Structural and nanomechanical properties of sol–gel prepared (K,Na)NbO3 thin films

Perovskite (K, Na)NbO₃ (KNN) thin films (~100 nm) were prepared by sol–gel/spin coating process on Pt/SiO₂/Si substrates and annealed at 650 °C. The structural properties of KNN films were confirmed by X‐ray diffraction analysis (XRD), Raman spectroscopy and scanning electron, transmission electron and atomic force microscopy (SEM, TEM and AFM) analysis. Pure perovskite phase of K_0.65Na_0.35NbO₃ in nonstoichiometric composition with monoclinic symmetry in film was revealed. Uniform homogeneous microstructure of KNN film with the roughness (~6.9 nm) contained spherical particles (~50–90 nm). Nanoindentation technique was used to characterize the mechanical properties of KNN films. Elastic modulus and hardness of Pt, SiO₂ and KNN thin films were calculated from their composite values of KNN/Pt/SiO₂/Si film/substrate system. The modulus and hardness of KNN film (71 and 4.5 GPa) were lower in comparison with SiO₂ (100 and 7.5 GPa). Pt film (~30 nm) did not influence the composite modulus, but had effect on hardness of KNN film. Copyright © 2015 John Wiley & Sons, Ltd.     

Fabrication and properties of fullerodendron thin films

Thin films of fullerodendron (C(60)(Gn-COOMe) (n = 0.5, 1.5, 2.5)), which was synthesized from fullerene and anthracenyl poly(amido amine) dendron with methyl ester terminals and different generations (G), were fabricated by the Langmuir-Blodgett (LB) and adsorption techniques. It was characterized by X-ray reflectometry that the LB films possessed well-ordered structure, although the adsorption method led to random orientation of molecules. As to C(60)(G0.5-COOMe) and C(60)(G1.5-COOMe), the LB films took a four-layer structure consisting of a double layer of molecules, and fullerene moieties exist in the interior of the LB films. On the other hand, C(60)(G2.5-COOMe) led to a two-layer structure in which the fullerene moieties were at the air side and the dendron moieties were at the substrate side. With increasing generation of dendron, the monolayer formation ability at the air/water interface as amphiphilic molecule strengthens and the amphiphilic property becomes superior to the fullerene-fullerene attractive interaction that prevents the monolayer formation. Furthermore, in the case of C(60)(G0.5-COOMe) and C(60)(G1.5-COOMe), the reduction peak in cyclic voltammetry of the LB film remained even after UV light irradiation. On the contrary, the peak of the C(60)(G2.5-COOMe) LB film disappeared, indicating that molecular arrangement in the films affects electrochemical properties.     

Carbon nanotube thin films modified with a mixture of Prussian blue and ruthenium purple: combining materials and properties

Thin films of iron-filled carbon nanotubes prepared through the liquid/liquid interfacial method were modified with a mixture of hexacyanometallates (HCMs) Prussian blue and ruthenium purple. Two different approaches were used in order to obtain both materials in the composites, based on a direct reaction starting from a mixture of both precursors or a step-by-step deposition of each compound. The modified films were characterized by cyclic voltammetry, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and UV-Vis spectroscopy, confirming the formation of a mixture of HCMs in both methods of synthesis. Stability studies were evaluated in different supporting electrolytes, and composites presented good performances due to carbon nanotube stabilization. Electrochromic properties were also evaluated for selected composites, showing high electrochromic efficiency and stability.

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Optical properties of pentacene and perfluoropentacene thin films

The optical properties of pentacene (PEN) and perfluoropentacene (PFP) thin films on various SiO(2) substrates were studied using variable angle spectroscopic ellipsometry. Structural characterization was performed using x-ray reflectivity and atomic force microscopy. A uniaxial model with the optic axis normal to the sample surface was used to analyze the ellipsometry data. A strong optical anisotropy was observed, and enabled the direction of the transition dipole of the absorption bands to be determined. Furthermore, comparison of the optical constants of PEN and PFP thin films with the absorption spectra of the monomers in solution shows significant changes due to the crystalline environment. Relative to the monomer spectrum, the highest occupied molecular orbital to lowest unoccupied molecular orbital transition observed in PEN (PFP) thin film is reduced by 210 meV (280 meV). A second absorption band in the PFP thin film shows a slight blueshift (40 meV) compared to the spectrum of the monomer with its transition dipole perpendicular to that of the first absorption band.     

Sol-gel thin films with anti-reflective and self-cleaning properties

Self-cleaning photocatalytic TiO₂ films are beneficial since they reduce the maintenance cost and enhance the efficiency of various optical systems, especially thermal and photovoltaic solar systems. However, the presence of a TiO₂ layer on glass reduces the transmission of incident light, which leads to a decrease in efficiency. This drawback can be overcome by applying a layer of anti-reflective coating beneath the TiO₂ layer. Generally, the anti-reflective layer is porous silica. The presence of the anti-reflective layer compensates for the loss of light transmittance caused by the photocatalytic TiO₂ top layer. This paper reviews some of the previous and the latest fundamental studies in the literature on anti-reflective, self-cleaning and multi-functional films.     

Electrical and mechanical properties of thin metal films: Size effects

A general expression for the function of electron scattering in thin films of a grain structure is derived which takes account of both the external and internal size effects. Limiting and particular values of this function are given for polycrystalline and single-crystal films. Theoretical results are compared to the experimental results obtained for aluminium and tin. The relationship between size effects and resistivity, temperature coefficient of resistance, longitudinal and transverse strain coefficient of resistance and thermoelectric power is studied. The dependence of the orientation of monocrystalline copper and aluminium films on thermal stress, the direction of the energy density of elastic strains and the anistropy of elastoresistance coefficients in these films are examined. An expression for the gauge factor in single-crystal metal films of given orientations is derived.     

Chemical surface deposition and growth rate of thin CdSe films

Chemical surface deposition of thin CdSe films was studied. The conditions for preparing thin films were examined, the degrees of Cd conversion in the starting compounds were determined, and the film thicknesses were measured.     

Electronic properties of conjugated polyelectrolyte thin films

The electronic properties of conjugated polyelectrolytes (CPEs) with poly(fluorene-co-phenylene) backbones and different counterions and charges have been investigated using absorption and ultraviolet photoelectron spectroscopy (UPS). The optical energy band gap of CPEs depends mainly on their conjugated backbone and are nearly insensitive to the charges or counterions. UPS measurements reveal that electron injection from Au to polymers with cationic groups is more efficient than for the neutral and anionic counterparts. The vacuum levels of CPEs were also shifted toward higher or lower binding energy, relative to that of Au, depending on the charge and counterion presence, and provide insight into the general alignment of dipoles at the metal/organic interface.     

Photoelectrochemical properties of MoO2 thin films

Thin MoO₂ films were electrodeposited on a selenium pre-deposited SnO₂|glass plate. The photoelectrochemical properties of MoO₂ films were investigated in 0.1 M Na₂SO₄ solution by the ultraviolet–visible spectrophotometry, linear sweep voltammetry, and altering current impedance measurement techniques. It was found that under illumination with the incident light of λ?=?366 nm, the photo response of the MoO₂|SnO₂|glass electrode resulted from the MoO₂ layer, while the SnO₂ layer served as a sink for photogenerated charge carriers. The MoO₂ film exhibited n-type conductivity. A schematic band structure diagram of MoO₂ in 0.1 M Na₂SO₄ solution was constructed. The flat band potential (E _fb), the donor concentration (N _D), the photogeneration current efficiency depended on MoO₂ film thickness. The [Fe(CN)₆]^4?/3? redox PEC cell with MoO₂|SnO₂|glass plate as a photoanode was constructed. Power output characteristics such as the open circuit voltage (V _OC), short circuit current (I _SC), the fill factor (FF), and the light-to-electrical conversion efficiency (η) were determined. The maximum light-to-electrical conversion efficiency exhibited by the PEC cell was 0.94 %.     

Gas-sensitive properties of thin nickel oxide films

The results of a study of the gas-sensitive properties of nickel oxide layers with respect to n-hexane, acetone, ethanol, benzene, o-xylene, toluene and ammonia are presented. NiO layers 100 ± 5 nm thick were obtained by chemical vapor deposition in the systems (EtCp)₂Ni–О₂–Ar and (EtCp)₂Ni–О₃–О₂–Ar. The electrical resistance of the layers changes in the presence of hexane, ethanol, benzene, and ammonia vapors. The electrical resistance of the obtained layers changed in the presence of vapors of hexane, ethanol, benzene and ammonia. Response and recovery time of the sensing element of the gas sensors did not exceed 6 s in the temperature range 500–600 K.     

Nonlinear optical properties of thin organic films

A brief survey is given on our recent work on the linear and nonlinear optical properties of thin films of polymers with a conjugated π–electron system. Third harmonic generation and degenerate four wave mixing experiments are used to study magnitude and response time of the third order nonlinear optical susceptibility of poly(p-phenylenevinylene) and poly(phenyl acetylene). Phthalocyanine derivatives show a strong influence of the intermolecular electronic coupling on the response time of transient gratings. The influence of energy transfer on the relaxation process is discussed.     

Optical and dielectrical properties of azo quinoline thin films

In this study, the optical and dielectrical properties of a novel series of quinoline azodyes (5-(4′-derivatives phenyl azo)-8-hydroxy-7-quinolinecarboxaldehyde) (AQL₁–AQL₅) were investigated and the obtained results were analyzed. The X-ray diffraction (XRD) patterns of AQL_n show that the materials in the powder form are a mixture of amorphous and crystalline structure, while the thermally deposited thin films are completely amorphous. The optical constants such as the refractive index, n, the absorption index, k and the absorption coefficient, α, were determined using spectrophotometric measurements of transmittance (T) and reflectance (R) in the wavelength range 200–2500 nm. According to the single oscillator model (SOM), some related parameters such as oscillation energy (E_o), the dispersion energy (E_d), the optical dielectric constant (ε_∞), the lattice dielectric constant (ε_L) and the ratio of free carrier concentration to its effective mass (N/m*) are estimated. The emission spectra of azo quinoline ligands (AQL_n) exhibit dual fluorescence peaks in the region 512–580 nm. This finding reveals the formation of two stoichiometric hydrogen-bonding in the ground and excited state. The dielectrical properties and alternating current conductivity (σ_AC) are investigated in temperature range 298–483 K and frequency range 0.1–100 KHz.     

Nonlinear optical properties of polymers and thin polymer films

An introduction to nonlinear optics (NLO) and the major challenges in the field of NLO-properties of polymeric materials, is given in this paper. Methods for the investigation of nonlinear optical properties of [4-(2-methacryloxyethyl)methylamino]-4′-cyanoazobenzene copolymers with methyl methacrylate (MMA) are demonstrated: Electric Field Induced Second Harmonic Generation (EFISHG), Hyper Rayleigh Scattering (HRS), Second Harmonic Generation (SHG) in floating monolayers and SHG in poled polymer films. An example of phase-transition analysis by SHG is given.     

Structure and properties of plasma-polymerized thin films of polyaniline

Plasma polymerization of aniline and in-situ doping of polvaniline with iodine was carried out using radio frequency glow discharge. Thin films of polyaniline were deposited on platinum and glass. The infrared spectrum shows that the aromatic ring is retained under the plasma conditions. The electrical conductivity measurements indicate that the conductivity increases by more than seven orders of magnitude when the polyaniline is doped by iodine. The scanning electron microscopic studies reveal the formation of irregular pentagons on glass substrate while on platinum, polvaniline forms a fibrillar network. In both the cases a continuous film is obtained.     

Multi-electron transfer in composite phthalocyanine thin films: structure and electrochromic properties

Both sequentially deposited double-layered and codeposited composite thin films were prepared by using two kinds of phthalocyanines. The structure and the electrochromic property of these thin films were compared with those of simple phthalocyanine films. The structures of the films were analyzed by scanning electron microscopy (SEM), X-ray diffrction (XRD) and electron spin resonance (ESR) spectra. From the viewpoint of morphology and crystallinity, codeposited thin films have the same structure as the simple one, having sharp peaks at ca. 2θ=7.0° in the XRD pattern and narrow crystal grains in SEM photographs. ESR measurements have revealed that phthalocyanine molecules disperse very well in the codeposited thin films in a molecular level in comparison with the physical mixture of phthalocyanine powders. This high dispersibility of the molecules in the codeposited thin films can play a role to improve the reversibility in the electrochromism. Thus, the reversibility of the phthalocyanine, which shows irreversible electrochromism in the simple film form, can be improved by the codeposition with another phthalocyanine with reversible electrochromism. In contrast, sequentially deposted double-layered thin film gives completely different results. The electrochromism of the double-layered film depends on the property of the simple phthalocyanine thin film which is in contact with the substrate.     

Structural and magnetic properties of nano-crystalline FeCoNiN thin films

Iron cobalt nickel nitride (FeCoNiN) thin films are prepared by sol-gel spin coating route. The structural, magnetic and surface properties of the thin films are evaluated. The crystalline nature of thin films was enhanced upon annealing, leading to increased crystallite size. The X-ray diffraction shows mixed phases with crystallite size in the range of 20–26.93 nm. Thin films show ferromagnetism at room temperature. Coercivity and saturation magnetization are in the range of 642–716 Oe and 2.5–7.5 emu/cm³ respectively. Both coercivity and saturation magnetization increased with annealing of thin films. Magnetic properties are related to the crystallinity of thin films. The increase in crystallite size results into an increase of magnetic properties. Rectangular shaped particles are seen on the surface of thin films. The same type of grains can be seen on the surface of thin films which confirmed the formation of FeCoNiN as predicted by XRD. These novel thin films might be used in memory devices and optoelectronic applications.     

ORMOSIL thin films: tuning mechanical properties via a nanochemistry approach

The mechanical properties (hardness and elastic modulus) of organically modified silicate thin films can be finely tuned by varying the degree of alkylation and thus the fraction of six- and four-membered siloxane rings in the organosilica matrix. This opens the way to large tunability of parameters that are of crucial practical importance for films that are finding increasing application in numerous fields ranging from microelectronics to chemical sensing.