Wavelength dependencies in interferometric measurements of thin protein films

Summary The evaluation of the spectral modulation in reflectance measurements at thin dielectric films allows the characterisation of layers in the m-range. Diode array spectrometers make this technique a useful tool in sensor development. The variation of the optical pathlength in thin films due to change of refractive index or to change of physical thickness of a homogeneous layer has been applied to refractometry and detection of hydrocarbons by polymer swelling. More recently, the monitoring of solid-phase affinity reactions, like immunoassays has successfully been demonstrated. While the homogeneous layer concept is useful for data evaluation in the first two cases, it has its limitations for the treatment of adlayer formation as in the latter case. This is discussed with respect to results from affinity reactions carried out at optically different interference layers.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

AFM,ellipsometry, XPS and TEM on ultra-thin oxide/polymer nanocomposite layers in organic thin film transistors

Here we report on the fabrication and characterization of ultra-thin nanocomposite layers used as gate dielectric in low-voltage and high-performance flexible organic thin film transistors (oTFTs). Reactive sputtered zirconia layers were deposited with low thermal exposure of the substrate and the resulting porous oxide films with high leakage currents were spin-coated with an additional layer of poly-α-methylstyrene (PαMS). After this treatment a strong improvement of the oTFT performance could be observed; leakage currents could be eliminated almost completely. In ellipsometric studies a higher refractive index of the ZrO₂/PαMS layers compared to the “as sputtered” zirconia films could be detected without a significant enhancement of the film thickness. Atomic force microscopy (AFM) measurements of the surface topography clearly showed a surface smoothing after the PαMS coating. Further studies with X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) also indicated that the polymer definitely did not form an extra layer. The polymer chains rather (self-)assemble in the nano-scaled interspaces of the porous oxide film giving an oxide–polymer “nanocomposite” with a high oxide filling grade resulting in high dielectric constants larger than 15. The dielectric strength of more than 1 MV cm⁻¹ is in good accordance with the polymer-filled interspaces.     

Single-step fabrication of asymmetric dual-phase composite membranes for oxygen separation

Asymmetric dual-phase composite membranes for oxygen separation were conveniently fabricated by an acid leaching technique. A thin dense layer of Ce_0.85Sm_0.15O_1.925/Sm_0.6Sr_0.4FeO_3−δ was left by controlling the degree of acid leaching, and a porous substrate of Ce_0.85Sm_0.15O_1.925 with a fluorite structure was formed after dissolution of Sm_0.6Sr_0.4FeO_3−δ with a perovskite structure in HCl. Thus, a thin dense layer and a porous substrate can be fabricated in a single step in which traditional shrinkage mismatch and chemical reaction between thin dense layers and porous substrates can be avoided. The thickness of the dense layer can be controlled by varying the acid leaching time. Hence, dual-phase composite membranes with high oxygen flux can be obtained.     

Study on optical interference effect of graphene oxide films on SiO2 and Si3N4 dielectric films

The optical interference effect has enabled the visualization of thin layers, even monolayers, of graphene by simple optical microscopy. In this study, we have controlled the optical interference effect by changing the thickness and types of dielectric films, i.e. SiO₂ and Si₃N₄. By investigating differences in RGB parameters between the graphene oxide layer and the dielectric layer, conditions for the highest visibility of the graphene oxide layer were determined. We also studied colors as a function of graphene oxide layer thickness and dielectric layer thickness. These color patterns can be effectively presented as two-dimensional color charts. When comparing SiO₂ and Si₃N₄ as dielectric layers, each layer was found to exhibit different interference fringe patterns, which is due to a mismatch of optical properties between the material layer and dielectric layer. The effects of optical properties (n, k) of the material layer on interference colors were also investigated.     

Recent advances in the development of graphene-based surface plasmon resonance (SPR) interfaces

Surface plasmon resonance (SPR) is a powerful technique for measurement of biomolecular interactions in real-time in a label-free environment. One of the most common techniques for plasmon excitation is the Kretschmann configuration, and numerous studies of ligand–analyte interactions have been performed on surfaces functionalized with a variety of biomolecules, for example DNA, RNA, glycans, proteins, and peptides. A significant limitation of SPR is that the substrate must be a thin metal film. Post-coating of the metal thin film with a thin dielectric top layer has been reported to enhance the performance of the SPR sensor, but is highly dependent on the thickness of the upper layer and its dielectric constant. Graphene is a single-atom thin planar sheet of sp2 carbon atoms perfectly arranged in a honeycomb lattice. Graphene and graphene oxide are good supports for biomolecules because of their large surface area and rich π conjugation structure, making them suitable dielectric top layers for SPR sensing. In this paper, we review some of the key issues in the development of graphene-based SPR chips. The actual challenges of using these interfaces for studying biomolecular interactions will be discussed and the first examples of the use of graphene-on-metal SPR interfaces for biological sensing will be presented.     

Structural and optical properties of TiO2 thin films prepared by spin coating

Transparent semiconducting thin films of titanium oxide (TiO₂) were deposited on glass substrates by the sol–gel method and spin-coating technique. The physical properties of the prepared films were studied as a function of the number of spun-cast layers. The microstructure and surface morphology of the TiO₂ films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM), with respect to the film thickness. The XRD analysis reveals that the films are polycrystalline with an anatase crystal structure and a preferred grain orientation in the (101) direction. The morphological properties were investigated by AFM, which shows a porous morphology structure for the films. The optical properties of the films were characterized by UV–Visible spectrophotometry, which shows that the films are highly transparent in the visible region and their transparency is slightly influenced by the film thickness, with an average value above 80 %. The dependence of the refractive index (n), extinction coefficient (k), and absorption coefficient (α) of the films on the wavelength was investigated. A shift in the optical band gap energy of the films from 3.75 to 3.54 eV, as a function of the film thickness, has been observed.     

Ellipsometry porosimetry (EP): thin film porosimetry by coupling an adsorption setting with an optical measurement, highlights on additional adsorption results

Ellipsometry porosimetry (EP) is an emerging technique that is well adapted to porous thin films analysis; it is non contact and non destructive. EP tools developed at SOPRA, allows us to obtain adsorption isotherms with many different adsorptives at an ambient temperature. EP leads to the same results as classical adsorption experiments (e.g. porosity, pore size distribution …), but it also has some particular features leading to new information. For instance, our optical setup (Spectroscopic Ellipsometry) allows us to determine the variation of the thickness of the samples during the adsorption experiment. It is also very sensitive to interfaces; it is thus possible to detect a porosity gradient or to study a bi-layer sample and plot the two corresponding adsorption isotherms at the same time (Bourgeois et al. 2004). For porous thin films with a non porous barrier layer deposited on top, it is also possible to study the lateral diffusion phenomenon in the film (see figure below). In this paper, we will demonstrate a part of the different features of EP for adsorption on porous thin films.     

A molecular beacon approach to measuring the DNA permeability of thin films

A new method for determining the permeability of thin films has been developed. A molecular beacon immobilized inside a porous silica particle that is subsequently encapsulated within a thin film can be used to determine the size of DNA that can permeate through the film. Using this technique, it has been determined that over 3 h, molecules larger than 4.7 nm do not permeate 15-nm thick polyelectrolyte multilayers and after 75 h molecules larger than 6 nm were excluded. This technique has applications for determining the permeability of films used for controlled drug and gene delivery.     

Orientation dependence of the dielectric and piezoelectric properties for the Ba0.98Ca0.02Ti0.96Sn0.04O3 thin films

Lead free Ba_0.98Ca_0.02Ti_0.96Sn_0.04O₃ (BCST) thin films with (110), (111) and (001) orientations were processed via chemical solution deposition, and effects of orientation on the dielectric and piezoelectric properties were investigated in some aspects. The (110) orientated BCST thin films exhibit highest Curie temperature (T _c of 85 °C) and lowest dielectric loss (tan δ of 0.02). While, the (111) orientated BCST thin films exhibit highest dielectric tunability (74 %) and largest piezoelectric coefficient (d ₃₃ of 78 pm/V), which indicate that it is a promising lead-free replacement for lead-based applications. The anisotropic dielectric and piezoelectric properties in the three kinds of oriented BCST films has been attributed to the difference of structure, in-plane stress and polarization rotation in orientation engineered BCST films. This work clearly reveals the dielectric and piezoelectric properties of BCST films exhibit a strong sensitivity to orientation.     

Fluorescence labeling of gelatin and methylcellulose: monitoring their penetration behavior into paper

For the conservation of artworks on paper, powdery paint layers on the paper matrix are stabilized with dilute solutions of adhesives (0.25–1 %), commonly gelatin or methylcellulose, which are applied as aerosols. This technique allows non-contact application. The distribution of the adhesives must be carefully controlled: they have to be delivered to unstable paint layers in the right quantity to avoid visual alterations of the artwork during the stabilization treatment. To visualize the distribution of aerosol-misted adhesives in porous substrates, gelatin and methylcellulose were labeled with fluorescent dyes, purified from excess label, and applied on sample specimen featuring powdery pigment layers on handmade rag paper. As blank comparisons, sample papers without pigment layers were included to verify whether aerosol-misted adhesives are a suitable method to stabilize fragile papers. Penetration of the adhesive-label-conjugates was observed at thin sections of the samples by fluorescence microscopy. The fluorescence labeling of gelatin with Texas Red? allowed an excellent visualization of aerosol-misted adhesive (0.5–1 %) in all sample types. Methylcellulose (Methocel? A4C) labeled with Texas Red? C2-dichlorotriazine enabled fluorescence tracing if applied in 0.5 % solutions by immersion. Aerosol application permitted local adhesive application, making it a suitable technique for stabilizing fragile papers. If applied to samples with low porosity, aerosol-misted gelatin was mainly deposited at the surface, whereas in porous filter paper, penetration dominated over surface deposition. Intermediate drying between repetitive applications apparently limited the penetration of aerosol-misted gelatin.     

Preparation of electrolyte membranes for micro tubular solid oxide fuel cells

Yttria-stabilized zirconia (YSZ) micro tubular electrolyte membranes for solid oxide fuel cells (SOFCs) were prepared via the combined wet phase inversion and sintering technique. The as-derived YSZ mi- cro tubes consist of a thin dense skin layer and a thick porous layer that can serve as the electrode of fuel cells. The dense and the porous electrolyte layers have the thickness of 3-5 μm and 70-90 μm, respectively, while the inner surface porosity of the porous layer is higher than 28.1%. The two layers are perfectly integrated together to preclude the crack or flake of electrolyte film from the electrode. The presented method possesses distinct advantages such as technological simplicity, low cost and high reliability, and thus provides a new route for the preparation of micro tubular SOFCs.     

基于高度非对称结构电解质中空纤维的微管式固体氧化物燃料电池制备

提出了一种简单而方便的微管式固体氧化物燃料电池(MT-SOFCs)的制备新方法.首先应用改进相转化-烧结技术制备由致密电解质表皮薄层和多孔支撑层构成的高度非对称结构电解质中空纤维膜(微管),在电解质中空纤维膜的多孔支撑层内通过化学镀法沉积Ni催化剂作为电池阳极,而致密电解质表皮层直接作为电解质膜,在电解质微管外表面用浆料涂层法制备电池的多孔阴极,烧结后即得到完整的MT-SOFC.应用该方法制备了Ni-YSZ|YSZ|LSCF微管式电池,该电池以H2/空气作原料气,在800℃时最大输出功率达到159.6mWcm-2.     

Preparation of microtubular solid oxide fuel cells based on highly asymmetric structured electrolyte hollow fibers

A simple and cost-effective method has been developed for the fabrication of microtubular solid oxide fuel cells (MT-SOFCs). Highly asymmetric electrolyte hollow fibers composed of a thin dense skin layer and a thick porous substrate are first prepared by a modified phase inversion/sintering technique. The porous substrate is then formed into the anode by deposition of a Ni catalyst via an electroless plating method inside the pores while the thin dense skin layer serves directly as the electrolyte film of ...     

表面配位金属-有机框架薄膜HKUST-1在光电应用中的研究进展北大核心CSCD

金属-有机框架(MOFs)作为一种无机-有机杂化材料,由于其结构的多样性和独特的功能而在众多领域有着潜在的应用价值。尤其是液相外延层层组装的MOFs薄膜(称为表面配位MOFs薄膜,SURMOFs)因其具有可控的厚度、优选的生长取向以及均匀的表面等优点备受关注。本文总结了液相外延(LPE)层层组装MOFs薄膜的技术方法,如层层浸渍法、层层泵式法、层层喷雾法、层层旋涂法等组装方法,并介绍了经典的SURMOF HKUST-1的层层组装策略以及其在光致发光、光致变色、光催化以及电催化方面的相关应用。HKUST-1是经典的SURMOF材料之一,在光电领域具有广泛的应用,SURMOF HKUST-1具有以下独特的性能:可以作为发光载体实现良好的光学性能;具有独特的Cu催化活性位点的优势,有效地降解水中的污染物;因其具有介电特性而在电子器件方面有着潜在的应用。虽然HKUST-1在许多方面均具有独特的性能,但也面临着一些挑战:需要将薄膜的合成步骤简单化;薄膜结构和电催化行为间的机理也需要进一步的研究;降低HKUST-1的内阻的方法也需要进行改进。SURMOFs在大规模工业应用和扩展到其它未探索的领域还任重道远。     

Growth of silicon thin film by LPE on porous silicon bilayers

The fabrication of solar cells based on the transfer of a thin silicon film on a foreign substrate is an attractive way to realise cheap and efficient photovoltaic devices. The aim of this work is to realise a thin mono-crystalline silicon film on a double porous silicon layer in order to detach and transfer it on mullite. The first step is the fabrication of a double porous silicon layer by electrochemical anodisation using two different current densities. The low current leads to a low porosity layer and during annealing, the recrystallisation of this layer allows epitaxial growth. The second current leads to a high porosity which permits the transfer on to a low cost substrate. Liquid Phase Epitaxy (LPE) performed with indium (or In+Ga) in the temperature range of 950–1050°C leads to almost homogeneous layers. Growth rate is about 0.35 μm min⁻¹. Crystallinity of the grown epilayer is similar on porous silicon and on single crystal silicon. In this paper, we focus on the realisation of porous silicon sacrificial layer and subsequent LPE growth. This revised version was published online in July 2006 with corrections to the Cover Date.     

Positronium chemistry in porous materials

Porous materials have fascinated positron and positronium chemists for over decades. In the early 1970s it was already known that ortho-positronium (o-Ps) exhibits characteristic long lifetimes in silica gels, porous glass and zeolites. Since then, our understanding of Ps formation, diffusion and annihilation has been drastically deepened. Ps is now well recognized as a powerful porosimetric and chemical probe to study the average pore size, pore size distribution, pore connectivity and surface properties of various porous materials including thin films. In this paper, developments of Ps chemistry in porous materials undertaken in the past some 40 yr are surveyed and problems to be addressed in future are briefly discussed.     

Preparation of Doped Ceria Electrolyte Films for SOFCs by Spray Coating Method

Spray coating method is a cost-effective technique suitable for the preparation of uniform and large-area thin films. This article presents findings on the preparation of dense electrolyte thin films by spray coating method. Dense, crack-free Gd-doped CeO₂ (GDC) thin films with a thickness of approximately 2 µm were successfully prepared on porous NiO-GDC substrates. The influence of the dispersion of GDC nanopowders in susupension on the microstructure of the thin films was investigated. Results show that agglomeration of GDC nanopowders in suspension resulted in a porous microstructure and a densely packed microstructure was obtained for the film prepared from a well-dispersed suspension.     

Characterization of multilayer nanofiltration membranes using positron annihilation spectroscopy

Positron annihilation spectroscopy (PAS) coupled with a slow positron beam was used to characterize in situ the layer structure and depth profile of the cavity size in thin film composite (TFC) polyamide nanofiltration (NF) membranes prepared by the interfacial polymerization method. Two techniques, using PAS coupled with a slow positron beam of Doppler broadening energy spectra (DBES) and positron annihilation lifetime spectroscopy (PALS) designed to reveal the layer structure and the cavity sizes contained in a multilayer thin film composite NF membrane, were assessed. To the best knowledge of the authors, a characterization of the depth profile of cavities in NF membranes using PAS coupled with a slow positron beam has never been reported. The membranes selected have a composite structure containing three layers: a selective polyamide layer, a transition layer, and a porous support prepared by the phase inversion technique. Furthermore, the cavity size distribution in the selective top layer plays an important role in determining the performance of the NF membranes.     

Tunable dielectric thin films by aqueous, inorganic solution-based processing

Sub-micron, nanolaminated, dielectric thin films comprised of amorphous aluminum oxide phosphate (AlPO) and hafnium oxide sulfate (HafSOx) layers were fabricated in open-air conditions from aqueous inorganic precursors by spin coating with minimal thermal processing. These nanolaminated thin film insulators display an averaging effect of effective dielectric permittivity in devices with controlled AlPO:HafSOx thickness ratios, enabling tunable dielectric properties. X-ray reflectivity measurements were used to characterize film thickness, smoothness, and uniformity. Scanning electron microscopy was used to analyze final nanolaminated devices. Electrical characterization of metal-insulator-insulator-metal capacitors revealed tunable relative dielectric constants ranging from approximately 5–10 with loss tangents less than 2% at 10 kHz in devices with approximately 300 nm total dielectric thickness. The results suggest a simple, inexpensive processing approach for fabricating devices that require insulating layers with specific dielectric properties.     

Effect of biphase on dielectric properties of Bi-doped lead strontium titanate thin films

Pb_0.4Sr_0.6TiO₃ (PST) thin films doped with various concentration of Bi were prepared by a sol-gel method. The phase status, surface morphology and dielectric properties of these thin films were measured by X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance analyzer, respectively. Results showed that the thin films with the maximum dielectric constant and minimum dielectric loss were obtained for x=0.15. For x<0.15, only pure PST perovskite phase were in the thin films. For 0.2<x<0.4, the PST/Bi₂Ti₂O₇ biphase were obtained. The thin films with pure Bi₂Ti₂O₇ pyrochlore phase were obtained for x=0.67. The biphase thin films had high tunability and high figure of merit (FOM). The FOM of PST/Bi₂Ti₂O₇ biphase thin film was about 6 times higher than that thin films formed with pure perovskite phase or pure pyrochlore phase.