pH sensing in aqueous solutions using a MnO2 thin film electrodeposited on a glassy carbon electrode

An electrolysis technique at a constant potential was used to develop a highly reproducible and fast elaboration method of adherent manganese dioxide thin films on a glassy carbon electrode from aqueous solutions containing sulfuric acid and manganese sulfate. The resulting films were found to have a nanostructured character presumably due rather to birnessite (δ-MnO₂) than to γ-MnO₂, as suggested by their Raman and XRD signatures. They lead to modified electrodes that present an obvious although complex pH dependent potentiometric response. This sensor indeed showed a single slope non-Nernstian linear behaviour over the 1.5–12 pH range for increasing pH direction (“trace”), whereas a Nernstian two slopes linear behaviour was observed for decreasing pH direction (“re-trace”). Preliminary EIS experiments carried out at a pH value of 1.8 seem to reveal a sensitivity mechanism based on proton insertion process at least at highly acidic pH values.     

Self-growth of nanocrystalline structures for amorphous Sr0.925Bi0.05TiO3 thin films with high energy density

Process of self-growth nanocrystalline structure was explored to improve the dielectric properties of amorphous Sr_0.925Bi_0.05TiO₃ (SBT) thin films through controlling the annealing temperature. The crystallinity of the material was 15% when annealed at 550?°C, and the resulting nanocrystalline particles were 14?nm in size as determined by XRD analysis. Therefore, the proposed process could produce a novel film of an amorphous matrix coating nanocrystalline particles. Finite element analysis results showed that the applied electric field was focused primarily in the amorphous matrix, which could effectively decrease the probability of low voltage breakdown of the nanocrystalline particles. Simultaneously, the nanocrystalline particles supplied more polarization charges, which helped to improve the dielectric constant of the inorganic composite. Combining the merits of amorphous and crystalline phases, the ultimate energy storage density of the modified sample was as high as 21.2?J/cm³, which represents an improvement of 5.1?J/cm³ compared with that of pure amorphous SBT thin film.     

Structural properties and sensing performance of CeTiO3 ceramic films as a solid-state pH sensor

In this paper, we have studied the impact of postannealing treatment on the structural properties and sensing characteristics of CeTiO₃ ceramic membranes deposited on Si substrate by sputtering for solid-state electrolyte-insulator-semiconductor (EIS) pH sensors. X-ray photoelectron spectroscopy, Auger electron spectroscopy, X-ray diffraction, and atomic force microscopy were used to study the chemical compositions, elemental depth profiles, film structures, and surface morphologies of CeTiO₃ ceramic membranes treated at three rapid thermal annealing (RTA) temperatures of 700, 800 and 900?°C. The sensing performance of the CeTiO₃ ceramic membranes annealed at three different RTA temperatures is strongly correlated to their structural properties. The CeTiO₃ EIS device after RTA at 800?°C exhibited the best sensing characteristics (pH sensitivity, hysteresis voltage and drift rate) among these RTA temperatures. We attribute this behavior to the optimal RTA temperature enhancing the Ce³⁺/Ce⁴⁺ ratio of CeTiO₃ ceramic membrane, reducing an interfacial layer at the CeTiO₃-Si interface, and increasing its surface roughness.     

TiO2 films prepared by micro-plasma oxidation method for dye-sensitized solar cell

Nanocrystalline TiO₂ films are widely investigated as the electrodes of dye-sensitized solar cell(s) with different preparation methods. In this paper, thin titanium dioxide films have been prepared on titanium plates by the micro-plasma oxidation method in the sulfuric acid solution. The thin TiO₂ films were sensitized with a cis-RuL₂(SCN)₂·2H₂O (L = cis-2,2′-bipyridine-4,4′-dicarboxylic acid) ruthenium complex and implemented into a dye-sensitized solar cell configuration. The influence of reaction current density (10, 15, 20, 25 and 30 A dm⁻²) on the structural and the surface morphology of the films was investigated by X-ray diffraction, scanning electron microscopy, atom force microscopy and X-ray photoelectricity spectroscopy. Impedance analysis for dye-sensitized solar cells was carried out by electrochemical impedance spectroscopy. The results show that the rise of current density leads to the increase in the amount of rutile and the thickness of the TiO₂ film, which makes the TiO₂ films have different photovoltages and photocurrents. The relatively higher photoelectricity properties were obtained in the TiO₂ films prepared at a current density of 20 A dm⁻². The open-circuit voltage and the short-circuit current are 605 mV and 165 μA cm⁻², respectively.     

A new regime for high rate growth of nanocrystalline diamond films using high power and CH4/H2/N2/O2 plasma

In this work, we report high growth rate of nanocrystalline diamond (NCD) films on silicon wafers of 2 inches in diameter using a new growth regime, which employs high power and CH₄/H₂/N₂/O₂ plasma using a 5 kW MPCVD system. This is distinct from the commonly used hydrogen-poor Ar/CH₄ chemistries for NCD growth. Upon rising microwave power from 2000 W to 3200 W, the growth rate of the NCD films increases from 0.3 to 3.4 μm/h, namely one order of magnitude enhancement on the growth rate was achieved at high microwave power. The morphology, grain size, microstructure, orientation or texture, and crystalline quality of the NCD samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and micro-Raman spectroscopy. The combined effect of nitrogen addition, microwave power, and temperature on NCD growth is discussed from the point view of gas phase chemistry and surface reactions.     

Modification of vertically aligned carbon nanotubes with RuO2 for a solid-state pH sensor

In this work, a novel type electrode based on RuO₂ nanoparticles-modified vertically aligned carbon nanotubes (RuO₂/MWCNTs) was prepared by magnetron sputtering deposition. This RuO₂/MWCNTs electrode not only shows a high capacity nature, but also possesses a good response to the pH value. The pH sensor based on the RuO₂/MWCNTs nanocomposite electrode exhibits some advantages over the conventional pH sensors. It shows good reproducibility, long-term storage stability (over 1 month) and linear response in the whole pH range (2-12) of Britton-Robinson (B-R) buffer solutions with near-Nernstian response (about −55 mV/pH). The hysteretic widths of the nanocomposite electrode are 6.4 mV, 5.1 mV and 10.2 mV in pH 7-4-7-10-7, pH 7-10-7-4-7 and pH 2-8-12-8-2 loop cycles, respectively. Moreover, the RuO₂/MWCNTs electrode displays an excellent anti-interference property and fast response time (less than 40 s). According to the electrochemical impedance measurements, the pH sensing properties of the RuO₂/MWCNTs electrode were also discussed.     

The phase formation process of Bi0.5(Na0.8K0.2)0.5TiO3 thin films prepared using the sol-gel method

Lead-free Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ (abbreviated as BNKT) thin films were grown on Pt(111)/Ti/SiO₂/Si substrates using a sol-gel/spin coating technique and were then annealed at different temperatures (350 °C, 550 °C, 750 °C and 850 °C). Analysis of the XRD patterns and FT-IR spectra were used to determine the main reactions and the phase formation process of BNKT thin films during the sol-gel process. The results show that the dielectric constant of the thin films attains a maximum at a set temperature and then decreases at higher annealing temperatures, which can be attributed to phase formation and transformation. Moreover, the morphologies of the BNKT thin films improve with the increase in grain size and the formation of distinct grain boundaries. Furthermore, through increasing the pH of the precursor solutions, the size of the sol-gel colloidal particles increases slightly and the grains formed from the corresponding solutions tend to be small and uniform.     

Synthesis and physical characteristics of ZnAl2O4 nanocrystalline and ZnAl2O4/Eu core-shell structure via hydrothermal route

Nanocrystalline zinc aluminate (ZnAl₂O₄) particles with a spinel structure were prepared by hydrolyzing a mixture of aluminum chloride hexahydrate and zinc chloride in deionized water. It was found that pH value and reaction temperature play critical roles in the formation of nano-sized ZnAl₂O₄. Depending on pH values in the precursor solution, ZnAl layered double hydroxide (ZnAl-LDH), ZnO, boehmite or gibbsite could be formed. At pH 7 and T>120 °C, the nanocrystalline ZnAl₂O₄ particles with average particle size of ∼5 nm are easily synthesized through ZnAl layered double hydroxide (ZnAl-LDH). After surface treatment with R-OH by using the cationic surfactant CTAB, the ZnAl₂O₄/Eu core-shell structure can be developed. The ZnAl₂O₄/Eu core-shell structure can show both emissions from ⁵D₀ to ⁷F₂ sensitivity energy level and ⁵D₂ to ⁷F₀ depth energy level.     

A pH sensor based on the TiO2 nanotube array modified Ti electrode

In this paper, a novel solid state pH sensor was fabricated by anodization of titanium substrate electrode. The relationship between pH sensitivity and hydrophilicity or surface morphology of TiO₂ film was investigated. Amorphous TiO₂ nanotube has better pH response than anatase TiO₂ nanotube. After being irradiated by ultraviolet light (UV), the potential response of the electrode modified by amorphous TiO₂ nanotube was close to Nernst equation (59 mV/pH). SEM, XRD, and XPS were used to characterize electrodes. Possible mechanism was discussed by analyzing surface hydroxyl groups, crystal structure and hydrophilicity of the electrodes. The electrode has been used to detect some kinds of soft drinks and shows good response.     

Elaboration and characterization of PVP-assisted NiO thin films for enhanced sensitivity toward H2 and NO2 gases

It is widely demonstrated that the synthesis conditions of sol-gel films have a great impact on their gas sensing properties. In this work, transparent PVP-assisted nickel oxide thin films with an average grain size of ~5?nm were synthesized using two distinctive deposition procedures combining the sol-gel method with the spin-coating technique then tested as optical gas sensors for the detection of hazardous pollutant gases. The first method is ascribed to a typical spin-coating deposition followed by a thermal annealing, and the second method consisted on a multistep coating annealing process. Structural and morphological studies showed enhanced crystallization rate and homogeneous surface morphology using a multistep deposition. The as prepared films exhibit a clear and reversible response toward H₂, CO and NO₂ gases and the multistep deposition process enhanced the sensitivity of about 113% and 194% toward 1% of H₂ and 0.1% of NO₂ respectively. The shrinkage of the band gap from 4.07 to 3.91?eV and the increased PL intensity indicate the presence of higher rate of charge density and intrinsic defect states that promoted the sensitivity of the film. Furthermore, improved response intensity was detected in the near UV region and higher stability with fast response was obtained for hydrogen gas.     

Structural and optical properties of MoO3 and V2O5 thin films prepared by Spray Pyrolysis

MoO₃ and V₂O₅ thin films were prepared on glass substrates by Spray Pyrolysis technique at a substrate temperature of 423 K. The precursor solutions were obtained by varying the concentrations of MoCl₅ and VCl₃ in bi-distilled water. The structural investigation conducted by X-ray diffraction showed that MoO₃ and V₂O₅ thin films were polycrystalline with orthorhombic structure. The optical properties studied in the 300–2500 nm range suggest that the thin film behaviours are related to bound electronic states. The optical band gaps have been estimated from slopes of ln(hν) versus hν plots of MoO₃ and V₂O₅ films were 3.35 and 2.44 eV, respectively. The electrical conductivity was measured using four probes method.     

Texture effect on the electrochemical properties of LiCoO2 thin films prepared by PLD

LiCoO₂ thin films were prepared by pulsed laser deposition (PLD) on Pt/Ti/SiO₂/Si (Pt) and Au/MgO/Si (Au) substrates, respectively. Crystal structures and surface morphologies of thin films were investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The LiCoO₂ thin films deposited on the Pt substrates exhibited a preferred (0 0 3) texture with smooth surfaces while the LiCoO₂ thin films deposited on the Au substrates exhibited a preferred (1 0 4) texture with rough surfaces. The electrochemical properties of the LiCoO₂ films with different textures were compared with charge-discharge, dQ/dV, and Li diffusion measurements (PITT). Compared with the (1 0 4)-textured LiCoO₂ thin films, the (0 0 3)-textured thin films exhibited relatively lower electrochemical activity. However, the advantage of the (1 0 4)-textured film only remained for a small number of cycles due to the relatively faster capacity fade. Li diffusion measurements showed that the Li diffusivity in the (0 0 3)-textured film is one order of magnitude lower than that in the (1 0 4)-textured film. As discussed in this paper, we believe that Li diffusion through grain boundaries is comparable to or even faster than Li diffusion through the grains.     

Synthesis of porous CeO2-SnO2 nanosheets gas sensors with enhanced sensitivity

Two-dimension (2D) CeO₂-SnO₂ nanosheets with uniform size and small rhombus nanopores were synthesized by the hydrothermal method. The structure of CeO₂-SnO₂ nanosheets was confirmed by X-ray diffraction (XRD), energy dispersive spectrometer (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM). The gas sensing behaviors of the fabricated sensors were systematically investigated. Under optimum operating temperature (340 °C), the response to 100 ppm ethanol of the CeO₂-SnO₂ sensor was 44, which was 2 times larger than that of the SnO₂ sensor (about 19). The response and recovery time of the CeO₂-SnO₂ sensor were 25 s and 6 s, while that of the SnO₂ sensor were 29 s and 7 s, respectively. The results revealed that porous CeO₂-SnO₂ nanosheets enhanced the gas sensing properties and shortened the response/recovery time, which were attributed to the porous structure and the effect of the CeO₂-doping. In addition, the ethanol sensing mechanism was carefully discussed.     

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.     

Li-ion diffusion kinetics in LiMn2O4 thin films prepared by pulsed laser deposition

LiMn₂O₄ thin films were deposited on Au substrates by pulsed laser deposition (PLD). The Li-ion chemical diffusion coefficients of the films, , were measured by cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT), potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). It was found that the values by CV and PITT were in the order of 10⁻¹³ cm² s⁻¹, and those by EIS and GITT were in the range of 10⁻¹³ to 10⁻¹¹ and 10⁻¹⁴ to 10⁻¹¹ cm² s⁻¹, respectively. These data were compared with the previously reported values.     

Effects of pH and surface modification of TiO2 with SiOx on the photocatalytic degradation of a pyrimidine derivative

A pyrimidine derivative, 2-isopropyl-6-methyl-4-pyrimidinol (IMP), could be completely decomposed following pseudo-first-order kinetics by photocatalytic reaction using TiO₂. The effects of pH and surface modification of TiO₂ with SiO_x were studied. The degradation rate of IMP was fast in mild acidic condition (pH=6.3) and slower in strong acidic (pH=2.0) or basic (pH=10.0) condition. The main reason of the slow IMP degradation was different in strong acidic and basic conditions. In strong acidic condition, the slow degradation rate was explained by electrostatic repulsion. On the other hand, a little formation of hydroxyl radicals was considered as a main reason in strong basic condition. The result was supported by the experiments using SiO_x-loaded TiO₂, which has a lower isoelectric point than pure TiO₂.     

Preparation, structural and optical characterization of BaWO4 and PbWO4 thin films prepared by a chemical route

Polycrystalline BaWO₄ and PbWO₄ thin films having a tetragonal scheelite structure were prepared at different temperatures. Soluble precursors such as barium carbonate, lead acetate trihydrate and tungstic acid, as starting materials, were mixed in aqueous solution. The thin films were deposited on silicon, platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and specular reflectance infrared Fourier transform spectroscopy, respectively. Nucleation stages and surface morphology evolution of thin films on silicon substrates have been studied by atomic force microscopy. XRD characterization of these films showed that BaWO₄ and PbWO₄ phase crystallize at 500 °C from an inorganic amorphous phase. FTIR spectra revealed the complete decomposition of the organic ligands at 500 °C and the appearance of two sharp and intense bands between 1000 and 600 cm⁻¹ assigned to vibrations of the antisymmetric stretches resulting from the high crystallinity of both thin films. The optical properties were also studied. It was found that BaWO₄ and PbWO₄ thin films have Eg=5.78 eV and 4.20 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of BaWO₄ and PbWO₄ thin films.     

Electrochemical oxidation of ammonia (NH4/NH3) on thermally and electrochemically prepared IrO2 electrodes

The electrochemical oxidation of ammonia (NH₄⁺/NH₃) in sodium perchlorate was investigated on IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor and the anodic oxidation of metallic iridium. The electrochemical behaviour of Ir(IV)/Ir(III) surface redox couple differs between the electrodes indicating that on the anodic iridium oxide film (AIROF) both, the surface and the interior of the electrode are electrochemically active whereas on the thermally decomposed iridium oxide films (TDIROF), mainly the electrode surface participates in the electrochemical processes.On both electrodes, ammonia is oxidized in the potential region of Ir(V)/Ir(IV) surface redox couple activity, thus, may involve Ir(V). During ammonia oxidation, TDIROF is deactivated, probably by adsorbed products of ammonia oxidation. To regenerate TDIROF, it is necessary to polarize the electrode in the hydrogen evolution region. On the contrary, AIROF seems not to be blocked during ammonia oxidation indicating its fast regeneration during the potential scan. The difference between both electrodes results from the difference in the activity of the iridium oxide surface redox couples.     

Preparation and characterization of nanostructured and high transparent hydrogel films with pH sensitivity and application

Novel nanostructured, high transparent, and pH sensitive poly(2‐hydroxyethyl methacrylate‐co‐methacryliac acid)/poly(vinyl alcohol) (P(HEMA‐co‐MA)/PVA) interpenetrating polymer network (IPN) hydrogel films were prepared by precipitation copolymerization of aqueous phase and sequential IPN technology. The first P(HEMA‐co‐MA) network was synthesized in aqueous solution of PVA, then followed by aldol condensation reaction, it formed multiple IPN nanostructured hydrogel film. The film samples were characterized by IR, SEM, DSC, and UV‐vis spectrum. The transmittance arrived at 93%. Swelling and deswelling behaviors showed the multiple IPN nanostuctured film had rapid response. The mechanical properties of all the IPN films improved than that of PVA film. Using crystal violet as a model drug, the release behaviors of the films were studied. The results showed that compared with PVA, which had low drug loading and exhibited high and burst release, the three IPN films had high drug loading and exhibited sustained release. Besides, the release followed different release mechanism at pH = 4.0 and pH = 7.4, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pulsed electrodeposition of p-type CuInSe2 thin films

CuInSe₂ thin films have been electrodeposited on conductive glass using cyclic pulse electrodeposition. One cycle consists of consequtively applying potentials E₁ and E₂, each during 10 s and a total of 90 cycles are applied. E₁ is chosen between −0.7 and −0.9 V_SCE while E₂ is fixed at −0.1 V_SCE. The films are annealed in argon and then etched in KCN solution to eliminate remnant secondary phases. The material is characterized employing grazing incident X-rays diffraction, Raman spectroscopy, scanning electron microscopy and energy dispersive scanning spectroscopy. The presence of secondary phases seems to be reduced when compared to films prepared at fixed potentials. The films are crystalline and the overall quality improves by annealing in Ar. Photoelectrochemical tests, Mott–Schottky plots and I–V curves confirm p-type conduction. The diffusion regime imposed by the potential pulses could be responsible for the different morphology and composition of samples prepared with pulsed and potentiostatic electrodeposition.