Photocurrent enhancement of interlocked LB film dye layers in a p-CuSCN sensitised photoelectrochemical cell

Dye sensitised photoelectrochemical (PEC) cells based on Cu/p-CuSCN/LB films have been studied with mixed Langmuir Blodgett (LB) films as the dye layer. The effects of mixed layers were investigated in detail by observing the changes of optical absorption and photocurrent in a PEC cell configuration. Enhancements in both optical absorption and photocurrent were found when a mixture of octadecyl methylviolet–C₁₈ (M–C₁₈) and dioctadecyl rhodamine (C₁₈–R–C₁₈) were deposited using the LB technique on p-CuSCN wide band gap semiconductor. The maximum photocurrent quantum efficiency of the PEC cell reached ≈36% in KI (10⁻² M)+I₂ (10⁻⁴ M) electrolyte solution when mixed LB films were used as the dye layer. Photocurrent enhancement is believed to be the enhancement of light absorption of the dye layers due to the interlocking of M–C₁₈ between the double C₁₈ chains of rhodamine.     

Photoelectrochemical properties of rhodamine-C18 sensitized p-CuSCN photoelectrochemical cell (PEC)

Surface states in p-type Cu^I thiocyanate (CuSCN) were detected from I−V characteristics, diffuse reflectance spectra, and photocurrent action spectra. The p-CuSCN films are sensitized by rhodamine with octadecyl-alkyl chain, and the sensitized photocurrent is observed with the visible light illumination. In spite of the surface states in p-CuSCN, the maximum photocurrent quantum efficiency (gf_max) at λ = 560 nm, in 1 × 10⁻⁴ M KI + I₂ solution, pH = 6, reached 8.6%, where the surface dye concentration of photocathode Cu/p-CuSCN/Dye was 1.1 × 10¹⁴ molecules cm⁻². Photocathodes were biased at −0.25 V versus AgCl/Ag to give a zero dark current. From the variation of φ values with the reduction potential of electron acceptors, the cathodic sensitization mechanism presented is further confirmed.     

Electrochemical deposition of Zn3P2 thin film semiconductors on tin oxide substrates

Zn₃P₂ semiconductor thin films were prepared by electrodeposition technique form aqueous solutions. The deposition mechanism was investigated by cyclic voltammetry technique. Crystal structure, morphology and composition of as deposited and annealed Zn₃P₂ thin films grown on SnO₂/glass substrates were determined by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. X-ray diffraction data indicated the formation of Zn₃P₂ as the predominant phase for both as-deposited and annealed films. The compositions of the deposited films were controlled by the bath temperature, deposition potential and Zn/P ratio in the solution.The dark current–voltage measurements of SnO₂/Zn₃P₂/C devices indicated a rectifying behavior and a reverse saturation current density of 1.7×10⁻⁷ A/cm², which is in good accordance with that obtained from films prepared using vacuum technique. Also, the capacitance–voltage measurements showed that the number of interface states and the built in potential are in the order of 5×10⁻⁹ cm⁻³ and 0.85 V, respectively. These preliminary results for Zn₃P₂ thin films reveal that, this semiconductor material can be used for solar cell applications.     

CuInxGa1−xSe2 thin films prepared by electron beam evaporation

CuIn_xGa_1−xSe₂ bulk compound of three different compositions x=0.75, 0.80 and 0.85 have been prepared using individual elements of copper, indium, gallium and selenium. Thin films of CuIn_xGa_1−xSe₂ have been deposited using the prepared bulk by electron beam evaporation method. The structural studies carried on the deposited films revealed that films annealed at 400 °C are crystalline in nature exhibiting chalcopyrite phase. The position of the (1 1 2) peak in the X-ray diffractogram corresponding to the chalcopyrite phase has been found to be dependent on the percentage of gallium in the films. The composition of the prepared bulk and thin films has been identified using energy dispersive X-ray analysis. The photoluminescence spectra of the CuIn_xGa_1−xSe₂ films exhibited sharp luminescence peaks corresponding to the band gap of the material.     

Optical and electrochromic properties of oxygen sputtered tungsten oxide (WO3) thin films

Thin films of tungsten oxide (WO₃) were deposited onto glass, ITO coated glass and silicon substrates by pulsed DC magnetron sputtering (in active arc suppression mode) of tungsten metal with pure oxygen as sputter gas. The films were deposited at various oxygen pressures in the range 1.5×10⁻²−5.2×10⁻² mbar. The influence of oxygen sputters gas pressure on the structural, optical and electrochromic properties of the WO₃ thin films has been investigated. All the films grown at various oxygen pressures were found to be amorphous and near stoichiometric. A high refractive index of 2.1 (at λ=550 nm) was obtained for the film deposited at a sputtering pressure of 5.2×10⁻² mbar and it decreases at lower oxygen sputter pressure. The maximum optical band gap of 3.14 eV was obtained for the film deposited at 3.1×10⁻² mbar, and it decreases with increasing sputter pressure. The decrease in band gap and increase in refractive index for the films deposited at 5.2×10⁻² mbar is attributed to the densification of films due to ‘negative ion effects’ in sputter deposition of highly oxygenated targets. The electrochromic studies were performed by protonic intercalation/de-intercalation in the films using 0.5 M HCl dissolved in distilled water as electrolyte. The films deposited at high oxygen pressure are found to exhibit better electrochromic properties with high optical modulation (75%), high coloration efficiency (CE) (141.0 cm²/C) and less switching time at λ=550 nm; the enhanced electrochromism in these films is attributed to their low film density, smaller particle size and larger thickness. However, the faster color/bleach dynamics is these films is ascribed to the large insertion/removal of protons, as evident from the contact potential measurements (CPD) using Kelvin probe. The work function of the films deposited at 1.5 and 5.2×10⁻² mbar are 4.41 and 4.30 eV, respectively.     

Optical and electrical studies on molybdenum sulphoselenide [Mo(S1−xSex)2] thin films prepared by arrested precipitation technique (APT)

Nanocrystalline stoichiometric [Mo(S_1−xSe_x)₂] thin films were deposited by using arrested precipitation technique (APT) developed in our laboratory. The precursors used for this are namely, molybdenum triethanolamine complex, thioacetamide and sodium selenosulphite; and various preparative conditions are finalised at the initial stages of deposition. Formation of [Mo(S_1−xSe_x)₂] semiconducting thin films are confirmed by studying growth mechanism, optical and electrical properties. X-ray diffraction analysis showed that the composites are nanocrystalline being mixed ternary chalcogenides of the general formula [Mo(S_1−xSe_x)₂]. The optical studies revealed that the films are highly absorptive (α×10⁴ cm⁻¹) with a band-to-band direct type of transitions and the energy gap decreased typically from 1.86 eV for pure MoS₂ down to 1.42 eV for MoSe₂. The thermoelectrical power measurement shows negative polarity for the generated voltage across the two ends of semiconductor thin films. This indicate that the [Mo(S_1−xSe_x)₂] thin film samples show n-type conduction.     

Preparation of dense and uniform La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) films for fundamental studies of SOFC cathodes

Thin films of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) were deposited on (1 0 0) silicon and on GDC electrolyte substrates by rf-magnetron sputtering using a single-phase oxide target of LSCF. The conditions for sputtering were systematically studied to get dense and uniform films, including substrate temperature (23–600 °C) background pressure (1.2 × 10⁻² to 3.0 × 10⁻² mbar), power, and deposition time. Results indicate that to produce a dense, uniform, and crack-free LSCF film, the best substrate temperature is 23 °C and the argon pressure is 2.5 × 10⁻² mbar. Further, the electrochemical properties of a dense LSCF film were also determined in a cell consisting of a dense LSCF film (as working electrode), a GDC electrolyte membrane, and a porous LSCF counter electrode. Successful fabrication of high quality (dense and uniform) LSCF films with control of thickness, morphology, and crystallinity is vital to fundamental studies of cathode materials for solid oxide fuel cells.     

Thermal cycle stability of BaO–B2O3–SiO2 sealing glass

Thermal cycle stability is very important for glass seals in planar solid oxide fuel cell (pSOFC) applications. In the present study, thermal cycle stability of a thermally stable sealing glass is investigated using a sealing fixture from 150 °C to 700 °C. SS410 alloy with the TEC (thermal expansion coefficient) of 12.2 × 10⁻⁶ K⁻¹ (room temperature to 700 °C) is used to evaluate the effect of TEC mismatch on the thermal cycle stability. The leak rates increase with thermal cycles and appear to be two different stages. Microstructure examinations are performed to investigate the degradation mechanism of the thermal cycle stability. It is found that the sealing glass interacts chemically with the SS410 alloy and the formation of BaCrO₄ new phase results in the rapid increase of the leak rates.     

An alkaline direct NaBH4–H2O2 fuel cell with high power density

A high performance alkaline direct borohydride–hydrogen peroxide fuel cell with Pt–Ru catalyzed nickel foam as anode and Pd–Ir catalyzed nickel foam as cathode is reported. The electrodes were prepared by electrodeposition of the catalyst components on nickel foam. Their morphology and composition were analyzed by SEM–EDX. The effects of concentrations of NaBH₄ and H₂O₂ as well as operation temperature on the cell performance were investigated. The cell exhibited an open circuit voltage of about 1.0 V and a peak power density of 198 mW cm⁻² at a current density of 397 mA cm⁻² and a cell voltage of 0.5 V using 0.2 mol dm⁻³ NaBH₄ as fuel and 0.4 mol dm⁻³ H₂O₂ as oxidant operating at room temperature. Electrooxidation of NaBH₄ on Pt–Ru nanoparticles was studied using a rotating disk electrode and complete 8e⁻ oxidation was observed in 2 mol dm⁻³ NaOH solution containing 0.01 mol dm⁻³ NaBH₄.     

Optical and electrochemical properties of V2O5:Ta Sol–Gel thin films

Vanadium and tantalum-doped vanadium pentoxide, V₂O₅ and V₂O₅:Ta thin films (2.5 and 5 mol% of Ta) were prepared using sol–gel dip-coating technique.The coating solutions were prepared by reacting vanadium (V) oxytripropoxide and tantalum ethoxide (V) as precursors using anhydrous isopropyl alcohol as solvent.The films were deposited on a transparent glass substrate with ITO conducting film by dip-coating technique, with a withdrawal of 20 cm/min from the vanadium–tantalum solution and heat treated at 300 °C for 1 h. The resulting films were characterized by cyclic voltammetry, optical spectroscopy and by X-ray diffraction analysis (XRD). XRD data show that the films thermally treated at 300 °C were crystalline.A charge density of 70 mC/cm² was obtained for the film with 5 mol% of Ta, with an excellent stability up to 1500 cycles.     

Electrical conduction studies of hot wall deposited CdSexTe1−x thin films

CdSe_xTe_1−x thin films of different compositions have been deposited on cleaned glass substrates using the hot wall deposition technique under conditions very close to thermodynamical equilibrium with minimum loss of material. The electrical conductivity of the deposited films has been studied as a function of temperature. All the films showed a transition from phonon-assisted hopping conduction through the impurity band to grain-boundary-limited conduction in the conduction/valence band at temperature around 325 K. The conductivity has been found to vary with composition; it varied from 0.0027 to 0.0198 Ω⁻¹ cm⁻¹ when x changed from 0 to 1. The activation energies of the films of different compositions determined at 225 and 400 K have been observed to lie in the range 0.0031–0.0098 and 0.0285–0.0750 eV, respectively. The Hall-effect studies carried out on the deposited films revealed that the nature of conductivity (p or n-type) was dependent on film composition; films with composition x=0 and 0.15 have been found to be p-type and the ones with composition x=0.4, 0.6, 0.7, 0.85 and 1 have been observed to exhibit n-type conductivity. The carrier concentration has been determined and is of the order of 10¹⁷ cm⁻³. The majority of carrier mobilities of the films have been observed to vary from 0.032 to 0.183 cm² V⁻¹ s⁻¹ depending on film composition. The study of the mobility of the charge carriers with temperature in the range of 300–450 K showed that the mobility increased with power of temperature indicating that the type of scattering mechanism in the studied temperature range is the ionized impurity scattering mechanism.     

Formation of CuIn(S,Se)2 thin film by thermal diffusion of sulfur and selenium vapours into Cu–In alloy within a closed graphite container

The formation of CuIn(S,Se)₂ thin films by thermal diffusion of sulfur (S) and selenium (Se) vapours into co-sputtered Cu–In alloy within a closed-space graphite container is reported. All films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), Four-point-probe and hot-probe measurements. Cu–In alloy films with composition varying from Cu-rich to In-rich were deposited. The synthesized In-rich films yielded CuIn₅(S,Se)₈ spinel compound which gradually transformed into a single phase CuIn(S,Se)₂ as the film composition approached the Cu-rich region. The morphology of the CuIn₅(S,Se)₈ was found to differ from the stoichiometric and Cu-rich CuIn(S,Se)₂ as observed from SEM. EDX composition analysis of the films showed a Cu/In ratio varying from 0.36 to 1.54 and a (S+Se)/(Cu+In) varying from 0.97 to 1.32. The amount of S incorporated in the films was found to differ with changes in the composition. The resistivity of the films ranged between 10⁻¹ and 10⁷ Ω cm and it strongly followed the change in the alloy film composition.     

Electrochromic properties of heat-treated thin films of CeO2–TiO2–ZrO2 prepared by sol–gel route

CeO₂–TiO₂–ZrO₂ thin films were prepared using the sol–gel process and deposited on glass and ITO-coated glass substrates via dip-coating technique. The samples were heat treated between 100 and 500 °C. The heat treatment effects on the electrochromic performances of the films were determined by means of cyclic voltammetry measurements. The structural behavior of the film was characterized by atomic force microscopy and X-ray diffraction. Refractive index, extinction coefficient, and thickness of the films were determined in the 350–1000 nm wavelength, using nkd spectrophotometry analysis.Heat treatment temperature affects the electrochromic, optical, and structural properties of the film. The charge density of the samples increased from 8.8 to 14.8 mC/cm², with increasing heat-treatment temperatures from 100 to 500 °C. It was determined that the highest ratio between anodic and cathodic charge takes place with increase of temperature up to 500 °C.     

Electrophoretic deposition of dense BaCe0.9Y0.1O3−x electrolyte thick-films on Ni-based anodes for intermediate temperature solid oxide fuel cells

Proton conducting BaCe_0.9Y_0.1O_3−x (BCY10) thick films are deposited on cermet anodes made of nickel–yttrium doped barium cerate using electrophoretic deposition (EPD) technique. BCY10 powders are prepared by the citrate–nitrate auto-combustion method and the cermet anodes are prepared by the evaporation and decomposition solution and suspension method. The EPD parameters are optimized and the deposition time is varied between 1 and 5 min to obtain films with different thicknesses. The anode substrates and electrolyte films are co-sintered at 1550 °C for 2 h to obtain a dense electrolyte film keeping a suitable porosity in the anode, with a single heating treatment. The samples are characterized by field emission scanning electron microscopy (FE-SEM) and energy dispersion spectroscopy (EDS). A prototype fuel cell is prepared depositing a composite La_0.8Sr_0.2Co_0.8Fe_0.2O₃ (LSCF)–BaCe_0.9Yb_0.1O_3−δ (10YbBC) cathode on the co-sintered half cell. Fuel cell tests that are performed at 650 °C on the prototype single cells show a maximum power density of 174 mW cm⁻².     

New hybrid inorganic–organic polymer electrolytes based on Zr(O(CH2)3CH3)4, glycerol and EMIm-TFSI ionic liquid

This report presents detailed studies on the elemental analysis, vibrational spectroscopy, thermal stability and electrical spectroscopy of two new hybrid inorganic–organic polymers which have been synthesised by a sol–gel method using glycerol and zirconium(IV)butoxide as precursors. These materials have been doped by means of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm-TFSI) ionic liquid (IL), which is insoluble in water. The elemental composition of the obtained polymers [Zr(C₆O₅H₁₁)] (1) and [Zr(C₁₁O₄H₃₁)] (2) has been determined by CHN analysis and by ICP-AES measurements. FT-IR and FT-Raman spectroscopy investigations have been performed to study the molecular structure of the polymers and the interactions of EMIm-TFSI with the host networks. Differential scanning calorimetry measurements show the presence of at least one glass transition temperature (T_g) in both 1 and 2 materials. The broadband dielectric spectroscopic measurements have been carried out between 10⁻² Hz to 10 MHz from −100 °C to 100 °C with a 5 °C step. The conductivities of the polymers 1 and 2 have been found to be in the order of 10⁻⁸ to 10⁻¹¹ S cm⁻¹ at 25 °C, so they can be defined as dielectric materials. After doping 2 with EMIm-TFSI, the conductivity at 25 °C of the obtained complex [Zr(C₁₁O₄H₃₁)]₁₅/(EMIm-TFSI) (2′) increased three orders of magnitude resulting ca. 10⁻⁵ S cm⁻¹. The permittivity spectra revealed two relaxation bands which were attributed to the α relaxation modes of the polymer networks.     

Synthesis of CuInS2 by chemical route: optical characterization

CuInS₂ powder was prepared by wet chemical route. The chalcopyrite structure of the powder was revealed by XRD studies. Raman measurements of the powder sample indicated four prominent peaks at 292, 305, 340 and 472 cm⁻¹. The possible origin of the 305 cm⁻¹ peak was investigated and was found to be some local vibration in the structure. The peaks at 292 and 340 cm⁻¹ were ascribed to A₁ and B₂ modes, respectively. The peak at 472 cm⁻¹ which was due to the formation of SO₄⁻² ion at lower pH value of the precursor solution could be eliminated by using pH>11.0. Photoluminescence (PL) studies of the CuInS₂ powder indicated two distinct peaks at 1.49 and 1.42 eV. Post deposition annealing treatment in H₂ atmosphere revealed the formation of excess sulphur vacancy leading to the peak at 1.42 eV in the PL spectra while O₂ annealing of the powder created a deep defect level at 1.10 eV. Thick CuInS₂ films were prepared by Doctor's blade technique. Optical transmittance studies of these films indicated direct allowed transition at 1.5 eV.     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

A poly(R1R2R3)–N/H3PO4 composite membrane for phosphoric acid polymer electrolyte membrane fuel cells

A poly(R₁R₂R₃)–N⁺/H₃PO₄ composite membrane has been developed for use in a polymer electrolyte fuel cell (PEMFC). The quaternized polysulfone (QNPSU) membrane doped with H₃PO₄ showed high proton conductivity (0.12 S cm⁻¹) at 160 °C and gave good performance in a single fuel cell tests. The peak power density with the QNPSU/H₃PO₄ composite membrane (at 150 °C, with dry H₂/O₂) was greater than 0.7 W cm⁻². The effect of the phosphoric acid doping level on fuel cell performances with the QNPSU membrane was investigated. The data show that the QNPSU/H₃PO₄ composite membrane is promising for higher temperature PEMFC applications. The study demonstrated that the poly(R₁R₂R₃)–N⁺/H₃PO₄ composite system produced an effective method to connect phosphoric acid to a non-conducting polymer structure, to produce a promising membrane for phosphoric acid polymer electrolyte membrane fuel cells.     

Electrochemical lithium insertion in sol-gel deposited LiNbO3 films

Inorganic LiNbO₃ ion conducting films were prepared by sol-gel process involving two alkoxides, lithium ethoxide and niobium ethoxide. The films were analyzed by ellipsometry, X-ray diffractometry, scanning electron microscopy and impedance spectroscopy. Impedance spectroscopy indicated that the Li⁺ conductivity values were in the range of 6–8 × 10⁻⁷ S cm⁻¹. The morphology and thickness of these films played an important role in the insertion of lithium ions. Spectrophotometric investigation showed that LiNbO₃ films exhibit very weak cathodic coloration from 350 to 900 nm spectral region. The electrochemical and optical properties clearly indicate that sol-gel deposited LiNbO₃ films can be used as lithium ion conducting layers for electrochromic device application.     

MoO3 nanorods/Fe2(MoO4)3 nanoparticles composite anode for solid oxide fuel cells

MoO₃ nanorods/Fe₂(MoO₄)₃ nanoparticles composite has been prepared by a hydrothermal method combined with an in situ diffusion growth process. Single cells based on 300 μm LSGM electrolyte have been fabricated with the MoO₃ nanorods/Fe₂(MoO₄)₃ nanoparticles composite anode and a composite cathode consisting of Sr_0.9Ce_0.1CoO_3−δ and Sm-doped ceria (SDC). The peak power densities reach 225, 50, 75 mW cm⁻² at 900 °C in H₂, CH₄ and C₃H₈, respectively. The cell shows excellent long-term stability at 850 °C. The preliminary results demonstrate that the MoO₃ nanorods/Fe₂(MoO₄)₃ nanoparticles composite is a promising alternative anode for solid oxide fuel cells.