Characteristics of Ag/Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>/p-Si heterostructure prepared by sol-gel processing

The metal-ferroelectric-semiconductor (MFS) heterostructure has been fabricated using Bi_3.25La_0.75Ti₃O₁₂ (BLT) as a ferroelectric layer by sol-gel processing. The effect of annealing temperature on phase formation and electrical characteristics of Ag/BLT/p-Si heterostructure were investigated. The BLT thin films annealed at from 500°C to 650°C are polycrystalline, with no pyrochlore or other second phases. The C-V curves of Ag/BLT/p-Si heterostructure annealed at 600°C show a clockwise C-V ferroelectric hysteresis loops and obtain good electrical properties with low current density of below 2×10⁻⁸ A/cm² within ±4 V, a memory window of over 0.7 V for a thickness of 400 nm BLT films. The memory window enlarges and the current density reduces with the increase of annealing temperature, but a annealing temperature over 600°C is disadvantageous for good electrical properties.     

Ag on Pt(111): Changes in Electronic and CO Adsorption Properties upon PtAg/Pt(111) Monolayer Surface Alloy Formation

The electronic and chemical (adsorption) properties of bimetallic Ag/Pt(111) surfaces and their modification upon surface alloy formation, that is, during intermixing of Ag and Pt atoms in the top atomic layer upon annealing, were studied by X‐ray photoelectron spectroscopy (XPS) and, using CO as probe molecule, by temperature‐programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS), respectively. The surface alloys are prepared by deposition of sub‐monolayer Ag amounts on a Pt(111) surface at room temperature, leading to extended Ag monolayer islands on the substrate, and subsequent annealing of these surfaces. Surface alloy formation starts at ≈600–650 K, which is evidenced by core‐level shifts (CLSs) of the Ag(3d_5/2) signal. A distinct change of the CO adsorption properties is observed when going to the intermixed PtAg surface alloys. Most prominently, we find the growth of a new desorption feature at higher temperature (≈550 K) in the TPD spectra upon surface alloy formation. This goes along with a shift of the CO_ad‐related IR bands to lower wave number. Surface alloy formation is almost completed after heating to 700 K.     

Effect of TaNx on electrical and optical properties of annealed TaNx/Ag/TaNx films

As‐deposited Ag(10 nm)/glass films exhibited agglomerated nanocrystals with seemingly thick boundaries. Introduction of a TaN_x layer below the Ag films resulted in dense and smooth structures, with a resistance at least three times lower than that of Ag/glass. For TaN_x(10 nm)/Ag(10 nm)/TaN_x(10 nm)/glass multilayer films, Auger electron spectroscopy results indicate that TaN_x acts as an effective barrier restraining the diffusion of Ag. After annealing (up to 573 K), no outward diffusion of Ag through either TaN_x layer was seen. However, partial oxidation of the outermost TaN_x layer to form Ta₂O₅ was observed. The films showed promising optical properties with 73% transmittance in the visible region and ~15% average transmittance in the near‐infrared region. The optical data obtained here was in good agreement with simulated predictions. Copyright © 2013 John Wiley & Sons, Ltd.     

Anodized Iron Oxide Nanostructures on Different Carbon Steels for Photoelectrochemical Water Splitting

In this study, two different nanostructural iron oxide films were prepared on two kinds of carbon steels (CS) with different contents of impurities via anodization in a mixture of aqueous ammonium fluoride solution and ethylene glycol, respectively, and apply to photoelectrochemical (PEC) water splitting. After annealing, iron oxide nanotubes (NTs) was coated on surface of lower purity CS and iron oxide nanoporous (NPs) was coated on surface of higher purity CS via scanning electron microscope. X‐ray diffraction pattern shows both of samples contain a major phase of α‐Fe₂O₃ and a slight phase of Fe₃O₄. Compared with NPs, NTs behaves better absorbance ability in visible spectra range via UV‐visible absorbance spectra. From PEC response, the iron oxide NTs showed higher water splitting performance (0.10 mA/cm² at 0.4 V vs. Ag/AgCl) than NPs (0.04 mA/cm² at 0.4 V vs. Ag/AgCl) due to better absorbance, higher car‐ rier concentration and low charge transfer resistance.     

Metal nanocomposite films prepared in situ from PVA and silver nitrate. Study of the nanostructuration process and morphology as a function of the in situ routes

Cast‐hybrid films composed of polyvinyl alcohol (PVA) and silver nitrate were treated according to three different ways, thermal annealing, UV‐irradiation, and chemical reduction by a borohydride solution, to obtain PVA/silver nanocomposite films. The nanostructuration process was studied as a function of the treatment conditions, and discussed as a function of the mobility state of the polymer chains in the nanocomposite matrix during treatment. A homogeneous dispersion of crystalline silver nanoparticles was obtained by thermal annealing above T_g and below T_m and UV‐lamp irradiation below T_g. For these two treatments, the major processing parameters were the annealing temperature and time and the UV‐exposure time, respectively. For low‐conversion rate in Ag(0), the films evolved upon ageing at room temperature. Totally different morphology and Ag(0) conversion were achieved by chemical reduction in a borohydride solution. All the silver ions were reduced into Ag(0), and crystalline silver nanoparticles layers parallel to the film surface were observed after the treatment. This morphology was related to the high‐swollen state of the polymer matrix during treatment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2062–2071, 2008     

A comparative studyof heat‐treated Ag:SiO2 nanocomposites synthesized by cosputtering and sol‐gel methods

In this work, we compared formation and properties of heat‐treated Ag nanoparticles in silica matrix synthesized by RF‐reactive magnetron cosputtering and sol–gel methods separately. The sol–gel and sputtered films were annealed at different temperatures in air and in a reduced environment, respectively. The optical UV‐visible spectrophotometry have shown that the absorption peak appears at 456 and 400 nm wavelength indicating formation of silver nanoparticles in SiO₂ matrix for both the sol–gel and sputtering methods at 100 and 800 °C, respectively. XPS measurements showed that the metallic Ag⁰ nanoparticles can be obtained from both the techniques at these temperatures. According to XPS and AFM analysis, by increasing annealing temperature, the concentration of the Ag nanoparticles on the surface decreased and the nanoparticles diffused into the substrate for the sol–gel films, while for the films deposited by cosputtering method, the Ag surface concentration increased by increasing the temperature. Based on AFM observations, the size of nanoparticles on the surface were obtained at about 25 and 55 nm for sputtered and sol–gel films, respectively, supporting our optical data analysis. In comparison, the sputtering technique can produce Ag metallic nanoparticles with a narrower particle size distribution relative to the sol–gel method. Copyright © 2008 John Wiley & Sons, Ltd.     

Interface analysis of pure Sn,pure Ag and Sn?Ag binary alloys in H2SO4

The electrochemical and passivation properties of three selected binary xSn? Ag (x = 26, 50 and 70 wt%) alloys were studied by means of open‐circuit potential variation, potentiodynamic curves and a.c. impedance spectroscopy techniques.The specimens were polarized between ?1.0 and 0.5 V versus saturated calomel electrode (SCE) in naturally oxygenated sulfuric acidsolutions of different concentrations The experimental results indicate that i_corr increases with increasing either the acid concentration or the Sn content in the solid phase. Electrochemical impedance spectroscopyresults measured at the free corrosion potential confirm that alloy I (26Sn? Ag) characterizes by thicker passive film with higher protective ability compared to the other two samples richer in tin component. The exponential variation of the relative thickness of the surface film on any of the tested samples assumes an almost constant thickness for a thin barrier layer and a much larger outer porous layer that dominates the total film thickness on the alloy. Copyright © 2010 John Wiley & Sons, Ltd.     

A new method for deposition nitrogen‐doped TiO2 nanofibers with mixed phases of anatase and rutile

A new method for deposition nitrogen‐doped TiO₂ nanofibers films was proposed. By using atmospheric pressure plasma jet generated by dual‐frequency power sources, the morphologies of these TiO₂ films were investigated by scanning electron microscopy. The structures of these films were characterized by X‐ray diffraction and Raman Shift Spectroscopy. The elemental composition of these films [Colour figure can be viewed at wileyonlinelibrary.com ] were characterized by means of X‐ray photoelectron spectroscopy. The optical absorption of these films were studied by UV‐vis absorbance spectra. These results indicated that the nitrogen‐doped nanofibers TiO₂ films have mixed phases of anatase and rutile. They also display narrow band gap. The I‐V characteristics curves exhibited good conductivity ability. Optical emission spectroscopy (OES) was measured to analyze the active group.     

Mechanical Properties and Orientation of Atactic Poly(methyl methacrylate): Sub‐Tg Annealing and Stereocomplex Formation

The mechanical properties and orientation behavior of atactic poly(methyl methacrylate) films cast from acetone (A‐aPMMA films) and chloroform (C‐aPMMA films), with subsequent sub‐T_g annealing, have been studied. The formation of a stereocomplex in sub‐T_g‐annealed A‐aPMMA films and C‐aPMMA films was demonstrated by means of differential scanning calorimetry. Stereocomplex in A‐aPMMA films is more pronounced than in C‐aPMMA films at each annealing temperature. It is proposed that stereocomplex formation can process at temperatures below T_g, leading to enhanced yield stress and higher orientation.     

Corrosion resistances of passive films on low‐Cr steel and carbon steel in simulated concrete pore solution

The passive ranges of carbon steel rebar and 3Cr steel rebar in saturated Ca(OH)₂‐simulated concrete pore solution with pH 12.6 were determined by means of cyclic voltammetry and potentiodynamic polarization curves. Chronopotentiometry was used to obtain steady‐state conditions for the formation of passive films on rebar samples at different anodic potentials. Electrochemical impedance spectroscopy, Mott–Schottky and X‐ray photoelectron spectrometer curves were employed to compare the formed passive films at different potentials. Additionally, cyclic polarization curves were used to compare the corrosion resistances of formed passive films on the two rebars in saturated Ca(OH)₂‐simulated concrete pore solution with different concentration of Cl^?. The results show that the passive ranges of the two rebars are all between ?0.15 and +0.6 V, and more stable passive films can be formed on both rebars at the anodic potential of +0.3 V. In the absence of Cl^?, the stability and corrosion resistance of the passive film formed on the 3Cr rebar are better than those of CS rebar. The passive film of 3Cr steel has the relatively better pitting corrosion resistance than carbon steel in saturated Ca(OH)₂‐simulated concrete pore solution that contains different concentration of Cl^?. Copyright © 2016 John Wiley & Sons, Ltd.     

Oxidation‐induced nanostructures on Cu{100}, Cu(Ag) and Ag/Cu{100} studied by photoelectron spectroscopy

Initial surface oxidation and nanoscale morphology on Cu{100}, Cu(Ag) and Ag/Cu{100} have been investigated in situ by X‐ray photoelectron spectroscopy (XPS), X‐ray induced Auger electron spectroscopy (XAES) and the inelastic electron background analysis as a function of oxygen exposure at 3.7 × 10^?2 and 213 mbar pressures at a surface temperature of 373 K. Relative Cu₂O concentrations have been quantified by analysis of the peak shape of the XAES Cu LMM transition. The surface morphology of Cu₂O islands and the Ag layer has been characterized by inelastic electron background analysis of XAES O KLL and Ag 3d transitions. Oxygen‐induced segregation of Cu, as well as the subsequent Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces, has been investigated quantitatively. Our results indicate that Ag has a clear inhibitive effect on the initial oxidation and Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces. The Cu₂O islands are also observed to remain highly strained on Ag/Cu{100} even at higher O₂ exposures. The results suggest that strained Cu₂O islands eventually penetrate through the buried Ag layer, and in conjunction with segregating Cu atoms enable the oxidation to proceed at a similar rate to or even faster than on the unalloyed Cu surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Controllable Growth of Perovskite Films by Room‐Temperature Air Exposure for Efficient Planar Heterojunction Photovoltaic Cells

A two‐step solution processing approach has been established to grow void‐free perovskite films for low‐cost high‐performance planar heterojunction photovoltaic devices. A high‐temperature thermal annealing treatment was applied to drive the diffusion of CH₃NH₃I precursor molecules into a compact PbI₂ layer to form perovskite films. However, thermal annealing for extended periods led to degraded device performance owing to the defects generated by decomposition of perovskite into PbI₂. A controllable layer‐by‐layer spin‐coating method was used to grow “bilayer” CH₃NH₃I/PbI₂ films, and then drive the interdiffusion between PbI₂ and CH₃NH₃I layers by a simple air exposure at room temperature for making well‐oriented, highly crystalline perovskite films without thermal annealing. This high degree of crystallinity resulted in a carrier diffusion length of ca. 800 nm and a high device efficiency of 15.6 %, which is comparable to values reported for thermally annealed perovskite films.     

Electrical and structural properties of Pd/V/n‐type InP (111) Schottky structure as a function of annealing temperature

Palladium/Vanadium (Pd/V) Schottky structures are fabricated on n‐type InP (100) and the electrical, structural and surface morphological characteristics have been studied at different annealing temperatures. The extracted barrier height of as‐deposited Pd/V/n‐InP Schottky diode is 0.59 eV (I–V) and 0.79 eV (C–V), respectively. However, the Schottky barrier height of the Pd/V Schottky contact slightly increases to 0.61 eV (I–V) and 0.84 eV (C–V) when the contact is annealed at 200 °C for 1 min. It is observed that the Schottky barrier height of the contact slightly decreases after annealing at 300, 400 and 500 °C for 1 min in N₂ atmosphere. From the above observations, it is clear that the electrical characteristics of Pd/V Schottky contacts improve after annealing at 200 °C. This indicates that the optimum annealing temperature for the Pd/V Schottky contact is 200 °C. Basing on the auger electron spectroscopy and X‐ray diffraction results, the formation of Pd‐In intermetallic compound at the interface may be the reason for the increase of barrier height upon annealing at 200 °C. The formation of phosphide phases at the Pd/V/n‐InP interface could be the reason for the degradation in the barrier heights after annealing at 300, 400 and 500 °C. From the AFM results, it is evident that the overall surface morphology of the Pd/V Schottky contacts is fairly smooth. Copyright © 2011 John Wiley & Sons, Ltd.     

Biomimetic Approach to the Formation of Titanium Dioxide Thin Films by Using Poly(2‐(dimethylamino)ethyl methacrylate)

We demonstrate that the biomimetic method—which has been used for the formation of silica thin films—also could be applied directly to the formation of titanium dioxide (TiO₂) thin films, which are technologically important materials because of their applications to photocatalytic purifiers, photochemical solar cells, and others. After generation of poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) films on gold surfaces by surface‐initiated polymerization, titanium bis(ammonium lactato)dihydroxide was used as a precursor of TiO₂. The TiO₂/PDMAEMA films were successfully formed on the surfaces in aqueous solution at neutral pH (pH 6.7) and room temperature, and were characterized by X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscopy, and X‐ray diffractometry. The formed TiO₂ films have an amorphous nature and large area uniformity in thickness. The degree of crystallization was controlled by annealing. We also investigated the pH effect and the phosphate incorporation in the films by using phosphate‐buffered solutions. The TiO₂ films were formed in all the employed pH values in the range of 2 to 12, but phosphate anions were found to be incorporated into the films facilely only at low pH.     

Latex film formation studied with the atomic force microscope: Influence of aging and annealing

The surface structure of latex dispersion films was examined with an atomic force microscope. All measurements were done in air on latex films having a minimum film formation temperature of 12°C and a glass transition temperature of 18°C. One aim of this study was to follow structural changes during film formation. Three minutes after spreading the film, its surface layer dried. Afterwards, the structure of the film did not change anymore. Only after 4 months could structural changes be observed: Though individual latex particles could be identified, the particles partly melted into one another.After annealing films at 50° or 60°C for 4 h, the latex particles partly melted into one another, but individual particles could still be identified. When annealing at or above 80°C, no individual latex particles were visible anymore. With increasing temperature the film roughness decreased from 3 nm without annealing to 0.8 nm at 100°C annealing temperature. In addition, islands of 2–4 nm thickness appeared on the film surface. These islands could be scraped off the film by increasing the force between tip and sample, indicating that they are composed of surfactant which was squeezed out of the film.     

Effect of swift heavy ion irradiation on the physical properties of CuIn(S0.4Se0.6)2 alloy thin films prepared by solution growth technique

Alloy thin films of CuIn(S_0.4Se_0.6)₂ material were deposited using the solution growth technique. The various deposition parameters such as pH of solution, time, concentration of ions and temperature have been optimized for the device grade thin films. The as-deposited films were annealed in a rapid thermal annealing (RTA) system at 450 °C in air for 5 min and subjected to high-energy Ag ion irradiations. Ag ion irradiation has been performed with an energy of 100 MeV at a fluency of 5×10¹² ions/cm² on the thin film. The changes in optical and electrical properties that occurred before and after post-deposition treatments in CuIn(S_0.4Se_0.6)₂ thin films were studied using X-ray diffraction (XRD) and AFM; increase in crystallinity was observed after annealing and irradiation. In addition, structural damages were observed in irradiated thin films. After annealing and irradiation, the surface roughness was seen to be increased. Decrease in resistivity was observed, which is consistent with the optical energy band gap. The results are explained by considering the high energy deposited due to the electronic energy loss upon irradiation, which modified the properties of the material.     

Submicron films prepared from aqueous dispersions of nanoscale polymer crystals

Thin and ultrathin films of polyethylene of variable thickness are obtained from aqueous dispersions of prefabricated nanoscale crystals by spin‐coating. Continuous films with a thickness of only 15 nm, up to 220 nm, homogeneous over hundreds of μm, or assembled discontinuous monolayers of flat‐on lamella particles were prepared, depending on the solids content of the dispersion employed, as revealed by AFM and TEM. The morphology of melt‐recrystallized films was not affected by the surfactant present. Homogeneous continuous films without undesirable dewetting were retained upon melting and recrystallization of the films upon cooling, composed of polygonal spherulites for a thicker film (220 nm), randomly grown edge‐on lamella for a 40 nm film, and dominant flat‐on lamella for a 15 nm thick film. Annealing below T_m resulted in lamella thickening, without changes of crystal orientation or structure of the particle assemblies for discontinuous monolayers. Surfactant adsorbed to the nanocrystals in the aqueous dispersion desorbs at least partially during formation of the nascent films, and upon annealing below the melting point surfactant migrates to the film‐air interface to form aggregates, which can be removed by rinsing, during which the film stays intact and structurally unaltered as revealed, amongst others, by water contact angles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6420–6432, 2009     

Effect of Glass Substrates on the Formation of Gold-Silver Colloids in Nanocomposite Thin Films

A sol-gel route to synthesize nanocomposite thin films containing phase separated metal colloids of gold (Au) and silver (Ag) was developed. Ag—Au colloids were prepared in silica films using dip coating technique. The annealing of the samples in air results in the formation of phase separated Ag and Au colloids in SiO₂ thin films, showing the surface plasmon peaks at 410 nm and 528 nm. For the synthesis of phase separated Ag and Au colloids on float glass substrates, formation of the silver colloids was found strongly dependent on the surface of the float glass. On the tin rich surface formation of both gold and silver colloids took place, whereas, on the tin poor surface the formation of only gold colloids was observed. The surface dependence of the formation of silver colloids was attributed to the presence of tin as Sn²⁺ state on the glass surface, which oxidizes into Sn⁴⁺ during heat treatment, reducing Ag⁺ into silver colloids.     

Preparation and characterization of nanocomposite ZnO–Ag thin film containing nano-sized Ag particles: influence of preheating,annealing temperature and silver content on characteristics

Nanocomposite ZnO–Ag thin film containing nano-sized Ag particles have been grown on glass substrate by spin-coating technique using zinc acetate dihydrate as starting precursor in 2-propanol as solvent and monoethanolamine as stabilizer. Silver nanoparticles were added in the ZnO sol using silver nitrate dissolved in ethanol-acetonitrile. Their structural, electrical, crystalline size and optical properties were investigated as a function of preheating, annealing temperature and silver content. The results indicated that the crystalline phase was increased with increase of annealing temperature up to 550 °C at optimum preheating temperature of 275 °C. Thermal gravimetric differential thermal analysis results indicated that the decomposition of pure ZnO and nanocomposite ZnO–Ag precursors occurred at 225 and 234 °C, respectively with formation of ZnO wurtzite crystals. The scanning electron microscopy and atomic force microscopy revealed that the surface structure (the porosity and grain size) of the ZnO–Ag thin film (the film thickness is about 379 nm) was changed compared to pure ZnO thin film. The result of transmission electron microscopy showed that Ag particles were about 5 nm and ZnO particles 58 nm with uniform silver nanoclusters. Optical absorption results indicated that optical absorption of ZnO–Ag thin films decreased with increase of annealing temperature. Nanocomposite ZnO–Ag thin films with [Ag] = 0.068 M and [Ag] = 0.110 M showed an intense absorption band, whose maximum signals appear at 430 nm which is not present in pure ZnO thin films. The result of X-ray photoelectron spectroscopy revealed that the binding energy of Ag 3d_5/2 for ZnO–Ag shifts remarkably to the lower binding energy compared to the pure metallic Ag due to the interaction between Ag and ZnO.     

Effects of diethanolamine on the evolution of silver/titanium dioxide sol–gel process

In order to clarify the effects of diethanolamine (DEA) in the silver (Ag)/titanium dioxide (TiO₂) sol–gel process, sols with and without DEA, and films derived from these sols were prepared. The samples were investigated by X-ray diffraction, transmission electron microscopy, electron diffraction and optical absorption spectra. The results showed that metallic Ag clusters were formed in the sol with DEA and was absent in the sol without DEA. This indicated that DEA worked not only as the stabilizer but also as the reduce agent in Ag/TiO₂ sol–gel process. After annealed, Ag metallic nanoparticles were generated in the films derived from both the sols with and without DEA. The particles in the films derived from the sol with DEA were smaller than those from the sol without DEA. This can be ascribed to the limitation of the growth of Ag cluster formed in the sol with DEA during heat treatment. Mechanisms for the formation of metallic Ag in the Ag/TiO₂ sols and films were discussed. The effects of DEA in the sols and films were studied in detail.