,它们的晶粒大小分布几乎趋向一致。     

Effect of modifying a methyl siloxane-based dielectric by a polymer thin film for pentacene thin-film transistors

We report on the fabrication of pentacene thin-film transistors (TFTs) utilizing a spun methyl siloxane-based spin-on-glass (SOG) dielectric and show that these devices can give a similar electrical performance as achieved by using pentacene TFTs with a silicon dioxide (SiO₂) dielectric. To improve the electrical performance of pentacene TFTs with the SOG dielectric, we employed a hybrid dielectric of an SOG/cross-linked poly-4-vinylphenol (PVP) polymer. The PVP film was deposited onto the spun SOG dielectric prior to pentacene evaporation, resulting in an improvement of the saturation field effect mobility (μ_sat) from 0.01 cm²/(V s) to 0.76 cm²/(V s). The good surface morphology and the matching surface energy of the SOG dielectric that was modified with the polymer thin film allow the optimized growth of crystalline pentacene domains whose nuclei are embedded in an amorphous phase.     

Effects of flow ratios on surface morphology and structure of hydrogenated amorphous carbon films prepared by microwave plasma chemical vapor deposition

A series of hydrogenated amorphous carbon (a-C:H) films were deposited on silicon substrates by microwave plasma chemical vapor deposition technique with a mixture of hydrogen and acetylene. The effects of flow ratio of hydrogen to acetylene on surface morphology and structure of a-C:H films were investigated using surface-enhanced Raman spectroscopy and scanning probe microscope (SPM) in the tapping AFM mode. Raman data imply a transition from graphite-like phase to diamond-like bonding configurations when the flow ratio increases. AFM measurements show that the increase in hydrogen content, to some extent, can smoothen the surface morphology and decrease the RMS roughness. Excessive hydrogen is found to cause the formation of polymeric hydrocarbon clusters in the films and reduce deposition rate.     

高阻隔碳氢膜的制备及性能研究

利用射频等离子体化学气象沉积法（r.f.PECVD），在12μm厚的聚对苯二甲酸乙二醇酯 (PET)上制备了碳氢膜. 用原子力显微镜（AFM），x射线光电子能谱（XPS），激光拉曼光谱，傅里叶红外光谱等仪器，对碳氢膜的表面形貌和内部结构特性进行了较详细研究. 镀碳氢膜PET的阻隔性能在标准透水蒸气测试仪上进行检测. 实验结果证明：沉积工艺参数对碳氢膜的生长速率及结构性能有重要影响；在PET上沉积的是纳米碳氢膜，该膜主要由sp2和sp3杂化的碳氢化合物组成；当PET上碳氢膜厚度为900nm时，阻水蒸气性能可提高7倍. 关键词： 碳氢膜 射频等离子体化学气象沉积法 聚对苯二甲酸乙二醇酯 阻隔性能     

A Fluoropolymer Coating on Carbon Fibers Improves Their Adhesive Interaction with PTFE Matrix

Carbon fibers were treated in a HF glow discharge in tetrafluoroethylene and octafluorocyclobutane in order to improve their adhesion to poly(tetrafluoroethylene) matrix. As the result of the plasma treatment, a thin (20–140 nm) fluoropolymer coating was deposited onto the fiber surface. The structure of this coating was studied by means of IR spectroscopy, XPS, AFM and SEM techniques. The coating material appeared to be similar to PTFE in its chemical composition but distinguished by branched, partially crosslinked, amorphous structure and included unsaturated chemical bonds. The coating thickness of 70 nm was sufficient to effectively screen the field of molecular forces of the initial substrate, thus, decreasing the surface energy of the fibers and improving their compatibility with the PTFE matrix. The adhesive strength in the PTFE–carbon fiber systems, measured by means of the microbond test, more than doubled upon the plasma treatment (the local interfacial shear strength increased from 10.7 to 29.7 MPa, apparent IFSS from 4.3 to 7.8 MPa), and the interfacial frictional stress increased by 70%. The new composite material consisting of 20% short coated carbon fibers in the PTFE matrix showed better mechanical, thermal and tribological characteristics as compared with the composite reinforced with untreated fibers.     

On one supramolecular mechanism of the nonlinear viscoelasticity of oriented polymers

A phenomenological model of the viscoelasticity of highly oriented polymer systems is developed based on the results of studying the relaxation of such systems (mainly, fibers of polyethylene terephthalate, polyamide-6, polyvinyl alcohol, and other polymers) in the loaded state. The effect of an applied load on their relaxation spectra agrees qualitatively with the deformation behavior of crystal-like bandles that are present in amorphous intercrystalline layers of the fibrillar supramolecular structure.     

CVD TiC/alumina multilayer coatings grown on sapphire single crystals

Multilayers of TiC/α-Al₂O₃ consisting of three (1 μm thick) alumina layers separated by thin (∼10 nm) oxidized TiC layers have been deposited onto c-, a- and r-surfaces of single crystals of α-Al₂O₃ by chemical vapour deposition (CVD). The aim of this paper is to describe and compare the detailed microstructure of the different multilayer coatings by using transmission electron microscopy (TEM).The general microstructure of the alumina layers is very different when deposited onto different surfaces of α-Al₂O₃ single crystal substrates. On the c- and a-surfaces the alumina layers grow evenly resulting in growth of single crystal layers of TiC and alumina throughout the coating. However, when deposited on the r-surface the alumina layers generally grow unevenly. No pores are observed within the alumina layers, while a small number of pores are found at the interfaces below the TiC layers. The TiC and alumina layers grow epitaxially on the c- and a-surface substrates. On the r-surface, epitaxy is present only at some rare locations. The TiC layers were oxidized in situ for 2 min in CO₂/H₂ prior to the alumina layer deposition. For all three samples chemical analyses show that the whole TiC layer is oxidized. On the c- and a-surfaces the TiC layer was oxidized to an fcc TiCO phase. On the r-surface the oxidation stage resulted in a transformation of the initially deposited fcc TiC to a monoclinic TiCO phase, which appears to be a modified TiO structure with a high carbon content.