Dielectric properties of doped polystyrene and polymethylmethacrylate

About 1 μm thick films of polystyrene (PS) and polymethylmethacrylate (PMMA) doped with diphenylsulfoxide (DS) up to 40 wt.% were prepared from solutions using spin-coating method. Glass transition temperature (T _g) of doped polymer films was determined by DSC technique. The depth profile and surface concentration of DS dopant were measured by RBS and XPS methods, respectively. The temperature dependence of relative permittivity of the films was determined from capacitance measurement. The dependence of polarization (P) on electric field (E) was measured using a standard Sawyer–Tower circuit. The glass transition temperature T _g of both composites was found to be decreasing function of the DS concentration. The DS doping leads to an increase of relative permittivity of the PS and PMMA films. RBS and XPS measurements reveal an outward diffusion of DS dopant in PS/DS films at elevated temperature. No such effect was observed in PMMA/DS films. PMMA/DS layers were found to be more thermally stable comparing to PS/DS.     

Conductance measurements of nanoscale regions with in situ transmission electron microscopy

Conductance measurements of nanostructures with simultaneous transmission electron microscopy (TEM) were performed on thin insulating SrF₂ films (3 nm thick) and Fe–SrF₂ granular films (10 nm thick) deposited on tip-shaped Au electrodes. By using a movable counter electrode, nanoscale regions were selected for investigation. Systematic measurements taken during the deformation of the SrF₂ film by the counter-electrode provided a tunnelling barrier height of about 2.5 eV. The conductance of Fe–SrF₂ in nanoscale (∼ 500 nm²) showed the Coulomb staircase like characteristics at room temperature. The staircase period approximately corresponded to the value estimated from the geometry observed by TEM. The feasibility of this method is briefly described.     

Photocatalytic properties of porous TiO2/Ag thin films

In this study, nanocrystalline TiO₂/Ag composite thin films were prepared by a sol-gel spin-coating technique. By introducing polystyrene (PS) spheres into the precursor solution, porous TiO₂/Ag thin films were prepared after calcination at a temperature of 500 °C for 4 h. Three different sizes (50, 200, and 400 nm) of PS spheres were used to prepare porous TiO₂ films. The as-prepared TiO₂ and TiO₂/Ag thin films were characterized by X-ray diffractometry (XRD) and by scanning electron microscopy to reveal structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.When PS spheres of different sizes were introduced after calcination, the as-prepared TiO₂ films exhibited different porous structures. XRD results showed that all TiO₂/Ag films exhibited a major anatase phase. The photodegradation of porous TiO₂ thin films prepared with 200 nm PS spheres and doped with 1 mol% Ag exhibited the best photocatalytic efficiency where ∼ 100% methylene blue was decomposed within 8 h under UV exposure.     

Nano-tribological characteristics of TiO<Subscript>2</Subscript> films on 3-mercaptopropyl trimethoxysilane sulfonated self-assembled monolayer

Silane coupling reagent (3-mercaptopropyl trimethoxysilane (MPTS)) was used to prepare twodimensional self-assembled monolayer (SAM) on silicon substrate. The terminal -SH group was in situ oxidized to −SO₃H group to endow the film with good chemisorption ability. Then TiO₂ thin films were deposited on the oxidized MPTS-SAM to form composite thin films, making use of the chemisorption ability of the −SO₃H group. Atomic force microscope (AFM) and contact angle measurements were used to characterize TiO₂ films. Adhesive force and friction force of TiO₂ thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. Results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. In order to study the effect of capillary force, tests were performed in various relative humidities. Results showed that the adhesive force of silicon substrate increases with relative humidities and the adhesive force of TiO₂ thin films only increases slightly with relative humidity. Research showed that surfaces with more hydrophobic property revealed the lower adhesive and friction forces.     

Synthesis and characterizations of three-dimensional ordered gold- nanoparticle-doped titanium dioxide photonic crystals

We developed a simple method to prepare gold-nanoparticle-doped titanium dioxide (GTD) sol-gel solution. The optimized GTD sol-gel solutions were a mixture of TEA, titanium (IV) butoxide, HAuCl₄, and deionized water in 0.3:1:0.5:3 volume ratios at room temperature. Using this sol-gel solution, we fabricated the GTD photonic crystal structure by infiltrating this solution by dip-coating into a polystyrene (PS) template. It was found that high quality of thin films was obtained by infiltrating twice the PS templates with the synthesized GTD sol-gel solutions. Energy dispersive X-ray spectroscopy and X-ray photoelectron spectra revealed the doping of TiO₂ and Au in the GTD photonic crystals. X-ray diffraction showed that TiO₂ and Au existed as anatase phase and metallic Au phase, respectively, in the GTD photonic crystals. The results indicated that the gold nanoparticles were doped into the framework of the photonic crystals.     

Structural and photoluminescence investigation of ZnSe nanocrystals dispersed in organic and inorganic matrices

In this work, we report on the investigation of the effect of dispersion of zinc selenide (ZnSe) nanocrystallites into polystyrene (PS) and silica (SiO₂) thin films on their structural, morphological and photoluminescence properties. The ZnSe/PS nanocomposites thin films were synthesized by a direct dispersion of ZnSe crystallites into polymers solution, whereas the ZnSe–SiO₂ films were prepared on glass substrates by the sol–gel dip-coating technique. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-rays (EDX), UV–visible spectrophotometry and photoluminescence spectroscopy (PL) techniques have been used to study the structural, morphological and optical properties of the prepared nanocomposite thin films. XRD patterns have demonstrated the incorporation of cubic ZnSe in both organic and inorganic matrices. SEM micrographs have indicated that ZnSe dispersion in the films is homogeneous. UV–visible absorption spectra of the nanocomposite thin films have put into evidence that the dispersion of ZnSe nanocrystals in the thin film matrices improved their optical absorption. Room temperature PL spectra have shown that the addition of ZnSe enhanced the UV emission of PS and all the emission of SiO₂ thin films.     

Percolation threshold for electrical resistivity of Ag-nanoparticle/titania composite thin films fabricated using molecular precursor method

To find the percolation threshold for the electrical resistivity of metallic Ag-nanoparticle/titania composite thin films, Ag-NP/titania composite thin films, with different volumetric fractions of silver (0.26 ≤ φ_Ag ≤ 0.68) to titania, were fabricated on a quartz glass substrate at 600 °C using the molecular precursor method. Respective precursor solutions for Ag-nanoparticles and titania were prepared from Ag salt and a titanium complex. The resistivity of the films was of the order of 10⁻² to 10⁻⁵ Ω cm with film thicknesses in the range 100–260 nm. The percolation threshold was identified at a φ_Ag value of 0.30. The lowest electrical resistivity of 10⁻⁵ Ω cm at 25 °C was recorded for the composite with the Ag fraction, φ_Ag, of 0.55. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), and transmission electron microscopic (TEM) evaluation of the effect of the morphology and the nanostructures of the Ag nanoparticles in the composite thin films on the electrical resistivity of the film revealed that the films consist of rutile, anatase, and metallic Ag nanoparticles homogeneously distributed in the titania matrix. It could be deduced that the electrical resistivity of the thin films formed at 600 °C was unaffected by the anatase/rutile content within the thin film, whereas the shape, size, and separation distance of the Ag nanoparticles strongly influenced the electrical resistivity of the Ag-nanoparticle/titania composite thin films.     

On the role of indium underlays in the prevention of thermal grooving in thin gold films

Thin gold films are potentially important for metallizations in microelectronic devices because of the high activation energy of gold for electrotransport. A high activation energy ensures a longer lifetime of microelectronic devices compared with those in which aluminum metallizations are used. When electromigration is no longer the principal failure mechanism, other failure mechanisms, caused by d.c. stressing, might become important. One possibility is grain boundary grooving. Preliminary studies have shown that grain boundary grooving in thin gold films is prevented by inserting an indium underlay between the gold film and the substrate. The objective of this work was to investigate the mechanisms for the prevention of grain boundary grooving in In/Au composite films by comparing the microstructural evolution of pure gold films with In/Au composite films during isothermal annealing. Microstructures were characterized in terms of grain size, grain size distribution, preferred orientation and surface morphology utilizing transmission electron microscopy (TEM), cross-sectional TEM, scanning electron microscopy and X-ray diffraction. The chemical reactions and the distributions of the phases were monitored by selected area diffraction in TEM, and by Auger electron spectroscopy sputter profiling.It was found that the principal mechanisms that inhibit grain boundary grooving in IN/Au composite films area as follows.

• 1.(1) Indium underlays modify the microstructure of gold films by randomizing the orientation of the grains, refining the grain size, narrowing the grain size distribution and roughening the surface of the gold films.
• 2.(2) Indium is redistributed on gold films and forms In₂O₃ on the free surface and within the film during air annealing.
• 3.(3) The In₂O₃ on the surface “caps” the surface of gold films and limits mass transport during annealing.
• 4.(4) The In₂O₃ within the gold film, presumably residing at grain boundaries, impedes grain growth by pinning the grain boundary migration.

     

Templated synthesis of ordered porous TiO2 films and their application in dye-sensitized solar cell

Ordered porous TiO₂ thin films were fabricated on conductive glass by using colloid crystal template of polystyrene (PS) spheres. Microstructural characterization by scanning electron microscopy techniques was carried out to explore the porous structural changes due to the PS templates which could be controlled by adjusting the drawing rate. Photovoltaic performance was measured and this revealed the effect of microstructural changes. The results showed that monolayer porous TiO₂ films and multilayer porous TiO₂ films could be successfully prepared. And multilayer porous TiO₂ films provided large surface area for dye absorption to increase the efficiency of dye-sensitized solar cells (DSSCs) which were assembled by porous TiO₂ films.     

The structure of solvent crazes in polystyrene

The structure of crazes grown in polystyrene (PS) immersed inn-heptane and methanol at room temperature has been determined using refractive index measurements, transmission electron microscopy, and fractographic analysis of craze fracture surfaces.n-heptane crazes in thin films exhibit a low number density of thick, load-bearing fibrils whereas methanol crazes consist of a highly interconnected network of fibrils not unlike the craze structure found in crazes grown in air. A row of large voids at the centre line of the craze which is typical of the structure observed in air crazes is not found, however, in either methanol orn-heptane crazes, indicating a different growth mechanism for the solvent crazes. The craze structure found in thin films is in agreement with the void contents determined from refractive index measurements and with the results from scanning electron microscopy of fracture surfaces of bulk crazes grown with methanol andn-heptane. Glass transition temperature measurements of equilibrium swollen PS films giveT _g=91° C for methanol andT _g=6° C forn-heptane. The results suggest that the structure of crazes grown with slowly diffusing crazing agents (methanol andn-heptane) is strongly dependent on whether the growth temperature is above or belowT _g, the glass transition temperature of the plasticized region just ahead of, and in, the craze. IfT _g is below the growth temperature, weak crazes are formed with a large void content. During the growth, thin fibrils break by viscous flow leaving only a small number of load-bearing fibrils. The stress in the neighbourhood of the growing craze is strongly relieved favouring propagation of a single craze. IfT _g is above the growth te'mperature, strong crazes are formed with the fibrils strain-hardened during the growth process. There is hardly any change in stress next to the craze and therefore multiple crazing (craze bundles) is favoured over the propagation of a single craze.     

Photocatalytic properties of nanocrystalline TiO2 thin film with Ag additions

In the present study, nanocrystalline TiO₂/Ag composite thin films were prepared by a sol–gel spin coating technique. While, by introducing polystyrene (PS) microspheres, porous TiO₂/Ag films were obtained after calcining at a temperature of 500 °C. The as-prepared TiO₂ and TiO₂/Ag thin films were characterized by X-ray diffractometry, and scanning electron microscopy to reveal the structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.After 500 °C calcination, the microstructure of PS-TiO₂ film without Ag addition exhibited a sponge-like microstructure while significant sintering effect was noticed with Ag additions and the films exhibited a porous microstructure. Meanwhile, coalescence of nanocrystalline anatase-phase TiO₂ can be observed with respect to the sharpening of XRD diffraction peaks. The photodegradation of porous TiO₂ doped with 1 mol% Ag exhibited the best photocatalytic efficiency where 72% methylene blue can be decomposed after UV exposure for 12 h.     

XPS study of palladium sensitized nano porous silicon thin film

Nano porous silicon (PS) was formed on p-type monocrystalline silicon of 2–5 Ω cm resistivity and (100) orientation by electrochemical anodization method using HF and ethanol as the electrolytes. High density of surface states, arising due to its nano structure, is responsible for the uncontrolled oxidation in air and for the deterioration of the PS surface with time. To stabilize the material PS surface was modified by a simple and low cost chemical method using PdCl₂ solution at room temperature. X-ray photoelectron spectroscopy (XPS) was performed to reveal the chemical composition and the relative concentration of palladium on the nanoporous silicon thin films. An increase of SiO₂ formation was observed after PdCl₂ treatment and presence of palladium was also detected on the modified surface. I–V characteristics of Al/PS junction were studied using two lateral Al contacts and a linear relationship was obtained for Pd modified PS surface. Stability of the contact was studied for a time period of around 30 days and no significant ageing effect could be observed.     

Fracture mechanisms in polystyrene/laponite nanocomposites prepared by emulsion polymerization

Transmission electron microscopy (TEM) has been used to investigate the effect of laponite clay on microdeformation in thin latex-based polystyrene (PS) films, in which the laponite was concentrated at the original interfaces between the PS particles. At room temperature, a transition was observed from crazing in pure PS to a coarser fibrillar deformation mode as the laponite content increased. Moreover, whereas pure PS showed increasingly homogeneous deformation as T approached T_g, the fibrillar deformation zones observed in the nanocomposites persisted up to T just below T_g, and there was some evidence for yielding behaviour at even higher T in the presence of laponite. The macroscopic fracture resistance of the films, as assessed from double edge-notched tensile specimens, initially increased with laponite content, but decreased for laponite contents greater than 5 wt% with respect to the styrene monomer. This was attributed to a decrease in local ductility, consistent with the observation of reduced deformation ratios in the deformation zones by TEM, and to the intrinsic weakness of the laponite stacks and/or the PS-laponite interface. Thus, specimens with laponite contents comparable with the estimated threshold for percolation of contacts between the laponite stacks showed extremely brittle behaviour, associated with crack propagation along the interfaces between the latex particles.     

The effect of Au and Pt nanoclusters on the structural and hydrogen sensing properties of SnO2 thin films

Au and Pt nanoparticle modified SnO₂ thin films were prepared by the sol-gel method on glass substrates targeting sensing applications. Structural and morphological properties of these films were studied using X-ray Diffraction and Scanning Electron Microscopy. It was proved that the films crystallized in tetragonal rutile SnO₂ crystalline structure. Scanning Electron Microscopy observations showed that the metallic clusters' dimensions and geometry depend on the kind of the metal (Au or Pt) while SnO₂ films surface remains almost the same: nanostructured granular very smooth. Optical properties of the films were studied using UV-visible spectroscopy. The modified SnO₂ films were tested as hydrogen sensors. The response of SnO₂, SnO₂-Au and SnO₂-Pt thin films against hydrogen was investigated at different operating temperatures and for different gas concentrations. The addition of metal nanoparticles was found to decrease the detection limit and the operating temperature (from 180 °C to 85 °C), while increasing the sensing response signal.     

Optical,structural and electrical investigations on PbTe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> alloys

The fabrication of devices with lead salts and their alloys with detecting and lasing capabilities has been an important technological development. The high quality polycrystalline thin films of PbTe_1−x S _x with variable composition (0 ≤ x ≤ 1) have been deposited onto ultra clean glass substrates by vacuum evaporation technique. Optical, structural and electrical properties of PbTe_1−x S _x thin films have been examined. Absorption coefficient and band gap of the films were determined by absorbance measurements in wavelength range 2,500–5,000 nm using FTIR spectrophotometer. Sample nature, crystal structure and lattice parameter of the films were determined from X-ray diffraction patterns. DC conductivity and activation energy of the films were measured in temperature range 300–380 K through I–V measurements.     

Properties of Tungsten Thin Films Produced with the RF-Sputtering Technique

For the purpose of building very sensitive light and phonon detectors, as e.g. applied in the Dark Matter (DM) experiment CRESST (Cryogenic Rare Event Search with Superconducting Thermometers), transition edge sensors (TESs) in combination with a massive absorber crystal are used. To ensure high sensitivity of the detectors, low heat capacities, i.e. low working temperatures of about 10 mK are aimed at. Therefore, TESs made of tungsten thin films exhibiting the alpha-tungsten (α-W) phase with transition temperatures of T _c =10–15 mK are required. We have produced tungsten thin films with T _c in the range of 25–55 mK by rf-sputtering. To decouple the thermometer production from the choice of the target material and to avoid heating cycles of the absorber crystal, a composite design for detector production is applied. The composite design includes fabrication of the TES on a separate substrate and then attaching of this separate TES to a massive absorber crystal by gluing. For this purpose small sapphire substrates are used for the deposition of the TES. Properties of tungsten thin films grown with the rf-sputtering technique as well as first results of composite detectors built with these films acting as TESs will be presented.      

The effect of repeated annealing temperature on the structural,optical, and electrical properties of TiO<Subscript>2</Subscript> thin films prepared by dip-coating sol–gel method

In this study, we have studied the effect of repeated annealing temperatures on TiO₂ thin films prepared by dip-coating sol–gel method onto the glasses and silicon substrates. The TiO₂ thin films coated samples were repeatedly annealed in the air at temperatures 100, 200, and 300 °C for 5 min period. The dipping processes were repeated 5 to 10 times in order to increase the thickness of the films and then the TiO₂ thin films were annealed at a fixed temperature of 500 °C for 1 h period. The effect of repeated annealing temperature on the TiO₂ thin films prepared on glass substrate were investigated by means of UV–VIS spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM). It was observed that the thickness, average crystallite size, and average grain size of TiO₂ samples decreased with increasing pre-heating temperature. On the other hand, thickness, average crystallite size, and average grain size of TiO₂ films were increased with increasing number of the layer. Al/TiO₂/p-Si metal–insulator–semiconductor (MIS) structures were obtained from the films prepared on p-type single silicon wafer substrate. Capacitance–voltage (C–V) and conductance–voltage (G/ω–V) measurements of the prepared MIS structures were conducted at room temperature. Series resistance (R _s) and oxide capacitance (C _ox) of each structures were determined by means of the C–V curves.     

Irradiation induced effects on Ni3N/Si bilayer system

The irradiation effect in Ni₃N/Si bilayers induced by 100 MeV Au ions at fluence 1.5 × 10¹⁴ ions/cm² was investigated at room temperature. Grazing incidence X-ray diffraction determined the formation of Ni₂Si and Si₃N₄ phases at the interface. The roughness of the thin film was measured by atomic force microscopy. X-ray reflectivity was used to measure the thickness of thin films. X-ray photoelectron spectroscopy has provided the elemental binding energy of Ni₃N thin films. It was observed that after irradiation (Ni 2p_3/2) peak shifted towards a lower binding energy. Optical properties of nickel nitride films, which were deposited onto Si (100) by ion beam sputtering at vacuum 1.2 × 10⁻⁴ torr, were examined using Au ions. In-situ I–V measurements on Ni₃N/Si samples were also undertaken at room temperature which showed that there is an increase in current after irradiation.     

Preparation and tribological characteristics of sulfonated self-assembled monolayer of 3-mercaptopropyl trimethoxysilane TiO2 films

Silane coupling reagent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared on silicon substrate to form two-dimensional self-assembled monolayer (SAM) and the terminal–SH group in the film was in situ oxidised to–SO₃H group to endow the film with good chemisorption ability. Thus, TiO₂ thin films were deposited on the oxidised MPTS-SAM to form composite thin films, making use of the chemisorption ability of the–SO₃H group. Atomic force microscope (AFM), and contact angle measurements were used to characterise TiO₂ films. Adhesive force and friction force of TiO₂ thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. Results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. In order to study the effect of capillary force, tests were performed in various relative humidity (RH). Results showed that the adhesive force of silicon substrate increases with RH and the adhesive force of TiO₂ thin films only increases slightly with RH. Research showed that surfaces with more hydrophobic property revealed the lower adhesive and friction forces.     

Processing and magneto-electric properties of sol–gel-derived Pb(Zr0.52Ti0.48)O3–Ni0.8Zn0.2Fe2O4 2-2 type multilayered films

Pb(Zr_0.52Ti_0.48)O₃–Ni_0.8Zn_0.2Fe₂O₄ (PZT–NZFO) multilayered thin films with various volume fractions of the PZT phase (100, 74, 58, 48, 33, and 0%) were prepared on Pt/Ti/SiO₂/Si substrates using sol–gel spin-coating method. X-ray diffraction shows polycrystalline structure and scanning electron microscopy reveals good multilayer morphology of the composite thin film as annealed at 700 °C in air. The thickness of the composite films was estimated in the range of ~400 to ~600 nm. The ferroelectric and magnetic properties were measured as function of the volume fractions of the PZT phase. The magnetoelectric (ME) effect was investigated under various bias magnetic fields. The maximum ME voltage coefficient (α _E  = dE/dH) is 278 mV/cmOe for the composite film with the volume fractions of the PZT phase of ~48%.