Fabrication and electroanalytical characterization of label-free DNA sensor based on direct electropolymerization of pyrrole on p-type porous silicon substrates

Label-free DNA sensors based on porous silicon (PS) substrate were fabricated and electrochemically characterized. p-type silicon wafer was electrochemically anodized in an ethanolic hydrofluoric (HF) solution to construct a PS layer on which polypyrrole (PPy) film was directly electropolymerized. To achieve direct electropolymerization of PPy on PS substrate without pre-deposition of any metallic thin-film underlayer, a low resistivity wafer (0.01–0.02 Ω cm) was used. The rough surface of the PS layer allowed for a strong adsorption of the PPy film. Intrinsic negative charge of the DNA backbone was exploited to electrostatically adsorb 26 base pairs of probe DNA (pDNA) into the PPy film by applying positive bias. The pDNA was designed to hybridize with the target DNA (tDNA) which is the insertion element (Iel) gene of Salmonella enterica serovar Enteritidis. Dependence of peak current (i _p ) around 0.2 V vs Ag/AgCl on tDNA concentration and incubation time were shown from the cyclic voltammograms of PS/PPy + pDNA + tDNA substrates in a 0.01 M potassium perchlorate solution. Plot of i _p vs incubation time showed a reduction in current density (J) by ca. 29 μA cm⁻² every hour. Sensitivity obtained from a plot of i _p vs tDNA concentration was −166.6 μA cm⁻² μM⁻¹. Scanning electron microscopy (SEM) image of the cross-section of a PS/PPy + pDNA + tDNA multilayered film showed successful direct electropolymerization of PPy for a nano-PS DNA biosensor.     

Carbon nanotube-modified glassy carbon electrode for anodic stripping voltammetric detection of Uranyle

A multi-wall carbon nanotube (MWNT) modified glassy carbon electrode (GCE) is described for the measurement of trace levels of uranium by anodic stripping voltammetry. In a pH 4.4 NaAc-Hac buffer containing 0.010 mol L⁻¹ Mg(NO₃)₂, UO₂ ²⁺ was adsorbed onto the surface of a MWNT film coated glassy carbon electrode and then reduced at −0.40 V vs. Ag/AgCl. During the positive potential sweep the reduced uranium was oxidized and a well-defined stripping peak appeared at +0.20 V vs. Ag/AgCl. Low concentrations of Mg²⁺ significantly enhanced the stripping peak currents since they induced UO₂ ²⁺ to adsorb at the electrode surface. The response was linear up to 1.2 × 10⁻⁷ mol L⁻¹ and the relative standard deviation at 2.0 × 10⁻⁸ mol L⁻¹ uranium was 5.2%. Potential interferences were examined. The attractive behavior of the new “mercury-free” uranium sensor holds promise for on-site environmental and industrial monitoring of uranium.     

Pt film electrodes prepared by the Pechini method for electrochemical decolourisation of Reactive Orange 16

Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil. Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (λ = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L⁻¹ NaCl + 0.5 mol L⁻¹ H₂SO₄ solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L⁻¹ NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction, was 0.024 min⁻¹ and 0.069 min⁻¹, for Pt and Pt/Ti electrodes, respectively.     

Direct electrochemistry of chemically modified catalase immobilized on an oxidatively activated glassy carbon electrode

Catalase (Ct) was modified using Woodward’s reagent K (WRK) as a specific modifier of carboxyl residues. The modified Ct was immobilized on an oxidatively activated glassy carbon electrode surface to investigate its direct electrochemistry. Using cyclic voltammetry an irreversible reduction peak was obtained at approximately −0.362 V vs. Ag/AgCl in buffer solution, pH 7, and at a scan rate of 0.1 V s⁻¹. The electrochemical parameters, including charge-transfer coefficient (0.27), apparent heterogeneous electron transfer rate constant (13.51 ± 0.42 s⁻¹) and formal potential of the Ct film (−0.275 V) were determined. The prepared enzyme electrode exhibited a response to H₂O₂.     

Deposition of Erbium Containing Film in Porous Silicon from Ethanol Solution of Erbium Salt

Electrochemical treatment of porous silicon (PS) in ethanol solution of Er(NO₃)₃ was investigated to obtain material suitable for optoelectronic application. The voltammograms of n⁺-type and p-type PS vs. an Ag/AgCl reference electrode were examined and compared with these of a Pt electrode. The basic cathode reactions were marked out the voltammograms: (i) the formation and the adsorption of atomic hydrogen; (ii) the formation of molecular hydrogen; (iii) the electrolysis of water and ethanol. No zones relating to on electrochemical transitions of Er ions were revealed on the voltammograms. Nevertheless, with the cathode polarization, the formation of an Er-containing deposit was observed at the surface of the cathode. The IR and SIMS analysis were used to study the composition of the deposits. The scheme of the electrochemical and chemical reactions at the cathode is discussed.     

Direct Biomass Fuel Cell (BMFC) with Anode/Catalyst Comprising a Nanocomposite of a Mesoporous n-Semiconductor Film and a Metal Thin Layer: A New Concept of Catalyst Design

Abstract  

We designed an efficient direct biomass fuel cell (BMFC) anode and prepared a nanocomposite [base electrode/mesoporous n-semiconductor (SC) thin film/metal thin layer]. A Pt thin layer was photodeposited onto a mesoporous 20-μm thick TiO₂ thin film having a roughness factor of 2000, which was coated on an F-doped tin oxide/glass base electrode (FTO). This anode/catalyst nanocomposite was efficient at decomposing aqueous solutions of glucose and other biomass-related compounds in combination with an O₂-reducing cathode the other side of which was exposed to ambient air. The nanocomposite exhibited sharp optimum conditions at the atomic ratio of Pt/Ti = 0.33 in the BMFC, generating high electrical power of 2 mW cm⁻² without any light irradiation or bias potential when using a 1 M glucose aqueous solution. This output power is 20 times as large as that generated by a mesoporous TiO₂ film anode under UV-light (18 mW cm⁻²) irradiation. At this ratio, the coated Pt specifically exhibited metallic luster, and its average Pt thickness on the mesoporous TiO₂ nanostructure was calculated to be 0.40 nm. The high BMFC activity was interpreted by the simultaneous Schottky-junction/Ohmic contact nature of the nanocomposite. Other biomass compounds such as sucrose, ethanol and polysaccharides were also effective as direct fuels for the BMFC. Immediately after soaking this composite anode without a cathode in a glucose aqueous solution, continuous evolution of H₂ bubbles was observed from the anode surface. The electrical power generation and H₂ production are easily changed by connecting and disconnecting a cathode, respectively. Based on a simple design and calculation, the present system with glucose fuel has the potential to construct a module stack of 2 kW m⁻³. Simultaneous material/energy circulation by using the BMFC with biomass and its waste fuel is proposed for application in future social systems.     

Thickness dependent wavelength selective NIR-UV-visible photoresponse in ZnO nanowires and silicon heterojunction

In this paper, we report ZnO nanowires (NWs) and silicon-based type-II PN heterojunction for UV–Visible–Infrared self-powered photodetection. The as-grown ZnO NWs were highly crystalline and aligned along the c-axis in the [002] direction revealed in the HRTEM and XRD measurements. The Hall measurements revealed the n-type behavior for ZnO and p-type for p-Si with carrier concentrations of 4.09 × 10¹⁶ cm^?3 and 1.38 × 10¹⁷ cm^?3, respectively. The depletion widths were estimated to be ～35 nm and ～120 nm, respectively for p-Si and n-ZnO NWs. The Ag/n-ZnO NWs/p-Si/Ag PN heterojunction showed large photoresponse, even at zero bias, under the illumination of commercially available UV–Visible–NIR LEDs, thus acting as a self-powered photodetector. It was interesting to observe that the photoresponse was dependent on the growth time and hence the thickness of ZnO NWs thin film. A maximum zero bias responsivity of ～0.1 A/W at green (515 nm) was observed and was large for the junction with thicker ZnO NWs film (5 h growth), compared with thinner (3 h growth) device under IR (950 nm) LED illumination, however, it was observed otherwise for UV (395 nm) LED. This suggests that tuning the thickness of the ZnO NWs thin film results in the wavelength selective photoresponse, consequently, paving the way towards UV blind IR-visible photodetector based on ZnO NWs. The transient short circuit current (I_sc vs t) and open circuit voltage (V_oc vs t) properties showed fast and large responses under periodic illumination of all LEDs (UV–Vis–NIR). The response was observed to depend on the intensity of light and the maximum V_oc comes out to be ～102 mV and I_sc ～5.58 μA, under the illumination of a red laser diode.     

Green synthesized Au–Ag bimetallic nanoparticles modified electrodes for the amperometric detection of hydrogen peroxide

Simple and eco-friendly electro deposition method was employed for the fabrication of Au–Ag bimetallic nanoparticles modified glassy carbon electrode. Nano Au–Ag film modified glassy carbon electrode surface morphology has been examined using atomic force microscopy. Electrodeposited Au–Ag bimetallic nanoparticles were found in the average size range of 15–50 nm. The electrochemical investigations of nano Au–Ag/1-butyl-3-methylimidazolium tetrafluoroborate-nafion film have been carried out using cyclic voltammetry and electrochemical impedance spectroscopy. The nano Au–Ag/1-butyl-3-methylimidazolium tetrafluoroborate-nafion film modified glassy carbon electrode holds the good electrochemical behavior and stability in pH 7.0 phosphate buffer solutions. The nano Au–Ag/1-butyl-3-methylimidazolium tetrafluoroborate-nafion modified glassy carbon electrode was successfully employed for the detection of H₂O₂ in the linear range of 1–250 μM in lab samples, and 1 × 10⁻³–2 × 10⁻² M in real samples, respectively.     

Multilayer porous Pd-doped SnO2 thin film: Preparation and H2 sensing performance

Porous pure and Pd-doped SnO₂ films are prepared using sol-gel synthesis with polystyrene (PS) microspheres as the template. Different characterizations are performed to analyze the microstructure and morphology of the films. The sensing performance of the films at various temperatures and hydrogen concentrations is investigated. Results show that high concentration of PS template significantly influences the continuity of films and the H₂ sensing performance. The porous SnO₂ film with 0.1 wt% PS microspheres exhibits the best performance. At 225 °C, the response magnitude of the porous 1 mol% Pd-doped SnO₂ thin film to 1000 ppm H₂ is 93.18, which is approximately 10.58 times of the pure sample.     

Electrode metallization for high permittivity oxide RF thin film capacitors

High permittivity oxide thin film capacitors for RF components should be integrated on the chip to form a complete miniaturized module, with other semiconductor or thin film components such as inductors, isolation capacitors, and bias resistors. The quality factor (Q) values of the RF capacitors are strongly dependent on electrode conductivity. Alas the best conducting metals (e.g. Ag, Cu, Al) are not thermodynamically stable during deposition of high permittivity oxide films with high temperature and oxygen atmosphere. On the other hand, refractory metals (e.g. Mo, W) endure high temperatures, but are prone to oxidation. Therefore, a diffusion barrier is a prerequisite for integrating refractory metals to achieve a stable electrode structure.In this study both non-reactive and sacrificial diffusion barriers with Mo metallization were investigated on Si/SiO₂ substrates. Also, noble metals (Au and Pt) as oxidation resistant materials were examined. Annealing at 650 °C was performed to the electrode stacks in an open-end air furnace and in vacuum with protective gas.The chemically inert materials Au and Pt failed to endure the high annealing temperature. Au became extremely rough and cracks appeared. Massive grain growth and adhesion loss occurred with Pt film. Mo electrode withstood the oxidizing ambient conditions with a sacrificial Si or Al–Ti diffusion barrier. Moderate increase in surface roughness was observed after the annealing due to oxidation. Also, thermally stable AlN, Si₃N₄, and SiO₂ diffusion barriers were able to block oxygen from the Mo electrode.     

Voltammetric study of polyviologen and the application of polyviologen-modified glassy carbon electrode in amperometric detection of vitamin C

The voltammetric behavior of viologen oligomers prepared from butylviologen dibromide and the factors influencing polyviologen film formation were investigated at a glassy carbon electrode (GCE). Based on the voltammetric observations, phosphoric acid is crucial to the formation of a stable polyviologen film on a GCE. The polyviologen-modified glassy carbon electrode (PVGCE) was employed to determine vitamin C (i.e., ascorbic acid) in order to demonstrate the electroanalytical application of the electropolymerized polyviologen film. The PVGCE was found capable of accumulating vitamin C at electrode surface in a slightly basic solution (pH = 7.8) and induce a negative shift of oxidation potential of vitamin C. Vitamin C was detected by hydrodynamic amperometry at +0.1 V (vs. Ag/AgCl) in a batch-injection cell; no accumulation time is required. The dependence of oxidation current on concentration was linear from 5.00 × 10⁻⁷ M to 1.22 × 10⁻⁴ M with a regression coefficient of 0.9993. Several real samples were analyzed and the results exhibit good agreement with those determined by iodimetric titration.     

Electrical properties of chemical solution deposited (Bi0.9RE0.1)(Fe0.975Cu0.025)O3−δ (RE=Ho and Tb) thin films

Pure BiFeO₃ (BFO) and (Bi_0.9RE_0.1)(Fe_0.975Cu_0.025)O_3?δ (RE=Ho and Tb, denoted by BHFCu and BTFCu) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. The BHFCu and BTFCu thin films showed improved electrical and ferroelectric properties compared to pure BFO thin film. Among them, the BTFCu thin film exhibited large remnant polarization (2P_r), low coercive field (2E_c) and reduced leakage current density, which are 89.15 C/cm² and 345 kV/cm at 1000 kV/cm and 5.38×10^?5 A/cm² at 100 kV/cm, respectively.     

Electrochemical deposition of Co–Sb thin films on nanostructured gold

The electrochemical behavior of the Co–Sb system on Au substrate during cyclic voltammetry and potentiostatic deposition was investigated. Electrochemical behavior of Co and Sb was studied and compared to the Co–Sb system. At a negative potential (−0.9 V vs. Ag/AgCl) the electrochemical behavior of this binary system was similar to that of individual Co and Sb combined. For more negative vertex potentials (e.g., −1.2 V vs. Ag/AgCl), results from cyclic voltammetry have shown the presence of a new compound different from Co and Sb which could only be detected at slow sweep rate. The deposition performed at constant potentials between −1.0 and −1.2 V have resulted in films that were made of CoSb₃ and Sb as indicated by XRD. Surface film studied by SEM and EDS has shown morphological and compositional non-uniformities caused by hydrogen evolution.     

Electropolymerization of benzotriazole in room temperature ionic liquid [bmim]PF<Subscript>6</Subscript>

The electropolymerization of benzotriazole on an Au electrode was investigated via cyclic voltammetry and chronoamperometry in a room temperature ionic liquid medium, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF₆) containing glacial acetic acid. The chronoamperometric investigation revealed that the instantaneous nucleation predominated the potentiostatic electropolymerization of benzotriazole at the oxidation peak potential. Scanning electron microscopy indicated that the polymer film was compact and relatively smooth and infrared spectroscopy suggested the polymer chains were formed mainly via coupling of the unsaturated nitrogen atoms. The polymer was found to be highly electroactive, showing a quasi-reversible and stable pair of redox peaks centering at 0.9 V versus Ag/AgCl in 0.1 mol L⁻¹ H₂SO₄.     

The influence of chemical passivation on the PZT/Pt electrode interface

It has been recognized that the interdiffusion of atomic species between a PZT film and the Pt bottom electrode leads to the gradual degradation of a PZT capacitor. In order to prevent this interdiffusion, experimental studies on chemical passivation to the bottom electrode surface were carried out by the sulfurization method. It was observed that a sulfur layer was built up on the Pt substrate with small grains, which resulted in a structural change at the Pt surface. Atomic force microscopy (AFM) showed that the film roughness of the Pt surface was increased by sulfur treatment. Pb(Zr_0.5Ti_0.5)O₃(PZT) thin films were prepared on a Pt/Ti/SiO₂Si bottom electrode by spin-coating techniques. The microstructure and the preferred orientation of the PZT films were shown to depend on the sulfur-treated electrode. The PZT capacitor on a clean Pt electrode was confirmed to be ferroelectric with Pr=17.7 μC/cm² and Ec=65 kV/cm from the P-E hysteresis curves. The fatigue behavior of a PZT film capacitor prepared on a sulfur-treated one was observed to be relaxed, but the absolute value of Pr was paid off.     

Influence of Ag incorporation on the structural,optical and electrical properties of ITO/Ag/ITO multilayers for inorganic all-solid-state electrochromic devices

Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm²and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiO_x/LiPON/WO₃/ITO and ITO/NiO_x/LiPON/WO₃/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiO_x/LiPON/WO₃/ITO), the ECD with the IAI top electrode (ITO/NiO_x/LiPON/WO₃/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.     

Catalytic activity of ultrathin Pt films on aligned carbon nanotube arrays

Uniform ultrathin Pt films were electrodeposited onto an aligned array of carbon nanotubes (CNTs) for high-area chemically stable methanol fuel cell anodes. Electrochemical treatment of the graphitic CNT surfaces by diazoniumbenzoic acid allowed for uniform Pt electroplating. The mass activity of the Pt thin film can reach 400 A/g at a scan rate of 20 mV/s and in a solution of 1 M CH₃OH/0.5 M H₂SO₄. A programmed pulse potential at 0 V was also seen to nearly eliminate the effects of carbon monoxide poisoning. The mass activity of Pt for methanol oxidation can be maintained at 300 A/g for more than 3000 s, which is 19 times of that under a constant potential of 0.7 V (vs. Ag/AgCl).     

Thermal treatment effect on the magnetoelectric properties of (Ni0.5Zn0.5)Fe2O4/Pt/Pb(Zr0.3Ti0.7)O3 heterostructured thin films

Magnetoelectric (ME) property modulation in heterostructured (Ni_0.5Zn_0.5)Fe₂O₄/Pt/Pb(Zr_0.3Ti_0.7)O₃ (NZFO/Pt/PZT) thin films on platinized Si substrate by thermal annealing condition variation was studied. In an attempt to prevent interfacial reaction between NZFO and PZT layers during high temperature annealing, thin Pt layer was deposited which can serve as inter-diffusion barrier as well as electrode. The ferroelectric, magnetic, and ME properties of the heterostructured film were noticeably modulated due to microstructural evolution and clamping relaxation developed during thermal annealing process. Room temperature ME voltage coefficient of the heterostructured thin films was enhanced with increasing annealing temperature and reached to 29 mV/cm·Oe when annealed at 650 °C.     

High performance NiO/Ag/NiO transparent conducting electrodes for p-Si/n-ZnO heterojunction photodiodes

A NiO/Ag/NiO (NAN) transparent conducting electrode (TCE) was fabricated using a magnetron-sputtering system, and the NAN TCE was applied to p-Si/n-ZnO heterojunction photodiodes (HPDs). The NAN TCE exhibits a 50% higher transmittance than the Al electrode (less than 1%). However, a very low sheet resistance of 0.27 Ω/sq is obtained in Al electrode than in NAN TCE (6.5 Ω/sq). The NAN TCE could effectively enhance the photo response of p-Si/n-ZnO HPDs for both ultraviolet (UV) and visible bands as compared to the p-Si/n-ZnO HPDs with the traditional Al electrode. Compared to the traditional p-Si/n-ZnO HPDs using the Al electrode, for the p-Si/n-ZnO HPDs using NAN TCE, the 500 nm photo response is increased by approximately 10 times and the 280 nm photo response is significantly enhanced by approximately 100 times at a reverse-bias voltage of 1 V. The dark current of p-Si/n-ZnO HPDs with NAN TCE is two orders of magnitude lower than that of p-Si/n-ZnO HPDs with an Al electrode. The improved performance enhances the photo (500 nm) to dark current ratio from 2 for the p-Si/n-ZnO HPDs with Al electrode to 1.4 × 10³ for the one with NAN TCE. The photo (280 nm) to dark current ratio is enhanced from 8.5 × 10² to 6.8 × 10⁵. The mechanism results from the high transmittance in the NAN TCE and Ni diffusion in ZnO. The Ni diffusion in ZnO suppresses its defects and hence decreases electron scattering from crystallites/grains, thereby increasing carrier mobility.     

Influence of underpotentially deposited Sb onto Pt anode surface on the performance of direct formic acid fuel cells

We first reported on electrocatalytic activity and stability of antimony modified platinum (PtSb_upd) as anode catalyst in direct formic acid fuel cells. Sb modified Pt (PtSb_upd) was prepared by underpotential deposition technique applying constant potential of 0.2 V (vs. Ag/AgCl, 3M KCl) and its modified surface was characterized by XRD and XPS. The electrocatalytic oxidation activity by cyclic voltammograms and the single cell power performance of Sb modified Pt were measured and their results were compared with the data of unmodified Pt electrode. PtSb_upd induced lower onset potential of formic acid oxidation and twice higher power density of 250 mW cm⁻² was observed.