Self-organization and morphological characteristics of selenium-containing nanostructures based on rigid-chain polymers

Macroinitiators containing β-diketonate fragments were prepared by copolymerization of styrene with cobalt(II) 5-Formation and morphological characteristics of selenium-containing nanostructures formed by reduction of selenious acid with ascorbic acid in the presence of ionic or nonionic polymeric stabilizer in aqueous solutions were studied by methods of nonlinear optics and flow birefringence at widely varied selenium to polymer weight ratio in solution ν. The molecular weights, root-mean-square and hydrodynamic sizes, and mean density of the nanostructures were calculated, and the trends in variation of these quantities were compared.     

Effect of potassium permanganate on morphological,structural and electro-optical properties of graphene oxide thin films

This work investigated the effect of Potassium Permanganate (KMnO₄) on graphene oxide (GO) properties, especially on electrical properties. The GO thin films were deposited on a glass substrate using drop casting technique and were analysed by using various type of spectroscopy (e.g. Scanning Electron Microscopy (SEM), Ultra- Violet Visible (UV–VIS), Fourier Transform Infrared (FTIR), X-Ray Diffraction (XRD), optical band gap, Raman Spectroscopy). Furthermore, the electrical experiments were carried out by using current–voltage (I-V) characteristic. The GO thin film with 4.5 g of KMnO₄ resulted in higher conductivity which is 3.11 × 10^?4 S/cm while GO with 2.5 g and 3.5 g of KMnO₄ achieve 2.47 × 10^?9 S/cm and 1.07 × 10^?7 S/cm, respectively. This further affects the morphological (SEM), optical (band gap, UV–Vis, FTIR, and Raman), and crystalline structural (XRD) properties of the GO thin films. The morphological, elemental, optical, and structural data confirmed that the properties of GO is affected by different amount of KMnO₄ oxidizing agent, which revealed that GO can potentially be implemented for electrical and electronic devices.     

Recent advances in ZnO nanostructures and thin films for biosensor applications: Review

Biosensors have shown great potential for health care and environmental monitoring. The performance of biosensors depends on their components, among which the matrix material, i.e., the layer between the recognition layer of biomolecule and transducer, plays a crucial role in defining the stability, sensitivity and shelf-life of a biosensor. Recently, zinc oxide (ZnO) nanostructures and thin films have attracted much interest as materials for biosensors due to their biocompatibility, chemical stability, high isoelectric point, electrochemical activity, high electron mobility, ease of synthesis by diverse methods and high surface-to-volume ratio. ZnO nanostructures have shown the binding of biomolecules in desired orientations with improved conformation and high biological activity, resulting in enhanced sensing characteristics. Furthermore, compatibility with complementary metal oxide semiconductor technology for constructing integrated circuits makes ZnO nanostructures suitable candidate for future small integrated biosensor devices. This review highlights recent advances in various approaches towards synthesis of ZnO nanostructures and thin films and their applications in biosensor technology.     

Control of wettability of molecularly thin liquid films by nanostructures

The patterning of liquid thin films on solid surfaces is very important in various fields of science and engineering related to surfaces and interfaces. A method of nanometer-scale patterning of a molecularly thin liquid film on a silicon substrate using the lyophobicity of the oxide nanostructures has recently been reported (Fukuzawa, K.; Deguchi, T.; Kawamura, J.; Mitsuya, Y.; Muramatsu, T.; Zhang, H. Appl. Phys. Lett. 2005, 87, 203108). However, the origin of the lyophobicity of the nanostructure with a height of around 1 nm, which was fabricated by probe oxidation, has not yet been clarified. In the present study, the change in thickness of the liquid film on mesa-shaped nanostructures and the wettability for the various combinations of the thickness of the liquid films and the height of ridge-shaped nanostructures were investigated. These revealed that lyophobicity is caused by a lowering of the intermolecular interaction between the liquid and silicon surfaces by the nanostructure and enables the patterning of a liquid film along it. The tendency of the wettability for a given liquid film and nanostructure size can be predicted by estimating the contributions of the intermolecular interaction and capillary pressure. In this method, the height of the nanostructure can control the wettability. These results can provide a novel method of nanoscale patterning of liquid thin films, which will be very useful in creating new functional surfaces.     

Surface enhanced second harmonic generation from macrocycle, catenane, and rotaxane thin films: experiments and theory

Surface enhanced second harmonic generation (SE SHG) experiments on molecular structures, macrocycles, catenanes, and rotaxanes, deposited as monolayers and multilayers by vacuum sublimation on silver, are reported. The measurements show that the molecules form ordered thin films, where the highest degree of order is observed in the case of macrocycle monolayers and the lowest in the case of rotaxane multilayers. The second harmonic generation activity is interpreted in terms of electric field induced second harmonic (EFISH) generation where the electric field is created by the substrate silver atoms. The measured second order nonlinear optical susceptibility for a rotaxane thin film is compared with that obtained by considering only EFISH contribution to SHG intensity. The electric field on the surface of a silver layer is calculated by using the Delphi4 program for structures obtained with TINKER molecular mechanics/dynamics simulations. An excellent agreement is observed between the calculated and the measured SHG susceptibilities.     

Self-organization of disc-like molecules: chemical aspects

The hierarchical self-assembly of disc-shaped molecules leads to the formation of discotic liquid crystals. These materials are of fundamental importance not only as models for the study of energy and charge migration in self-organized systems but also as functional materials for device applications such as, one-dimensional conductors, photoconductors, light emitting diodes, photovoltaic solar cells, field-effect transistors and gas sensors. The negative birefringence films formed by polymerized nematic discotic liquid crystals have been commercialized as compensation foils to enlarge the viewing angle of commonly used twisted nematic liquid crystal displays. To date the number of discotic liquid crystals derived from more than 50 different cores comes to about 3000. This critical review describes, after an in-depth introduction, recent advances in basic design principles and synthetic approaches towards the preparation of most frequently encountered discotic liquid crystals.     

Effect of substrates on the structural,morphological, and optical properties of sprayed CdO thin films using nebulizer

CdO thin films were deposited on glass, quartz, FTO, silicon wafers of p-type and n-type at 200?°C of substrate temperature employing spray pyrolysis technique using nebulizer. As deposited cadmium oxide thin films were analyzed to find crystallite size, morphology of the substrate, elemental composition and band gap using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDAX) and UV–Vis spectrophotometer. Nature of the thin film was found to be polycrystalline with face centered cubic structure with (111) preferential orientation and evaluated structural parameters show significant effect of used substrates. Spherical sized grains were observed on the surface of the thin films using SEM. The EDAX analysis confirmed that cadmium and oxygen were present in the sample. Direct allowed transition with band gap values lying in the range 2.34–2.44?eV for all the films deposited on various substrates. Among, these thin film coated on FTO substrate was found to have high crystallinity with a narrow band gap, which may be more suitable for opto-electronic applications.

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The absorption co-efficient spectra and inset of transmittance spectra with wavelength of CdO thin films at different substrates (Glass, Quartz and FTO).

     

Self-organization of polystyrenes into ordered microstructured films and their replication by soft lithography

We report on the formation of ordered arrays of micrometric holes on the surface of polystyrene (PS) films cast from volatile solvents in the presence of humidity at different temperatures. The formation mechanism is investigated for PS having different molecular weights, polydispersities, and carboxylic terminations. Among the chosen materials, a highly regular honeycomb microstructured morphology is obtained on the surface of films prepared with dicarboxy-terminated PS with = 100,000. Experiments and observations on film formation indicate that polar groups are playing a fundamental role in this process. Tuning the surface tension by means of polar terminations allows the film morphology to be modified and in particular the preparation of two- or three-dimensional microstructured films. Finally, we show how these structures can be replicated by soft lithography and then used in the fields of photonic crystals and organic electronics.     

Au nanoparticle monolayers covered with sol-gel oxide thin films: optical and morphological study

In this work, we provide a detailed study of the influence of thermal annealing on submonolayer Au nanoparticle deposited on functionalized surfaces as standalone films and those that are coated with sol-gel NiO and TiO(2) thin films. The systems are characterized through the use of UV-vis absorption, X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and spectroscopic ellipsometry. The surface plasmon resonance peak of the Au nanoparticles was found to red-shift and increase in intensity with increasing surface coverage, an observation that is directly correlated to the complex refractive index properties of Au nanoparticle layers. The standalone Au nanoparticles sinter at 200 °C, and a relationship between the optical properties and the annealing temperature is presented. When overcoated with sol-gel metal oxide films (NiO, TiO(2)), the optical properties of the Au nanoparticles are strongly affected by the metal oxide, resulting in an intense red shift and broadening of the plasmon band; moreover, the temperature-driven sintering is strongly limited by the metal oxide layer. Optical sensing tests for ethanol vapor are presented as one possible application, showing reversible sensing dynamics and confirming the effect of Au nanoparticles in increasing the sensitivity and in providing a wavelength dependent response, thus confirming the potential use of such materials as optical probes.     

Challenges in the structural characterization of thin organic films

This review addresses the special problems associated with the micro-structural characterization of thin and ultrathin organic films, primarily by optical spectroscopies. Films which are deposited by Langmuir-Blodgett techniques, self-assembly chemistry, and bulk film deposition techniques are considered. The use of enhanced optical excitation using surface phasma resonances and integrated optical structures is discussed extensively, as is the use of ellipsometry. Discussion of the spectroscopies used is broken into a section on electronic spectroscopies and an extensive discussion of vibrational spectroscopies. Vibrational information may be obtained with photons (absorption or scattering) or electrons (loss spectra), and the types of experimental systems amenable to each, along with the advantages and disadvantages of each are explored.     

Optical and morphological characterization of bispyrazole thin films for gas sensing applications

The optical gas recognition capabilities of thin film layer of 4-[bis[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-amino]phenol deposed on quartz substrates were studied. The dynamic gas responses to the following analytes have been investigated as air pollutants (SO₂, NO₂, CO, CH₄ and NH₃). The spin-coated bispyrazole layer appears to have reversible response towards SO₂ and a very low and irreversible response to NO₂. The selectivity of the thin film based on bispyrazole layer with respect to other analytes was also examined and the present data show that the thin sensing layer in the presence of CO, CH₄ and NH₃ in low concentration does not influence its optical properties.     

Crystallographic and morphological characterization of thin pentacene films on polycrystalline copper surfaces

The degree of crystallinity, the structure and orientation of crystallites, and the morphology of thin pentacene films grown by vapor deposition in an ultrahigh vacuum environment on polycrystalline copper substrates have been investigated by x-ray diffraction and tapping-mode scanning force microscopy (TM-SFM). Depending on the substrate temperature during deposition, very different results are obtained: While at 77 K a long-range order is missing, the films become crystalline at elevated temperatures. From a high-resolution x-ray-diffraction profile analysis, the volume-weighted size of the crystallites perpendicular to the film surface could be determined. This size of the crystallites increases strongly upon changing temperature between room temperature and 333 K, at which point the size of individual crystallites typically exceeds 100 nm. In this temperature region, three different polymorphs are identified. The vast majority of crystallites have a fiber texture with the (001) net planes parallel to the substrate. In this geometry, the molecules are oriented standing up on the substrate (end-on arrangement). This alignment is remarkably different from that on single-crystalline metal surfaces, indicating that the growth is not epitaxial. Additionally, TM-SFM images show needlelike structures which suggest the presence of at least one additional orientation of crystallites (flat-on or edge-on). These results indicate that properties of thin crystalline pentacene films prepared on technologically relevant polycrystalline metal substrates for fast electronic applications may be compromised by the simultaneous presence of different local molecular aggregation states at all temperatures.     

Effects of lithium insertion and deinsertion into V2O5 thin films: Optical,structural, and absorption properties

The lithiated/delithiated vanadium pentoxide films deposited by sol‐gel spin coating on indium tin oxide–coated glass substrates were analyzed by sputter‐induced photon spectroscopy, X‐ray diffraction, and optical absorption techniques. First, it is shown that the crystalline structure of V₂O₅ after intercalation remains practically unchanged. Particularly, in the optical spectra during 5 keV Kr⁺ ion bombardment of clean, intercalated, and deintercalated V₂O₅ films, a series of sharp lines and unexpected continuum radiation were observed and well explained. It is also demonstrated that the intercalation and deintercalation of lithium have strong influences on various characteristics of pentoxide vanadium. The interpretations of the obtained results in the 3 experiments—X‐ray diffraction, sputter‐induced photon spectroscopy, and optical absorption techniques—are coherent and complement each other.     

Lithium intercalation into amorphous-silicon thin films: An electrochemical-impedance study

Lithium intercalation into 0.25-μm-thick films of amorphous silicon is studied using the electrochemical-impedance technique. An equivalent circuit, proposed for such electrodes, comprises the electrolyte resistance and three units connected in series, each unit being a parallel combination of a resistance and a constant-phase element. The units relate to the charge transfer processes at the silicon/electrolyte interface, charge transfer though the passive film on the silicon, and the lithium diffusion into the silicon bulk. During potential cycling, changes occur largely in the unit related to the passive film. The lithium diffusion coefficient in the amorphous silicon is estimated as ～ 10^?13 cm² s^?1.     

Solid state structural aspects of electrochemically prepared poly (p -phenylene) thin films – crystalline order and spherulite morphology

The electrochemical polymerization of benzene via the microemulsion approach yields highly crystalline and anisotropic “spherulitic” polyparaphenylene (PPP) thin films. The crystalline order and the origin of spherulite morphology are discussed. Received: 29 July 1997 / Accepted: 27 October 1997     

Preparation of long-range ordered nanostructures in semicrystalline diblock copolymer thin films using micromolding

Long-range ordered nanostructures are prepared in the poly(styrene)-block-poly(ε-caprolactone) diblock copolymer thin films using micromolding. We evaluated the change in crystallinity based on grazing-incidence X-ray diffraction and proved that the crystallinity increased with the decrease of the mold size. This means that ordered nanostructures with atomic length scale order can be adjusted by tuning the mesoscale confinement. The inherent mechanism was the cooperation of geometric confinement, microphase structure and surface-induced ordering of PS-b-PCL in the melt, which paved the way for the subsequent crystal growth. These findings establish a route to promote the cost-effective nanofabrication by combining the mature microfabrication technique with the emerging directed self-assembly of block copolymers.     

Controlling the size of nanostructures in thin films via blending of block copolymers and homopolymers

The effects of molecular weight and concentration of poly (methyl methacrylate) (PMMA) homopolymer or symmetric short polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) diblock copolymer on the size of the nanostructures of its blends with symmetric long PS-b-PMMA diblock copolymer have been investigated by atomic force microscopy. By careful controlling of the film thickness, solvent selectivity, and annealing time, PMMA cylindrical microdomains oriented normal to the film surface were obtained in all thin films. With the addition of both low- and high-molecular-weight PMMA homopolymers, the cylindrical domain sizes increased although it was less obvious for the lower molecular weight homopolymer. In contrast to the homopolymer, adding the short chain diblock copolymer resulted in a decrease in the cylindrical domain size, which was ascribed to the reduction of the interfacial tension and increase in the stretching energy.     

Systematic study on structural phase behavior of CdSe thin films

Cadmium selenide (CdSe) thin films were chemically deposited at room temperature, from aqueous ammoniacal solution using Cd(CH(3)COO)(2) as Cd2+ and Na(2)SeSO(3) as Se2- ion sources. The as-deposited films were uniform, well adherent to the glass substrate, specularly reflective, and red-orange in color. The as-deposited CdSe layers grew with nanocrystalline sphalerite cubic structure along with the amorphous phase present in it, with optical band gap E(g) = 2.3 eV. The films were annealed in air atmosphere for 4 h at different temperatures and characterized for compositional, structural, morphological, and optical properties. XRD and SEM studies clearly revealed the systematic phase transformation of CdSe films from metastable nanocrystalline cubic (zinc blende type) to a mixture of cubic and hexagonal (wurtzite type), and finally into stable hexagonal through different intermediate phases with an improvement in the crystal quality. The films showed a red shift in their optical spectra after annealing.