Effect of post annealing treatment on electrochromic properties of spray deposited niobium oxide thin films

Niobium oxide thin films were deposited on the glass and fluorine doped tin oxide (FTO) coated glass substrates using simple and inexpensive spray pyrolysis technique. During deposition of the films various process parameters like nozzle to substrate distance, spray rate, concentration of sprayed solution were optimized to obtain well adherent and transparent films. The films prepared were further annealed and effect of post annealing on the structural, morphological, optical and electrochromic properties was studied. Structural and morphological characterizations of the films were carried out using scanning electron microscopy, atomic force microscopy and X-ray diffraction techniques. Electrochemical properties of the niobium oxide thin films were studied by using cyclic-voltammetry, chronoamperometry and chronocoulometry.     

Scanning microelectrochemical characterization of the anti-corrosion performance of inhibitor films formed by 2-mercaptobenzimidazole on copper

The aim of this work is to explore the applicability of the scanning electrochemical microscope (SECM) to characterize the inhibiting effect of 2-mercaptobenzimidazole against the corrosion of copper. SECM was operated in the feedback mode by using ferrocene-methanol as redox mediator, and the sample was left unbiased at all times. The kinetic changes in the corrosion processes were monitored over time from the Z-approach curves. Furthermore, inhibitor-modified copper samples presenting various surface finishes were imaged by SECM and the scanning vibrating electrode technique (SVET), allowing changes both in the surface activity of metal-inhibitor films and in the extent of corrosion attack to be spatially resolved. Differences in the local electrochemical activity between inhibitor-free and inhibitor-covered areas of the sample were successfully monitored.     

Tribocorrosion behaviour of TiCxOy thin films in bio-fluids

Decorative coatings require not only an attractive appearance for market applications, but also an ability to protect the surface underneath. Because of this, corrosion, wear and their combined effects (termed tribocorrosion) are particularly important for lifetime prediction. In this paper, the tribocorrosion behaviour of a range of single layered titanium oxycarbide, TiC_xO_y, coatings, produced by DC reactive magnetron sputtering, has been studied and reported as a function of electrode potential and applied load. The study was conducted in a reciprocating sliding tribo-system (Plint TE 67/E) in a bio-fluid (an artificial perspiration solution) at room temperature. During the wear tests, both the open-circuit potential and the corrosion current were monitored. The results showed that electrode potential and load have a significant influence on the total material loss. The variations in R_p (polarization resistance) and C_f (capacitance) before and after sliding, obtained by Electrochemical Impedance Spectroscopy (EIS) were evaluated in order to provide an understanding of the resistance of the film in such conditions. Tribocorrosion maps were generated, based on the results, indicating the change in mechanisms of the tribological and corrosion parameters for such coatings, as a function of load and applied potential.     

甲烷浓度对金刚石薄膜(100)织构生长的影响

以H2和CH4的混合气体为气源,用微波等离子体辅助化学气相沉积法(MPECVD)在1 cm×1 cm S i(100)基体上沉积了金刚石薄膜。研究了不同的甲烷浓度对金刚石薄膜(100)织构生长趋势的影响。分别采用扫描电子显微镜(SEM),Ram an光谱对金刚石膜的表面形貌、质量进行了分析。结果表明,当基体温度为750℃,气压为4.8×103Pa,甲烷浓度为1.4%时,薄膜表面为(100)织构。     

Growth of faceted, ballas-like and nanocrystalline diamond films deposited in CH4/H2/Ar MPCVD

The influence of Ar addition to CH₄/H₂ plasma on the crystallinity, morphology and growth rate of the diamond films deposited in MPCVD was investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. X-Ray diffraction patterns indicate that diamond films of strong (111) and weak (400) texture are produced in these samples. Faceted diamond gradually turns into ballas-like diamond with graphitic inclusions when the Ar concentration increases to above 30 vol.%, as indicated by Raman spectra. As the Ar concentration goes above 90 vol.%, nanocrystalline diamond films are formed, characterized by a 1150-cm⁻¹ peak in the Raman spectra and morphology observation. Diamond growth by CH₃ or by C₂ mechanism is proposed to interpret the change in the growth rate of diamond films with the variation of Ar content in the plasma.     

Effect of N doping on properties of diamond-like carbon thin films produced by RF capacitively coupled chemical vapor deposition from different precursors

In this paper, we report results concerning properties of diamond-like carbon (DLC) thin films obtained in different experimental conditions: various RF power values and different precursors (methane, acetone and toluene or in combination with nitrogen). The deposition rate of DLC thin films obtained from precursors with low ionizing energy and high number of carbon atoms in molecule as acetone and toluene was higher (142 nm/min for acetone and 607 nm/min for toluene as compared with 79 nm/min for methane at 400 W input power). The highest value of hardness was obtained from methane (18 GPa). In the case of acetone and toluene precursors, the hardness increased with input power to the highest values of 16.8 and 14.8 GPa. By utilizing nitrogen as doping element, the resistivity of DLC thin films obtained from methane and acetone decreased from values higher than 10⁷ Ω cm to lower values of 12.5×10³ Ω cm for 3.79% nitrogen atomic concentration in the case of films obtained from methane and 40×10³ Ω cm for 4.26% nitrogen atomic concentration in the case of films obtained from acetone.     

The effect of thermal annealing on the adherence of Al2O3 films deposited by LP-MOCVD on several high alloy steels

Thin alumina films, deposited at 280°C on several high alloy steels by low-pressure metal-organic chemical vapor deposition (LP-MOCVD), were annealed at 0.17 kPa in a nitrogen atmosphere for 2, 4, and 17 h at 600 and 800°C. Film adhesion was studied by scanning scratch testing (SST) and Auger electron spectroscopy (AES). The best adhesion properties were obtained with commercial oxide dispersion-strengthened (ODS) high-temperature alloys, especially PM 3030. Among the 'normally' high alloy stainless steels, type AISI-321 showed the best adhesion. The other stainless steel-alumina combinations exhibited a reduced critical load, L_c, after thermal treatment. Alumina on ODS alloys exhibited an increased adhesion. AES studies revealed that this increase could be explained by: (1) the presence of sulfur-trapping elements, preventing segregation of sulfur at the interface; and (2) titanium and carbon enrichment at the interface, resulting in an anchoring effect between the oxide and the substrate.     

Scanning electrochemical microscopy studies of micropatterned copper sulfide (CuxS) thin films fabricated by a wet chemistry method

Patterned copper sulfide (Cu_xS) microstructures on Si (1 1 1) wafers were successfully fabricated by a relatively simple solution growth method using copper sulfate, ethylenediaminetetraacetate and sodium thiosulfate aqueous solutions as precursors. The Cu_xS particles were selectively deposited on a patterned self-assembled monolayer of 3-aminopropyltriethoxysilane regions created by photolithography. To obtain high quality Cu_xS films, preparative conditions such as concentration, proportion, pH and temperature of the precursor solutions were optimized. Various techniques such as optical microscopy, atomic force microscopy (AFM), X-ray diffraction, optical absorption and scanning electrochemical microscopy (SECM) were employed to examine the topography and properties of the micro-patterned Cu_xS films. Optical microscopy and AFM results indicated that the Cu_xS micro-pattern possessed high selectivity and clear edge resolution. From combined X-ray diffraction analysis and optical band gap calculations we conclude that Cu₉S₅ (digenite) was the main phase within the resultant Cu_xS film. Both SECM image and cyclic voltammograms confirmed that the Cu_xS film had good electrical conductivity. Moreover, from SECM approach curve analysis, the apparent electron-transfer rate constant (k) in the micro-pattern of Cu_xS dominated surface was estimated as 0.04 cm/s. The SECM current map showed high edge acuity of the micro-patterned Cu_xS.     

SECM imaging of electrocatalytic activity for oxygen reduction reaction on thin film materials

The oxygen reduction reaction (ORR) on sputtered Pt thin films in acidic solution was successfully studied by scanning electrochemical microscopy (SECM) in a modified tip generation-substrate collection (TG-SC) mode. SECM images of ORR activity in different sample areas were obtained and it is shown that this TG-SC SECM technique can be used to screen electrocatalytic activity of continuous thin film samples efficiently and quickly for the ORR in an acidic medium. It is observed that this technique is not very sensitive to the tip-substrate separation within a certain range. The SECM images obtained are strongly dependent on the substrate potential. The advantages of this technique for studying ORR electrocatalysts are discussed.     

Characterizing the relationship between hyperstoichiometry, defect structure and local corrosion kinetics of uranium dioxide

The ability of the UO₂ fluorite structure to accommodate large amounts of interstitial oxygen in various lattice sites leads to the formation of hyper-stoichiometric phases. The defect structures occurring in hyper-stoichiometric UO_2 + x over the range 0.02 ≤ x ≤ 0.1 have been characterized by SEM/EDX and Raman analyses. The results demonstrate that as the nominal stoichiometry increases from 2.002 to 2.1, the diversity of defective structures existing on the UO_2 + x surface also increases. Scanning electrochemical microscopy (SECM) measurements combined with a theoretical model were used to determine the rate constant for the reduction of the redox mediator ferrocene methanol, acting as a cathodic oxidant to corrode the four UO_2 + x specimens. The rate constant was found to vary with location on the surface. Stoichiometric locations, with a well defined fluorite structure, exhibited very low corrosion rates. Higher rates were observed at more non-stoichiometric locations with the highest rates being obtained on locations exhibiting tetragonal distortions as their composition approached UO_2.33. The distribution of rates increases with the degree of nominal non-stoichiometry as the diversity of microstructures existing on the UO_2 + x surface increases.     

Atmospheric flame vapor deposition of WO3 thin films for hydrogen detection with enhanced sensing characteristics

Nowadays, with the increasing demand for hydrogen, sensors that can detect low concentrations of this gas are essential for its safe use. In this paper, Pd/WO₃ film hydrogen sensors are developed using a solid-feed flame vapor deposition (SF-FVD), as an atmospheric, economical, and fast film fabrication method. The crystal structure and morphology of the samples were characterized by different means. The performance of the obtained sensors was investigated for different hydrogen concentrations (1–2500 ppm) and at different operating temperatures (100–250 °C). We attempted to determine the optimum deposition conditions, including feed and substrate to flame nozzle distances. In most of the sensing conditions, the response and recovery times were measured in the order of 20 to 30 s. The layer with a more open morphology showed sensitivity at ppb hydrogen level, good stability, and selectivity. The response behavior of the samples was explained according to the power-law in the metal oxide semiconductor (MOS) gas sensors.     

Ru-doped nanostructured carbon films

Pure and Ru-doped carbon films are deposited on Si (100) substrates by electron cyclotron resonance chemical vapor deposition. The films are characterized by transmission electron microscopy, electron energy loss spectroscopy, energy dispersive X-ray spectroscopy and atomic force microscopy. In both the pure and Ru-doped samples, diamond nanocrystallites are formed in amorphous carbon matrices. The Ru-doped film contains much smaller diamond nanocrystallites (approx. 3 nm) than the pure samples (approx. 11 nm). Lower surface roughnesses are observed in both pure and Ru-doped samples as compared to other reported nanocrystalline diamond films. The conductivity of the Ru-doped film is significantly higher than that of the pure film. The results show that Ru-doped nanocrystalline diamond films have unique structures and properties as compared to pure nanocrystalline diamond films or metal doped diamond-like carbon films, which may offer advantages for electrochemical, optical-window, field emission or tribological applications.     

Impact of oxygen partial pressure on resistive switching characteristics of PLD deposited ZnFe2O4 thin films for RRAM devices

In this paper we show resistive switching characteristics of ZnFe₂O₄ thin films grown by pulsed laser deposition at various oxygen partial pressures. We discuss how the microstructure, surface roughness, oxidation condition, and resistive switching properties of ZnFe₂O₄ thin films are influenced by the oxygen partial pressure prevalent in the chamber during the deposition process. The films were deposited at oxygen partial pressure (pO₂) of 0.0013, 0.013, 0.13 and 1.3 mbar. The ZnFe₂O₄ thin film deposited at the lowest pO₂ (0.0013 mbar) did not display a resistive switching characteristic. The ZnFe₂O₄ device deposited at 0.13 mbar yielded the best results. These devices have a low SET variance and a large memory window (more than 2 orders of magnitude) due to an optimum amount of oxygen vacancies/ions contained in the ZnFe₂O₄ film, which is helpful for better resistive switching, than devices deposited at other oxygen pressures. We also find that the migration of oxygen vacancies is linked to the resistive switching process.     

A study of ion exchange at the poly(butyl viologen)-electrolyte interface by SECM

In this work, the ion exchange characteristics of poly(butyl viologen) (PBV) thin films on a platinum electrode has been investigated by cyclic voltammetric (CV) scans. Since ferrocyanide anions (Fe(CN)₆⁴⁻) were added during the polymerization of the PBV thin-film for its stability, Fe(CN)₆⁴⁻ could form charge transfer complex with monomer and co-deposited with polymer. Scanning electrochemical microscopy (SECM) was used to probe the released Fe(CN)₆⁴⁻ ions from PBV film with Os(bpy)₃Cl₂ as a mediator for the approaching process in 0.5 M KCl medium. Mass changes during the redox process of the film were also monitored in-situ by electrochemical quartz crystal microbalance (EQCM). The ion exchange and transport behavior was observed during CV cycling of the film of the SECM and EQCM. The insertion and extraction of anions were found to be potential-dependence. Moreover, the decrease in tip current of released Fe(CN)₆⁴⁻ with increasing cycle number accounted for the ion exchange between Fe(CN)₆⁴⁻ and Cl⁻ in the KCl electrolyte. However, the Fe(CN)₆⁴⁻/Fe(CN)₆³⁻ redox couple was found to be highly stable between 0.0 and 0.5 V (vs. Ag/AgCl/saturated KCl) in the phosphate buffer solution. Therefore, the electrochemical property of Fe(CN)₆⁴⁻/Fe(CN)₆³⁻ redox couple was studied at different scan rates using CV technique. The peak currents were directly proportional to the scan rate as predicted for a surface confined diffusionless system. The surface coverage (Γ) and the concentration of Fe(CN)₆⁴⁻ were determined to be 1.88 × 10⁻⁸ mol/cm² and 0.641 mol/dm³, respectively. By neglecting cations incorporation during redox reaction of the PBV film and also based on the results obtained from energy-dispersive X-ray spectroscopy for the films of as-deposited, reduced and oxidized states, an ion exchange mechanism was proposed.     

Deposition rate and temperature of carbon films during laser-induced CVD on a moving substrate

The feasibility of using pyrolytic laser-induced chemical vapor deposition (LCVD) to deposit carbon coatings on moving fused quartz substrates is investigated. This LCVD system uses a CO₂ laser to locally heat a substrate in open air to create a hot spot. Pyrolysis of hydrocarbon species occurs and subsequently deposits a layer of carbon film onto the substrate surface. The results of this study indicate that growth kinetics and the geometry of uniform carbon stripes deposited by pyrolytic LCVD strongly related to the laser power, the traverse velocity of the substrate, the type of hydrocarbon species used in deposition, and the diameter of the substrate. The deposition rate of carbon film increases exponentially with the laser power, while an increase in traverse velocity of the substrate will also increase the deposition rate until a maximum deposition rate is reached; further increases in the traverse velocity will decrease the deposition rate. We suspect that this optimal deposition rate is caused by substrate motion, which affects the substrate surface temperature, and consequently the effective surface area available for film deposition. The substrate temperature is observed to behave linearly with the deposition parameters considered in this study.     

The growth and conductivity of nanostructured ZnO films grown on Al-doped ZnO precursor layers by pulsed laser deposition

The structure and electrical properties of nanostructured Al-doped ZnO (AZO)/ZnO bilayers grown as potential solar cell electrodes by pulsed laser deposition on (0001) sapphire substrates are investigated. Transmission and scanning electron microscopy and X-ray diffraction show a narrow temperature window around 350–450 °C where nanostructures are formed. 2-D mapping of electrical conductivity by tunnelling atomic force microscopy showed that these nanostructures provided low resistance pathways, but that the overall film resistivity increased for substrate temperatures above 350 °C. The reasons for this are discussed.     

Local reactivity of diamond-like carbon modified PTFE membranes used in SO2 sensors

The local electrochemical activity of polytetrafluorethylene (PTFE) membranes coated with diamond-like carbon (DLC) was investigated using scanning electrochemical microscopy (SECM). During z-approach curves in the feedback mode of SECM unexpected local variations in the electron-transfer rate of [Fe(CN)₆]^3−/4− and [Ru(NH₃)₆]^3+/2+ were observed. This local heterogeneity of the electrochemical activity was further evaluated in a system adapted from SO₂ gas sensors. In this case, the Cu^2+/+ couple is used as dissolved reversible redox system. Reaction of SO₂ with Cu²⁺ yields Cu⁺ which is re-oxidized at the DLC-coated PTFE membrane. Gas permeation/tip-collection mode SECM experiments allowed visualizing the local pore distribution as sites where the SO₂ is permeating through the membrane and hence formation of Cu⁺ takes place.     

Seed-mediated electrochemical growth of gold nanostructures on indium tin oxide thin films

Two-dimensional gold nanostructures (Au NSs) were fabricated on amine-terminated indium tin oxide (ITO) thin films using constant potential electrolysis. By controlling the deposition time and by choosing the appropriate ITO surface, Au NSs with different shapes were generated. When Au NSs were formed directly on aminosilane-modified ITO, the surface roughness of the interface was largely enhanced. Modification of such Au NSs with n-tetradecanethiol resulted in a highly hydrophobic interface with a water contact angle of 144°. Aminosilane-modified ITO films further modified with colloidal Au seeds before electrochemical Au NSs formation demonstrated interesting optical properties. Depending on the deposition time, surface colors ranging from pale pink to beatgold-like were observed. The optical properties and the chemical stability of the interfaces were characterized using UV-vis absorption spectroscopy. Well-defined localized surface plasmon resonance signals were recorded on Au-seeded interfaces with λ_max = 675 ± 2 nm (deposition time 180 s). The prepared interfaces exhibited long-term stability in various solvents and responded linearly to changes in the corresponding refractive indices.     

The effect of solvent water content on the dielectric properties of Al2O3 films grown by atmospheric pressure mist-CVD

Aluminum oxide (Al₂O₃) dielectric layers were grown by a mist-chemical vapor deposition (mist-CVD) process at 300 °C, using solvent mixtures containing acetone and water. As the acetone to water ratio was varied from 9:1 to 7:3, the leakage current of Al₂O₃ at an electric field of 7 MV/cm² decreased from 9.0 × 10^?7 to 4.4 × 10^?10 A/cm², and the dielectric constant increased from 6.03 to 6.85 with improved hysteresis during capacitance-voltage measurements. Consequently, the most robust Al₂O₃ films were obtained at an acetone to water ratio of 7:3, with a dielectric constant (κ) close to the ideal value 7.0, and a breakdown field of approximately 9 MV/cm. Thin film transistors (TFTs) incorporating In-Sn-Zn-O (ITZO) as the semiconductor were fabricated with the Al₂O₃ (7:3) dielectric onto p⁺⁺-Si substrates. The devices exhibit high electrical performance, with a high field effect mobility of 42.7 cm²V^?1s^?1, and a small subthreshold swing (S.S.) value of 0.44 V/decade.     

Surface analysis with scanning electrochemical microscopy in the feedback mode: Monitoring of reactivity and pitting precursor sites on the Nd-Fe-B-type magnet

Scanning electrochemical microscopy (SECM) in the feedback mode was utilized for monitoring the surface reactivity and the localized corrosion processes occurring on the Nd_13.5Fe_79.5Si₁B₆ permanent magnet (intrinsically comprising iron inclusions). SECM imaging experiments, performed with the application of ferrocenecarboxylic acid as the mediator, revealed distinctly reactive areas at the magnet surface during early stages of its immersion in 0.1 mol dm⁻³ phosphate buffer (pH = 7). It was demonstrated that the iron inclusions were responsible for the existence of these reactive areas whereas the bulk material surface was practically unreactive (insulating). It was observed that the surface reactivity of the iron inclusions gradually decreased with time and after 7 h immersion the whole magnet surface became uniformly unreactive (insulating). The results were explained in terms of differences in the dynamics of the passive film formation on the iron inclusions and on the bulk material. Another factor that might be responsible for the observed non-uniform surface reactivity was also considered, namely, the differences in abilities to charge propagation through passive films existing on the iron inclusions and on the bulk material. The role of the iron inclusions as pitting precursor sites in the presence of chlorides in the phosphate buffer solution was also examined.