衬底温度对HfOxNy薄膜光学性质的影响

采用射频反应磁控溅射法制备了HfOxNy栅介质薄膜,并研究了HfOxNy栅介质薄膜的光学特性随淀积温度的变化而发生变化的规律．椭偏仪模拟结果显示HfOxNy薄膜的折射率和消光系数都是随衬底温度的升高而增加,根据消光系数和吸收系数还得到了HfOxNy薄膜的光学带隙值,随着衬底温度的升高,带隙减小,这主要是由于N含量的增加所致．     

Effect of Power Density on the Electrochemical Properties of Undoped Amorphous Carbon (a‐C) Thin Films

Undoped a‐C thin films were deposited with varying power density from 10 to 25 W/cm² using unbalanced closed‐field magnetron sputtering (CFUBMS). The effect of power density on the physical and electrochemical properties was investigated by experimental characterization methods and atomistic simulations. XPS indicated that the films were composed mostly of sp²‐bonded carbon (55–58 at.%) with a small amount of oxygen (8–9 at.%) in the surface region. The films appeared completely amorphous in XRD. The I_D/I_G ratio obtained by Raman spectroscopy indicated an increase from 1.76 to 2.34 with power density. The experimental and simulated data suggested a possible ordering and/or clustering of the sp² phase with power density as the cause of the improved electrical properties of the a‐C films. The electrochemical properties of a‐C were between those of glassy carbon and tetrahedral amorphous carbon with potential windows ranging from 2.77 to 2.93 V and double‐layer capacitance values around 0.90 μF cm^?2. Electron transfer for Ru(NH₃)₆^3+/2+ and FcMeOH^+1/0 was reversible whereas that for IrCl₆^2?/3? was quasi‐reversible. Peak potential separation of dopamine and oxidation potential of ascorbic acid decreased with power density, correlating with the structural and electrical changes of the films. The a‐C thin films deposited by CFUBMS are inherently conductive and their physical properties can be adjusted by varying the deposition parameters to a wide range of electrochemical applications.     

Photocatalytic Nanocomposite Films Fabricated by Layer‐by‐Layer Self‐assembly of TiO2 Nanoparticles and Lignosulfonates

Photocatalytic multilayer nanocomposite films composed of anatase TiO₂ nanoparticles and lignosulfonates (LS) were fabricated on quartz slides by the layer‐by‐layer (LBL) self‐assembly technique. X‐ray photoelectron spectroscopy (XPS), UV‐vis spectroscopy and atomic force microscopy (AFM) were used to characterize the TiO₂/LS multilayer nanocomposite films. Moreover, the photocatalytic properties (decomposition of methyl orange and bacteria) of multilayer nanocomposite films were investigated. XPS results indicated that the intensities of titanium and sulfur peaks increased with the LBL deposition process. A linear increase in absorbance at 280 nm was found by UV‐Vis spectroscopy, suggesting that stepwise multilayer growth occurs on the substrate and this deposition process is highly reproducible. AFM images showed that quartz slide was completely covered by TiO₂ nanoparticles when a 10‐bilayer multilayer film was formed. The decomposition efficiency of methyl orange by TiO₂/LS multilayer films under the same UV irradiation time increased linearly with the number of TiO₂ layers, and the results of decomposition of bacteria under UV irradiation showed that TiO₂/LS multilayer nanocomposite films exhibited excellent decomposition activity of bacteria (Escherichia coil).     

A Combinatorial Approach for Optimization of Oxygen Evolution Catalyst Loading on Mo‐doped BiVO4 Photoanodes

The incident photon to current efficiency (IPCE) of a photoactive surface strongly depends on the loading and thickness of the active materials. We present a combinatorial approach based on an optical scanning droplet cell for simultaneous deposition and systematic characterization of co‐catalysts for the oxygen evolution reaction (OER) on Mo‐doped BiVO₄ (Mo?BiVO₄) photoanodes electrochemically pre‐deposited on transparent conductive FTO substrates. The loading and photoelectrochemical characterization of 10 different OER co‐catalysts deposited by three different deposition techniques on FTO‐supported Mo?BiVO₄ were investigated aiming at determination of the suitable deposition parameters affording the highest enhancement of photoelectrochemical oxygen evolution for the different OER/Mo?BiVO₄ films. A comparison of the photoelectrochemical performance of films of various OER co‐catalyst deposited on FTO‐supported Mo?BiVO₄ by electrodeposition, photo‐assisted electrodeposition and photodeposition revealed the necessity of a material specific optimization with respect to co‐catalyst loading and deposition technique to achieve optimal IPCE for each co‐catalysts.     

Evolution of the local structure in GaN:O thin films grown by ion‐assisted deposition with film thickness

Optical and optoelectronic properties of gallium nitride strongly depend on the synthesis procedure, which may be related to specific structural characteristics of GaN inherent to each preparation condition. Amorphous and nanocrystalline GaN films have been prepared by ion‐assisted deposition (IAD). The films prepared at 10^?5 Torr for <50 min have shown exploitable optoelectronic properties, in spite of the high concentration of oxygen of these films (up to 25 at.%). We study here the evolution of the local structure around Ga atoms as the deposition time increases. Five IAD GaN films of thickness ranging between 140 and 450 nm on silicon substrates were analysed by x‐ray absorption fine structure (XAFS) at the Ga K‐edge. The first and second shells of neighbouring atoms are clearly identified in the radial distribution functions at approximately 1.9 and 3.2 Å, respectively. In all of the films, Ga seems to be tetrahedrally coordinated to four nitrogen atoms, some of which may be substituted by oxygen. For deposition times <50 min, analysis of both x‐ray adsorption near‐edge structure (XANES) and extended x‐ray adsorption fine structure (EXAFS) regions indicates that the material is highly amorphous. Above this threshold, a peak corresponding to the first coordination sphere of Ga atoms becomes discernible and increases in intensity for longer deposition times, indicating that the second shell of atoms is now more ordered. The pseudo Debye–Waller factor of the Ga shell is used for monitoring the average degree of amorphization in an ～100 nm thick top layer, which seems to be related to the film oxygen content. The XAFS results are compatible with a layered distribution of crystallinity, as has been suggested previously for these films. Copyright © 2005 John Wiley & Sons, Ltd.     

Substrate temperature influenced physical properties of silicon MOS devices with TiO2 gate dielectric

DC reactive magnetron sputtering technique was employed for deposition of titanium dioxide (TiO₂) films. The films were formed on Corning glass and p‐Si (100) substrates by sputtering of titanium target in an oxygen partial pressure of 6×10^?2 Pa and at different substrate temperatures in the range 303 – 673 K. The films formed at 303 K were X‐ray amorphous whereas those deposited at substrate temperatures ≥ 473 K were transformed into polycrystalline nature with anatase phase of TiO₂. Fourier transform infrared spectroscopic studies confirmed the presence of characteristic bonding configuration of TiO₂. The surface morphology of the films was significantly influenced by the substrate temperature. MOS capacitor with Al/TiO₂/p‐Si sandwich structure was fabricated and performed current–voltage and capacitance–voltage characteristics. At an applied gate voltage of 1.5 V, the leakage current density of the device decreased from 1.8 × 10^?6 to 5.4 × 10^?8 A/cm² with the increase of substrate temperature from 303 to 673 K. The electrical conduction in the MOS structure was more predominant with Schottky emission and Fowler‐Nordheim conduction. The dielectric constant (at 1 MHz) of the films increased from 6 to 20 with increase of substrate temperature. The optical band gap of the films increased from 3.50 to 3.56 eV and refractive index from 2.20 to 2.37 with the increase of substrate temperature from 303 to 673 K. Copyright © 2012 John Wiley & Sons, Ltd.     

Nanostructured ZrO2 and Zr‐C‐N Coatings from Chemical Vapor Deposition of Metal‐Organic Precursors

Nanocrystalline zirconium carbonitride (Zr‐C‐N) and zirconium oxide (ZrO₂) films were deposited by chemical vapor deposition (CVD) of zirconium‐tetrakis‐diethylamide (Zr(NEt₂)₄) and ‐tert‐butyloxide (Zr(OBu^t)₄), respectively. The films were deposited on iron substrates and characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The Zr‐C‐N films show blue, golden brown or bronze colours, with colour stability depending upon the precursor composition (pure metal amide or mixed with Et₂NH). The deposition temperature showed no pronounced effect on the granular morphology of the Zr‐C‐N films. The XRD data of the films correspond to the formation of carbonitride phase whereas the XPS analyses revealed a strong surface oxidation and incorporation of oxygen in the film. The films deposited using a mixture of Zr(NEt₂)₄ and Et₂NH showed higher N content, better adhesion and scratch resistance when compared to films obtained from the CVD of pure Zr(NEt₂)₄. Subject to the precursor composition and deposition temperature (550‐750 °C), the microhardness values of Zr‐C‐N films were found to be in the range 2.11‐5.65 GPa. For ZrO₂ films, morphology and phase composition strongly depend on the deposition temperature. The CVD deposits obtained at 350 °C show tetragonal ZrO₂ to be the only crystalline phase. Upon increasing the deposition temperature to 450 °C, a mixture of tetragonal and monoclinic modifications was formed with morphology made up of interwoven elongated grains. At higher temperatures (550 and 650 °C), pure monoclinic phase was obtained with facetted grains and developed texture.     

Cross‐linked Multilayer Polymer‐Clay Nanocomposites and Permeability Properties

Abstract

Electrostatically layered aluminosilicate nanocomposites have been prepared by the sequential deposition of poly(allylamine hydrochloride)/poly(acrylic acid)/poly(allylamine hydrochloride)/saponite (PAH/PAA/PAH/saponite)₁₀ on poly(ethylene terephtalate) (PET) film. Exfoliated saponite nanoplatelets were obtained by extensive shaking, sonication, and centrifugation of a water suspension. To minimize permeability and improve the mechanical integrity, cross‐linking of composite films was carried out at different temperatures. The formation of amide linkage induced through heating was observed by Fourier Transform Infrared (FT‐IR) and x‐ray photoelectron spectroscopy (XPS). The cross‐linking of nanocomposites (PAH/PAA/PAH/saponite)₁₀ showed 60% decrease in permeability of oxygen when compared with the pristine PET substrate film. In contrast, water permeability of the nanocomposite membrane was not affected by heating temperature and deposition cycles.     

Lower friction and higher wear resistance of fluorine‐incorporated amorphous carbon films

Plasma‐enhanced chemical vapor deposition was employed to fabricate hydrogenated amorphous carbon (a‐C:H) films and fluorine‐doped hydrogenated amorphous (a‐C:H:F) carbon films. For comparison purpose, the a‐C:H films were treated with CF₄ plasma. The bonding structure and tribological behavior of the films were investigated. The results indicate that the F presented mainly in the forms of C–F₃, C–F and C–F₂ groups in both the a‐C:H:F film and the surface CF₄ plasma processed hydrogenated amorphous carbon (F‐P‐a‐C:H) films. Moreover, the a‐C:H:F films, because of the transformation of sp³ to sp², possess a lower friction coefficient than that of the F‐P‐a‐C:H films. Copyright © 2013 John Wiley & Sons, Ltd.     

An iron (II) guanidinate compound: Synthesis,characterization, thermal properties and its application as a CVD precursor for iron oxide film

An iron compound containing guanidinate ligand [Fe((SiMe₃)₂NC(ⁱPrN)₂)₂] was synthesized using a conventional lithium‐salt‐elimination reaction, and its chemical structure was characterized through elemental analysis, ¹H‐NMR and single‐crystal X‐ray diffraction, respectively. The thermal properties of the compound were examined through thermogravimetric analysis (TGA), and the TGA results demonstrated that the compound possessed sufficient volatility and suitable thermal stability for the CVD process. Moreover, the deposition experiments were conducted using the synthesized compound as a precursor and O₂ as an oxygen source to confirm its applicability as a CVD precursor, and α‐Fe₂O₃ films were successfully deposited at a relatively low deposition temperature (300°C).     

Synthesis,Characterization, Thermal Property of Si(c‐C5H9NH)4 and Its Potential as CVD Precursor for SiC Film

Silicon(IV) amide Si(c‐C₅H₉NH)₄ ( 1 ), was synthesized and characterized by ¹H, ¹³C, and ²⁹Si NMR spectroscopy, EI‐MS, elemental analysis, and X‐ray diffraction. Its thermal stability and volatility were also investigated. The as‐grown film, which was characterized by SEM, AFM, XRD and XPS, was deposited using 1 as single precursor through a low‐pressure chemical vapor deposition (LPCVD) process at a temperature as low as 600 °C. The results demonstrated that silicon(IV) amides can be promising single‐precursor for deposition of low‐temperature SiC films.     

Bioactivity and mechanical properties of nickel‐incorporated hydrogenated carbon nanocomposite thin films

In this paper, the influence of nickel incorporation on the mechanical properties and the in vitro bioactivity of hydrogenated carbon thin films were investigated in detail. Amorphous hydrogenated carbon (a‐C:H) and nickel‐incorporated hydrogenated carbon (Ni/a‐C:H) thin films were deposited onto the Si substrates by using reactive biased target ion beam deposition technique. The films' chemical composition, surface roughness, microstructure and mechanical properties were investigated by using XPS, AFM, TEM, nanoindentation and nanoscratch test, respectively. XPS results have shown that the film surface is mainly composed of nickel, nickel oxide and nickel hydroxide, whereas at the core is nickel carbide (Ni₃C) only. The presence of Ni₃C has increased the sp² carbon content and as a result, the mechanical hardness of the film was decreased. However, Ni/a‐C:H films shows very low friction coefficient with higher scratch‐resistance behavior than that of pure a‐C:H film. In addition, in vitro bioactivity study has confirmed that it is possible to grow dense bone‐like apatite layer on Ni/a‐C:H films. Thus, the results have indicated the suitability of the films for bone‐related implant coating applications. Copyright © 2011 John Wiley & Sons, Ltd.     

Self‐Assembly of Gold Nanoparticles/Electroactive Polyelectrolyte Multilayer Films for Tunable Electrocatalysis

This study described fabrication, characterization, and application of multilayer films based on layer‐by‐layer assembly of ferrocene poly(ethylenimine) and gold nanoparticles. Assembly process of the multilayer film was investigated by atomic force microscopy, UV‐visible absorption spectroscopy and electrochemical impedance spectroscopy. The multilayer films exhibited a pair of well‐defined redox peaks as revealed by cyclic voltammetry, as well as bifunctional and fine‐tunable electrocatalysis for oxidation of ascorbic acid and reduction of oxygen. Both the outer layer and layer number had effect on the electrocatalytic response. Electrocatalytic activity of the films could be controlled with assemblies at the nanoscale level by simply adjusting deposition cycles or amount of component in the films.     

The structure and tribological properties of aluminum/carbon nanocomposite thin films synthesized by reactive magnetron sputtering

Hydrogenated nanocomposite aluminum/carbon thin films (Al/a‐C:H) were fabricated on stainless steel and silicon wafer substrates via unbalanced reactive magnetron sputtering from an Al target in CH₄/Ar plasma. The composition and structure of Al/a‐C:H films were investigated by high‐resolution transmission electron microscope (HRTEM), XPS and micro‐Raman spectroscopy. Nanoindenter, interferometer and ball‐on‐disc tribometer were carried out to evaluate the hardness, internal stress and tribological properties of Al/a‐C:H films. HRTEM observations confirmed that the metallic Al nanocrystallites were uniformly dispersed in the amorphous carbon matrix. XPS and Raman analyses indicated that the sp² content increased with the increase of Al content in the films. Nanoindenter and interferometer tests exhibited that the uniform incorporation of Al nanocrystallites can diminish drastically the magnitude of internal stress with maintaining the higher hardness of as‐deposited films. Especially, the ball‐on‐disc tribometer measurements revealed that the nanocomposite film with 2.3 at.% Al content exhibited relatively better wear resistance and self‐lubrication performance with a friction coefficient of 0.06 and wear rate of 3.1 × 10^?16 m³/ N·m under ambient air, which can be attributed to the relatively higher hardness, the formation of continuous graphitized transfer film on counterface and the reduced reaction of oxygen with carbon. Copyright © 2010 John Wiley & Sons, Ltd.     

TiOx Films Deposited by Plasma Enhanced Chemical Vapour Deposition Method in Atmospheric Dielectric Barrier Discharge Plasma

The plasma enhanced chemical vapour deposition method applying atmospheric dielectric barrier discharge (ADBD) plasma was used for TiO_x thin films deposition employing titanium (IV) isopropoxide and oxygen as reactants, and argon as a working gas. ADBD was operated in the filamentary mode. The films were deposited on glass. The films?? chemical composition, surface topography, wettability and aging were analysed, particularly the dependence between precursor and reactant concentration in the discharge atmosphere and its impact on TiO_x films properties. Titanium in films near the surface area was oxidized, the dominating species being TiO₂ and substoichiometric titanium oxides. The films exhibited contamination with carbon, as a result of atmospheric oxygen and carbon dioxide reactions with radicals in films. No relevant difference of the film surface due to oxygen concentration inside the reactor was determined. The films were hydrophilic immediately after deposition, afterwards their wettability diminished, due to chemical reactions of the film surface and chemical groups involved in the atmosphere.     

Mechanical and barrier properties of ternary nanocomposite films based on polycarbonate/amorphous polyamide blends modified with a nanoclay

Ternary polycarbonate (PC)/amorphous polyamide–nanoclay (naPA) nanocomposite (PC/naPA) films were obtained by melt mixing and drawing, and the effects of the naPA content and the draw ratio (DR) on the structure, morphology and mechanical and barrier properties were studied. Despite the presence of nanoclay, the films exhibited a negligible roughness and the excellent optical properties of PC and amorphous polyamide (aPA). The dispersed naPA phase was pure and small, indicating compatibility. The naPA did not hinder the drawing ability of PC. At low DRs the dispersed phase was elongated and oriented along the machine direction (extrusion flow direction), but at high DRs, it fibrillated due to the higher non‐isothermal elongational flow induced by drawing. The laminar structure of the nanoclay allowed the films to be reinforced both in the machine and the transverse directions. The oxygen permeability of PC was reduced by 42% in the nanocomposite with 25% of naPA, and dropped further with the DR, which is attributed to the increased tortuosity of the oxygen path induced by fibrillation. Copyright © 2015 John Wiley & Sons, Ltd.     

Atomic Layer Deposition of Cobalt Phosphide for Efficient Water Splitting

Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co‐P films were deposited by using PH₃ plasma as the phosphorus source and an extra H₂ plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self‐limited layer‐by‐layer growth, and the deposited Co‐P films were highly pure and smooth. The Co‐P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co‐P films prepared by the traditional post‐phosphorization method. Moreover, the deposition of ultrathin Co‐P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three‐dimensional (3D) architectures.     

Oxygen‐Assisted Cathodic Deposition of Zeolitic Imidazolate Frameworks with Controlled Thickness

Processing metal–organic frameworks (MOFs) as films with controllable thickness on a substrate is increasingly crucial for many applications to realize function integration and performance optimization. Herein, we report a facile cathodic deposition process that enables the large‐area preparation of uniform films of zeolitic imidazolate frameworks (ZIF‐8, ZIF‐71, and ZIF‐67) with highly tunable thickness ranging from approximately 24 nm to hundreds of nanometers. Importantly, this oxygen‐reduction‐triggered cathodic deposition does not lead to the plating of reduced metals (Zn and Co). It is also operable cost‐effectively in the absence of supporting electrolyte and facilitates the construction of well‐defined sub‐micrometer‐sized heterogeneous structures within ZIF films.     

Electrocatalytic Reduction of Oxygen at Glassy Carbon Electrodes Coated with Diazonium‐derived Porphyrin/Metalloporphyrin Films

In this study, the influence of the film structure was investigated on the electrocatalytic oxygen reduction at GC electrodes covered with porphyrin and metalloporphyrin rings via the diazonium modification method. For that purpose, primarily, tetraphenylporphyrin (TPP) films on GC electrode surfaces were prepared by electroreduction of in situ generated diazonium salts of 5‐(4‐aminophenyl)‐10,15,20‐triphenylporphyrin (APP) and 5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin (TAPP) molecules. Next, the formation of metalloporphyrin films on the modified surfaces was accomplished through the complexation reactions of surface porphyrin rings with metal ions in the salt solutions containing Mn(II), Fe(III) and Co(II) ions. The resulting porphyrin and metalloporphyrin layers were identified with XPS and ICP‐MS. The electrochemical barrier properties of the films on GC surfaces were examined by cyclic voltammetry in K₃Fe(CN)₆ aqueous solution. The electrocatalytic abilities of the resulting films were also investigated for the oxygen electrochemical reduction by employing cyclic voltammetry in PBS solutions saturated with oxygen. The results showed that the oxygen reduction potentials on modified GC electrodes were shifted to less negative potentials compared to that of bare GC electrode. Also, it was obtained that the oxygen reduction reaction was more effective on the GC electrodes modified with TPP rings by using TAPP molecules than those prepared by using APP molecules.     

Preparation of films from aluminum acetylacetonate by plasma sputtering

Aluminum acetylacetonate has been reported as a precursor for the deposition of alumina films using different approaches. In this work, alumina‐containing films were prepared by plasma sputtering this compound, spread directly on the powered lowermost electrode of a reactor, while grounding the substrates mounted on the topmost electrode. Radiofrequency power (13.56 MHz) was used to excite the plasma from argon atmosphere at a working pressure of 11 Pa. The effect of the plasma excitation power on the properties of the resulting films was studied. Film thickness and hardness were measured by profilometry and nanoindentation, respectively. The molecular structure and chemical composition of the layers were analyzed by Fourier transform infrared spectroscopy and energy dispersive spectroscopy. Surface micrographs, obtained by scanning electron microscopy, allowed the determination of the sample morphology. Grazing incidence X‐ray diffraction was employed to determine the structure of the films. Amorphous organic layers were deposited with thicknesses of up to 7 µm and hardness of around 1.0 GPa. The films were composed by aluminum, carbon, oxygen and hydrogen, their proportions being strongly dependent on the power used to excite the plasma. A uniform surface was obtained for low‐power depositions, but particulates and cracks appeared in the high‐power prepared materials. The presence of different proportions of aluminum oxide in the coatings is ascribed to the different activations promoted in the metalorganic molecule once in the plasma phase. Copyright © 2013 John Wiley & Sons, Ltd.