Analysis of the structure of block copolymer films by atomic force microscopy

The structure of thin films of the polysterene-polymethylacrylate-polysterene triblock copolymer was studied. Universal algorithms to analyze atomic-force-microscopy images of thin block-copolymer films were developed.     

Fluorescence enhancement of the conjugated polymer films based on well-ordered Au nanoparticle arrays

In this paper, well-ordered Au nanoparticle arrays on silicon substrates were employed as efficient metal-enhanced fluorescence (MEF) substrates for investigating the fluorescence properties of the conjugated polymer poly(3-hexylthiophene) (P3HT). The ordered Au nanoparticle arrays were fabricated by block copolymer self-assembly technology, and the particle sizes were controlled by adjusting the molar ratios of HAuCl₄ precursor to vinyl pyridine units. The approach is economical and suitable to fabricate large-area MEF substrates. The results about fluorescence properties of P3HT showed that the fluorescence intensities of the P3HT films were improved on ordered Au nanoparticle arrays compared to those on bare silicon substrate and were significantly enhanced with the Au nanoparticle sizes increasing. The mechanism is based on localized surface plasmon resonances, coupling and propagating surface plasmons, and the emission enhancement mainly resulted from the increase of the excitation rate. This work provides a new way to prepare efficient MEF substrates for high-performance fluorescence-based devices.     

Diblock and triblock copolymer thin films on a substrate with controlled selectivity

Using self-consistent field theory (SCFT), morphology development in symmetric linear ABC triblock copolymer films on neutral and selective substrates has been studied, and it is compared with the triblock copolymer morphologies in bulk. In particular, the effects of the substrate preferable to B (interior) block on nanopattern formation of the copolymer films are of our central interest. Here, we report various nanopatterns with tunable square morphologies. The domain patterns are much more diverse than those parallel to the substrate with substrate selectivity for end-block or those vertical to the substrate without substrate selectivity. Furthermore, in order to figure out an economical and efficient way to fabricate useful passive pattern transfer layers, which have potential applications in microelectronic processes and ultrahigh density storage media, we propose a two-step strategy and scrutinize the conditions for generating square symmetries using cylinder-forming or lamella-forming AB diblock copolymers deposited on substrates created from ABC triblock copolymer films. It is found that a thinner film with weak incompatibility can produce square patterns.     

Scaling of the coercive field in ferroelectrics at the nanoscale

The scaling of the coercive field in ferroelectric films at the nanoscale is investigated experimentally. The scaling in the films of copolymer vinylidene fluoride and BaTiO₃ with thickness equal by the order of value to the critical domain nucleus size 1–10 nm reveals deviation from the well-known Kay-Dunn law. At this thickness region coercive field does not depend on thickness and coincides with Landau-Ginzburg-Devonshire value.     

Phase transitions and low-frequency dielectric dispersion in ferroelectric Langmuir-Blodgett films of the copolymer vinylidene fluoride with trifluoroethylene

The dielectric properties of multilayer ferroelectric Langmuir-Blodgett films based on the copolymer vinylidene fluoride with trifluoroethylene with 70/30 composition are investigated. Good agreement with theoretical models on the basis of the phenomenological Landau-Ginzburg approach is demonstrated for the first time for ultrathin films. Expressions describing the temperature variation of the permittivity in the temperature range of hysteresis and giving quantitative agreement with experimental data are obtained. It is shown that the Langmuir-Blodgett films are conducting. This conductivity does not depend on the frequency of the field. The results are explained by the fact that the motion of charge in the films is not bounded by domain walls. The jumps observed in the frequency dispersion at volume and low-temperature (surface) phase transitions are explained by a sharp increase in the relaxation times at the transition into the ferroelectric state.     

Deposition of hexagonal boron nitride thin films on silver nanoparticle substrates and surface enhanced infrared absorption

Silver nanoparticle thin films with different average particle diameters are grown on silicon substrates. Boron nitride thin films are then deposited on the silver nanoparticle interlayers by radio frequency （RF） magnetron sputtering. The boron nitride thin films are characterized by Fourier transform infrared spectra. The average particle diameters of silver nanoparticle thin films are 126.6, 78.4, and 178.8 nm. The results show that the sizes of the silver nanoparticles have effects on the intensities of infrared spectra of boron nitride thin films. An enhanced infrared absorption is detected for boron nitride thin film grown on silver nanoparticle thin film. This result is helpful to study the growth mechanism of boron nitride thin film.     

Nanoscopic surface patterns of diblock copolymer thin films

The surface topography of thin diblock copolymer films is studied by atomic force microscopy (AFM). With AFM an island-to-ribbon transition is observed for symmetric polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP) on mica with increasing solution concentration. Our study also demonstrates how the formation of the pattern strongly depends on the copolymer composition based on the volume fraction. The substrate and solvent used both have great effects on the morphology of the thin films. Only by using highly polar substrate (mica), can we gain regular pattern. The reason why the regular islands cannot be obtained with symmetric PS-b-P4VP on graphite is also explained. On mica using nonselective and selective solvents, a rather regular pattern can be obtained. The difference is only in the solution concentration for forming regular patterns.     

Self-assembled silver nanoparticle films at an air-liquid interface and their applications in SERS and electrochemistry

In this paper, we present a novel technique to prepare silver nanoparticle films by controlling the self-assembly of nanoparticles at an air-liquid interface. In an ethanol-water phase, silver nanoparticles were prepared by reduction of AgNO₃ aqueous solution with NaBH₄ in the presence of cinnamic acid. It was found that the silver nanoparticles in this process could be trapped at the air-liquid interface to form 2-dimensional nanoparticle films. The morphology of nanoparticle films could be controlled by systematic variation of the experimental parameters. It is worth noting that the nanoparticle films could serve as the active substrates for surface-enhanced Raman scattering (SERS). 4-Aminothiophenol (4-ATP) molecule was used as a test probe to investigate the SERS sensitivity of different nanoparticle films. The results indicated that the nanoparticle films showed excellent Raman enhancement effect. Furthermore, the nanoparticle films prepared by our strategy were found to be efficient electrocatalysts for anodic oxidation of formaldehyde in alkaline medium.     

Laser-induced photoprocesses in solutions and films of the CdSe/ZnS nanoparticles

The photophysical properties of solutions and films with relatively high concentrations of CdSe/ZnS nanoparticles are studied in the presence of the visible laser irradiation in a wide range of power densities. The short-wavelength wing detected in the photoluminescence spectra of the solutions of quantum dots is due to the selective laser excitation of small-size nanoparticles. A comprehensive analysis of the anti-Stokes photoluminescence of the nanoparticles in solutions and films indicates the thermal mechanism of this phenomenon. The dimensional quantization effect, narrow spectra, and a relatively high luminescence yield are retained in the films with a high nanoparticle concentration. The luminescence spectra of the films remain unchanged when the laser flux density increases to 1 × 10⁶ W/cm². The effect of the laser radiation on the nanoparticle films is studied at the flux densities exceeding the damage threshold (5 × 10⁶–1 × 10⁹ W/cm²).     

The effect of ITO films thickness on the properties of flexible organic light emitting diode

Indium tin oxide (ITO) thin films were deposited on cyclic olefin copolymer substrate at room temperature by an inverse target sputtering system. The crystal structure and the surface morphology of the deposited ITO films were examined by X-ray diffraction and atomic force microscopy, separately. The electrical properties of the conductive films were explored by four-point probing. Visible spectrometer was used to measure the optical properties of ITO-coated films. The performance of the flexible organic light emitting diode device with different thickness anode was investigated in this study.     

Ultrasonic, chemical stability and preparation of self-assembled fullerene[C60]-gold nanoparticle films

C(60)-functionalized gold nanoparticle films were self-assembled on the reactive surface of glass slides functionalized with 3-aminopropyltrimethoxysilane. The functionalized glass slides were alternately soaked in the solutions containing unmodified C(60) and 4-aminothiophenoxide/hexane thiolate-protected gold nanoparticles. Organic reaction (amination) facilitated the layer-by-layer multilayer film assembly. C(60)-functionalized gold nanoparticle films have grown up to several layers (upto 5 layers were examined) depending on the immersion time. The assembled nanoparticle films were characterized using UV-vis spectroscopy. The chemical stability of C(60)-gold nanoparticle films was studied by monitoring the changes in absorbance after the immersion of the films in acidic solutions. The ultrasonic stability of these nanoparticle films was studied by exposing them to ultrasonic irradiated surrounding, which results in the aggregation of nanoparticles on solid surfaces.     

Effect of misfit strain on the electrocaloric effect of P(VDF-TrFE) copolymer thin films

Based on the phenomenological Landau-Devonshire theory, we investigate the effect of misfit strain on the electrocaloric effect of P(VDF-TrFE) copolymer thin films. Theoretical analysis indicates that the compressive misfit strain reduces the working temperature to a great extent where the electrocaloric effect is maximized, which is different from the result of the conventional ferroelectric thin films, such as BaTiO₃. Although the compressive or tensile misfit strain does not change the maximum of the electrocaloric coefficient, the compressive misfit strain decreases the maximum of the adiabatic temperature change and the tensile misfit strain results in the opposite effect. Consequently, control of the misfit strain provides potential means to vary the working temperature for use in cooling systems.     

Hybrid Nanoparticle Film Material

A new hybrid material consisting of a nanoparticle film on a flexible, porous substrate is formed. The hybrid nanoparticle films are non-redispersable in solvents, yet remain porous and flexible. Visually, the hybrid films are highly reflective and metallic gold in appearance. However, the electronic properties of the films are characteristic for materials made from separate, non-sintered nanoparticles. Films of large area (several tens of cm²) and several microns in thickness can be formed. The method of formation is based on cross-linking gold nanoparticles using alkane-dithiols followed by filtration onto nanoporous supports. The films were characterized by transmission electron microscopy, atomic force microscopy and resistance measurements. The effect of the ratio of alkane-dithiol cross-linker to gold nanoparticles on the resistance of the nanoparticle films was also studied.     

Homogeneous switching in ultrathin ferroelectric films

It is well known that there are two possible switching mechanisms in ferroelectric crystals and films (see, e.g., Tagantsev et al 2010 Domains in Ferroic Crystals and Thin Films (Berlin: Springer)). The first mechanism, which follows from the mean-field theory of Landau-Ginzburg, is a homogeneous one and does not connect domains. This mechanism was never observed before 1998. The second mechanism, connected with nucleation and domain movement, is common for the ferroelectrics and is well known from the time of domain discovery (1956). In the present paper the existence of a homogeneous mechanism of switching in ultrathin copolymer films is confirmed by piezoresponse force microscopy. The results of the present paper permit us to suppose that homogeneous switching exists in other ultrathin ferroelectric films.     

CdS及其包裹型纳米颗粒PVA基复合膜的特性研究

以聚乙烯醇 (PVA)、六偏磷酸钠为分散剂 ,采用溶胶法合成了 Cd S纳米胶体颗粒 ,制备出 Cd S及其包裹型纳米颗粒 PVA基复合膜。通过光子相干光谱粒度仪 (PCS)、紫外 -可见吸收光谱 (UV- VIS)、荧光光谱 (PL)对样品进行了初步表征。结果表明 ,Cd S纳米颗粒 PVA基复合膜的紫外 -可见吸收光谱有明显的蓝移现象 ,所发荧光主要由表面态发射引起 ;包裹型 PVA基复合膜所发荧光主要由带边发射引起     

AFM analysis of MgB2 films and nanostructures

For the fabrication of superconducting devices based on nanostructured thin films, the quality of the starting surface is often of crucial importance. For example, the transport properties of superconducting nanobridges are strongly affected by the geometry and the edge definition of the nanostructures. In this work, we report about AFM characterization of magnesium diboride films and nanobridges fabricated in view of application in superconducting electronics. MgB₂ films, obtained by co-deposition method followed by annealing in situ on silicon nitride substrate, have been nanostructured by electron beam lithography and ion milling. The analysis of the AFM images by the height-height correlation function shows that the films have a self-affine smooth textured surface with a RMS roughness of 20 nm. Furthermore, the nanobridges are continuous, with a well-defined geometry and a rounded profile, and the nanostructuration process does not significantly affect the film morphology.     

Low-voltage pulse exciting electron emission from ferroelectric copolymer film cathode: Role of film thickness and emission stability

Ferroelectric copolymer thin films P(VDF-TrFE) are used as a ferroelectric cathode for investigation of their electron emission properties. This ferroelectric copolymer films with different thicknesses are deposited by spin-coating method, and then the annealing process is carried out to improve the crystallinities of as-deposited copolymer films. The measurement results of ferroelectric electron emission showed that the copolymer P(VDF-TrFE) films had a desired ferroelectric electron emission ability excited at low-voltage pulse, and its peak emission current can reach to be ∼1.3 μA when the pulse voltage is 280 V. In addition, the effect of film thickness on electron emission property and emission stability of copolymer thin film P(VDF-TrFE) are discussed.     

Permeation of gases through modified polymer films III. Gas permeability and separation characteristics of gamma-irradiated teflon FEP copolymer films

A study has been made of the diffusion, solubility, and separation of nitrogen and methane gases at temperatures ranging from 15° to 50°C in a series of Teflon FEP copolymer films which were irradiated by γ rays in air and under vacuum. The irradiated films were subjected to postirradiation treatment temperatures above and below the glass I transition temperature of the copolymer. The effect of radiation on crystallinity and cross-linking was examined by density, thermal, and tensile strength measurements. Diffusion and permeability coefficients of both gases decreased with irradiation dose but solubility coefficients were not greatly affected. Nitrogen-methane separation factors for vacuum-irradiated films increased with irradiation dose, but little change was observed for the air-irradiated films. Chain scission appeared to be the predominant reaction in air-irradiated films whereas both cross-linking and chain scission occurred in vacuum-irradiated films depending on post-irradiation heat-treatment conditions. The permselectivity of the Teflon FEP films was increased by γ irradiation but this was achieved at the expense of the permeation rate.     

Sensor and microelectronic elements based on nanoscale granular systems

Specific effects observed in small metal particles due to their distinction from bulk material as well as phenomena inherent to an ensemble of these particles coupled by electron tunneling have attracted considerable attention to nanosized systems. Electron and photon emission was revealed as a power was fed into the metal nanoparticle films deposited on insulating substrates either by passage of an electrical current in the film plane or by laser irradiation in the infrared and visible range. The electrical conductivity of metal nanoparticle films close to the percolation threshold is sensitive to temperature, substrate bending and adsorption of various gases. Besides, the current–voltage characteristics of the conduction current of a system consisting of a metal nanoparticle film and an adsorbate exhibit a voltage-controlled negative resistance region. These peculiar properties enable nanosized particle systems to be used for various applications. The present review deals with a variety of sensors for physical properties and microelectronics elements based on nanoparticle films. The mechanisms underlying the special properties are discussed. Some technological methods ensuring better parameter definition and long-term stability of sensors are also described.     

General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors

A general approach to fabricate nanoparticle arrays of different kinds of materials is demonstrated in this paper. It was found that the center-to-center distance of the nanoparticles or the nanoclusters can be controlled using patterned block copolymer nanoreactors by adding polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin film. The number of the nanoparticles formed in the P4VP nanodomains can also be adjusted by addition of polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer. In fabrication of Au nanoparticle arrays, HAuCl₄ precursor was directly loaded into P4VP nanodomains of the diblock copolymer thin film by using a methanol solvent, which is a good solvent for P4VP but non-solvent for PS. The Au nanoparticle arrays were then obtained by reducing HAuCl₄ with sodium citrate dihydrate, and then in situ transferred to silicon substrate by a two-step calcination method. ZnO and Fe _x O _y nanoparticle arrays were also synthesized by this approach with thermal decomposition and double decomposition reactions, respectively. Additionally, the advantage of using two-step calcination method over the air plasma method was discussed.