Photocatalytic degradation of DBSNa using solar energy

This paper reports experimental results on photocatalytic degradation of sodium dodecylbenzene sulfonate (DBSNa), using the solar energy concentrator for photocatalysis studies (SECPS). The SECPS operation is based on the concentration of ultraviolet solar radiation on a reactor that contains contaminated water and a catalyst where the photocatalytic effect occurs. This effect produces ruptures in the toxic molecules, until transforming them into harmless compounds. The study focuses on determining how great is the contribution of the catalyst itself and the oxidant agent to the DBSNa photocatalytic degradation. Finally, three conditions were found as optimal for the photocatalytic degradation of DBSNa using the SECPS, which are 0.2 wt% TiO₂, 3000 ppm H₂O₂ and 60 min exposure time.     

CVD of CuGaSe2 for thin film solar cells with various transport agents

Chemical vapor deposition (CVD) in an open tube system was employed to deposit single-phase CuGaSe₂ thin films on plain and Mo-coated glass substrates. The use of HCl and ternary CuGaSe₂ source material resulted in non-stoichiometric volatilization of the source material. The use of binary source materials – Cu₂Se and Ga₂Se₃ – in combination with I₂ and HCl as the respective transport agents yielded single-phase CuGaSe₂ thin films while the source materials were volatilized stoichiometrically. Mo/CuGaSe₂/CdS/ZnO devices were fabricated from these samples exhibiting an open-circuit voltages up to V_oc=853 mV.     

Development and manufacturing of CIS thin film solar modules

Thin film modules based on CIS-technology with power outputs ranging between 5 and 40 W and corresponding circuit aperture area efficiencies between 9.6% and 11% have been introduced recently by Siemens Solar. Current status of production yield and performance is presented demonstrating significantly higher performance than alternative thin film technologies. Further developments have resulted in new champion efficiencies of 12.1% for a large commercial size modules and 14.7% for a small laboratory module.     

Floating photocatalysts based on TiO2 grafted on expanded polystyrene beads for the solar degradation of dyes

In this work, a highly active, low cost, simple and robust floating photocatalyst based on TiO₂ P25 grafted on expanded polystyrene (EPS) beads was developed. SEM and TG analyses showed that ca. 18 wt% of TiO₂ can be permanently grafted on the surface of EPS particles. This floating photocatalyst showed high efficiency for the degradation of three different dyes, i.e. methylene blue, indigo carmine and drimaren red, with UV (Hg 245 nm) or solar irradiation under constrained conditions, i.e. non-stirring and no-oxygenation. Under the same conditions pure TiO₂ showed very low activities. The floating photocatalyst can be reused for at least four consecutive times without any significant decrease on the discoloration and TOC removal after each reuse.     

Surface sulfurization studies of Cu(InGa)Se2 thin film

Sulfurization of copper indium gallium diselenide (CIGS) thin films solar cell absorber has been used to enhance the open-circuit voltage of the device by increasing the band gap of the absorber near the interface. Sulfurization of a homogeneous co-evaporated Cu(InGa)Se₂ thin film was studied in hydrogen sulfide and in a mixture of hydrogen sulfide and hydrogen selenide gases with the inclusion of oxygen. The structural and compositional properties of the absorber layer were investigated by XRD, EDS and AES. Sulfurization in hydrogen sulfide gas forms a fully converted sulfide layer at the top of the absorber layer, which in turn forms a barrier for the current collection. Sulfurization in a mixture of hydrogen sulfide and hydrogen selenide gases forms a wide band gap Cu(InGa)(SeS)₂ layer at the surface, but at the same time there is Ga diffusion away from the surface with the inclusion of sulfur at the surface.     

TiO2 thin films as protective material for transparent-conducting oxides used in Si thin film solar cells

Nb-doped TiO₂ films have been fabricated by RF magnetron sputtering as protective material for transparent-conducting oxide (TCO) films used in Si thin film solar cells. It is found that TiO₂ has higher resistance against hydrogen radical exposure, utilizing the hot-wire CVD (catalytic CVD) apparatus, compared with SnO₂ and ZnO. Further, the minimum thickness of TiO₂ film as protective material for TCO was experimentally investigated. Electrical conductivity of TiO₂ in the as-deposited film is found to be 10⁻⁶ S/cm due to the Nb doping. Higher conductivity of 10⁻² S/cm is achieved in thermally annealed films. Nitrogen treatments of Nb-doped TiO₂ film have been also performed for improvements of optical and electric properties of the film. The electrical conductivity becomes 4.5×10⁻² S/cm by N₂ annealing of TiO₂ films at 500 °C for 30 min. It is found that the refractive index n of Nb-doped TiO₂ films can be controlled by nitrogen doping (from n=2.2 to 2.5 at λ = 550 nm) using N₂ as a reactive gas. The controllability of n implies a better optical matching at the TCO/p-layer interface in Si thin film solar cells.     

Effect of 8 MeV electron irradiation on electrical properties of CuInSe2 thin films

Radiation damages due to 8 MeV electron irradiation in electrical properties of CuInSe₂ thin films have been investigated. The n-type CuInSe₂ films in which the carrier concentration was about 3×10¹⁶ cm⁻³, were epitaxially grown on a GaAs(0 0 1) substrate by RF diode sputtering. No significant change in the electrical properties was observed under the electron fluence <3×10¹⁶ e cm⁻². As the electron fluence exceeded 10¹⁷ e cm⁻², both the carrier concentration and Hall mobility slightly decreased. The carrier removal rate was estimated to be about 0.8 cm⁻¹, which is slightly lower than that of III–V compound materials.     

High fidelity transfer of nanometric random textures by UV embossing for thin film solar cells applications

We investigate the transfer of random nanostructures commonly used in thin film silicon solar cells onto inexpensive substrates, such as glass or flexible polyethylene sheets. Morphological and optical analyses of masters and replicas show the successful transfer of details with sizes much below 1 μm. These high-quality replicas are obtained by UV nano-imprinting, avoiding the use of PDMS as an intermediate mold, which has been identified as being responsible for the lack of resolution found in previous works.     

Enhanced heterogeneous ferrioxalate photo-fenton degradation of reactive orange 4 by solar light

A combined homogeneous and heterogeneous photocatalytic decolourisation and degradation of a chlorotriazine Reactive azo dye Reactive Orange 4 (RO4) have been carried out using ferrous sulphate/ ferrioxalate with H₂O₂ and TiO₂-P25 particles. Solar/ferrous/H₂O₂/TiO₂-P25 and solar/ferrioxalate/H₂O₂/TiO₂-P25 processes are found to be more efficient than the individual photo-Fenton and solar/TiO₂-P25 processes. A comparison of these two processes with UV/ferrous/H₂O₂/TiO₂-P25 and UV/ferrioxalate/H₂O₂/TiO₂-P25 reveals that ferrioxalate is more efficient in solar light whereas ferrous ion is more efficient in UV light. The experimental parameters such as pH, initial H₂O₂, Fe²⁺, ferrioxalate and TiO₂-P25 concentration strongly influenced the dye removal rate in solar processes. The optimum operating conditions of these two combined processes are reported.     

Development of thin film solar cell based on Cu2ZnSnS4 thin films

Cu₂ZnSnS₄ (hereafter CZTS) thin films were successfully formed by vapor-phase sulfurization of precursors on a soda lime glass substrate (hereafter SLG) and a Mo-coated one (hereafter Mo-SLG). From the optical properties, we estimate the band-gap energy of this thin film as 1.45–1.6 eV which is quite close to the optimum value for a solar cell. By using this thin film as an absorber layer, we could fabricate a new type of thin film solar cell, which was composed of Al/ZnO:Al/CdS/CZTS/Mo-SLG. The best conversion efficiency achieved in our study was 2.62% and the highest open-circuit voltage was 735 mV. These device results are the best reported so far for CZTS.     

Preparation and properties of CuInS2 thin film prepared from electroplated precursor

Thin CuInS₂ films were prepared by sulfurization of Cu/In bi-layers. First, the precursor layer was electroplated onto the treated surface of Mo-coated glass. Observation of the cross-section prepared by focused ion beam (FIB) etching revealed that the void-free film was initially formed on the top surface of the precursor layer and continued to grow until the advancing front of the film reached the Mo layer. The nucleation of voids near the bottom of the CuInS₂ film followed. To determine whether the condition of the Cu/In alloy influences the CuInS₂ quality we investigated the Cu/In alloy state using FIB. We found that the annealed precursor of low Cu/In ratio (1.2) has several voids in the mid position in the layer compared with Cu-rich precursor (1.6). The cross-sectional view of the Cu-rich absorber layer is uniform compared with the low copper absorber layer. Thin film solar cells were fabricated using the CuInS₂ film (Cu/In ratio: 1.2) as an optical absorber layer. It was found that the optimization of a sulfurization period is important in order to improve the cell efficiency. We have not yet obtained good results with high Cu-rich absorber because of a blister problem. This blister was found before sulfurization. So, we are going to solve this blister problem before sulfurization.     

Cathodic electrodeposition of Cu2S thin film for solar energy conversion

Cathodic electrodeposition in the presence of EDTA in aqueous solution was used to prepare Cu₂S thin film deposited on Ti substrate. The effect of deposition potential, concentration and deposition time was studied to determine the optimum condition for electro-deposition process. Cyclic voltammetry was performed to elucidate the electrodic processes that occur while potentials for electrodeposition were applied to determine the optimum potential for electrodeposition. The thin films are characterised by X-ray diffractometry. The photoactivity of the deposited films and their conduction types were evaluated using photoelectrochemical technique. The band gap energy and type of optical transitions were determined from optical absorbance data.     

CuInS2/In2S3 thin film solar cell using spray pyrolysis technique having 9.5% efficiency

Copper indium sulfide (CuInS₂)/In₂S₃ solar cells were fabricated using spray pyrolysis method and high short circuit current density and moderate open circuit voltage were obtained by adjusting the condition of deposition and thickness of both the layers. Consequently, a relatively high efficiency of 9.5% (active area) was obtained without any anti-reflection coating. The cell structure was ITO/CuInS₂/In₂S₃/Ag. We avoided the usual cyanide etching and CdS buffer layer, both toxic, for the fabrication of the cell.     

Photodegradation of methyl tertiary butyl ether (MTBE) vapor with immobilized titanium dioxide

A study on the photocatalytic degradation of methyl tertiary butyl ether (MTBE) vapor was performed with respect to reaction parameters, kinetics, and mechanism. A conventional TiO₂-coated plate system was used for this initial work on vaporized MTBE. On irradiating with UVBLB (5 mW/cm²), 0.6 mg/cm² of TiO₂ (P25) photocatalyst showed the highest reaction rate (0.85 μmol/min) for 25.76 μmole of MTBE (1000 ppmv). The numerical values obtained depended predictably with respect to light intensity, initial concentration, and quantity of P25. The photocatalytic degradation of MTBE followed Lanmuir-Hinshelwood kinetics with a linearity of 0.989. As far as the mechanism of degradation is concerned, attack by generated hydroxyl radicals on the methoxy group in the MTBE structure dominated and proceeded through tert-butyl formate (TBF) as an intermediate, instead of methyl group to proceed through producing 2-methoxy-2-methyl propionaldehyde (MMP). TBF finally degrades to CO₂ through acetone, which was shown easily converted to CO₂. This study shows that the use of sunlight seems to be possible given adequate tools for concentrating the light.     

Improved Cu(In,Ga)(S,Se)2 thin film solar cells by surface sulfurization

Surface sulfurization was developed as a technique for fabricating efficient ZnO : Al/CdS/graded Cu(In,Ga)(S,Se)₂/ Mo/glass solar cells. Prior to the sulfurization, single-graded Cu(In,Ga)Se₂ (CIGS) films were deposited by a multi-stage process. The sulfurization of CIGS films was carried out using a H₂S---Ar mixture at elevated temperatures. The crystallographic and compositional properties of the absorber layers were investigated by XRD, SEM and AES analyses. After sulfurization, sulfur atoms were substituted for selenium atoms at the surface layer of CIGS films to form a Cu(In,Ga)(S,Se)₂ absorber layer. The diffusion of sulfur depends strongly on the grain structure of CIGS film. The cell efficiency of the 8–11% range before sulfurization was improved dramatically to 14.3% with V_oc = 528 mV, J_sc = 39.9 mA/cm² and FF = 0.68 after the sulfurization process.     

Depth profile analysis of CuInSe2 (CIS) thin films grown by the electrodeposition technique

In this study, we report the results obtained from the auger electron spectroscopy (AES) depth profiling of CIS thin films grown by the electrodeposition technique. This result enables one to do a comparison between the bulk and superficial elemental compositions. The AES result is also compared with that obtained by the inductively coupled plasma (ICP) spectroscopy. These results support our proposition that the electrodeposited CIS film has a Cu-rich bulk region and an In rich surface, which leads to the formation of an n-layer (CuIn₂Se_3.5) on the top of the p-type CIS (CuInSe₂) phase     

Study on surface states of Pt/TiO2 thin film in different atmospheres

In this paper, the surface states of Pt/TiO₂ thin film were tested in air, H₂ and N₂ flows. Pt/TiO₂ was prepared by means of photoreduction of on anatase nano-TiO₂ powders and was coated on the microscopy glass using powder–sol technique. Powder conductivity method was applied in the analysis of surface states. The experimental results show that a new surface state was formed in air flow; which was 0.43 eV lower than the conduction band edge of TiO₂. In N₂ flow, three surface states, with the energy levels of 0.42, 0.62 and 0.90 eV, respectively, were detected. Compared with that tested in airflow, 0.42 and 0.62 eV could be attributed to Pt and floating bond of TiO₂ respectively, while 0.90 eV might have resulted from the Ti³⁺ formed at high temperature in N₂ flow. The conductivity of the sample tested in H₂ flow increased significantly and was almost unchanged with temperature, which could be interpreted by the dissociative adsorption of H₂ on Pt.     

Dynamic behavior of surface film on LiCoO2 thin film electrode

Electrochemical oxidation behavior of non-aqueous electrolytes on LiCoO₂ thin film electrodes were investigated by in situ polarization modulation Fourier transform infrared (PM-FTIR) spectroscopy, atomic force microscopy and X-ray photoelectron spectroscopy (XPS). LiCoO₂ thin film electrode on gold substrate was prepared by rf-sputtering method. In situ PM-FTIR spectra were obtained at various electrode potentials during cyclic voltammetry measurement between 3.5 V vs. Li/Li⁺ and 4.2 V vs. Li/Li⁺. During anodic polarization, oxidation of non-aqueous electrolyte was observed, and oxidized products remained on the electrode at the potential higher than 3.75 V vs. Li/Li⁺ as a surface film. During cathodic polarization, the stripping of the surface film was observed at the potential lower than 3.9 V vs. Li/Li⁺. Depth profile of XPS also showed that more organic surface film remained on charged LiCoO₂ than that on discharged one. AFM images of charged and discharged electrodes showed that some decomposed products deposited on charged electrode and disappeared from the surface of discharged one. These results indicate that the surface film on LiCoO₂ is not so stable.     

Enhanced H2 production activity under solar irradiation over N-doped TiO2 prepared using pyridine as a precursor: a typical sample of N-doped TiO2 series

A series of N-doped TiO₂ photocatalysts were synthesized by simple hydrolysis method using titanium isopropoxide and pyridine precusors. XRD studies of all the catalysts showed a single anatase phase and TEM results confirmed that the particles obtained by this procedure are of nano size and in the range of 3–5 nm. UV–vis DRS of N-doped TiO₂ catalysts clearly show an enhanced absorption in the visible light region, and the band gaps are seen decreasing as the content of doped nitrogen increases. The formation of oxynitride linkages is evidenced by the FTIR results. Further the XPS analysis confirms the presence of Ti-O-N linkage, and the binding energy values indicate that the doped nitrogen is either interstitial or chemisorbed. The photocatalytic activity of N-doped TiO₂ catalysts is evaluated for hydrogen production in methanol: water mixture under solar light irradiation and 0.5 wt% N-doped TiO₂ has shown a stable and high activity, 3500 μ mol/h/g.cat. The enhanced hydrogen production activity of N-doped TiO₂ catalysts is attributed to the high surface area of the catalysts containing doped nitrogen mostly at the interstitial positions and enhanced visible light absorption.     

TiO2 nanotubes incorporated with CdS for photocatalytic hydrogen production from splitting water under visible light irradiation

The CdS/TiO₂ composites were synthesized using titanate nanotubes (TiO₂NTs) with different pore diameters as the precursor by simple ion change and followed by sulfurization process at a moderate temperature. Some of results obtained from XRD, TEM, BET, UV–vis and PL analysis confirmed that cadmium sulfide nanoparticles (CdSNPs) incorporated into the titanium dioxide nanotubes. The photocatalytic production of H₂ was remarkably enhanced when CdS nanoparticles was incorporated into TiO₂NTs. The apparent quantum yield for hydrogen production reached about 43.4% under visible light around λ = 420 nm. The high activity might be attributed to the following reasons: (1) the quantum size effect and homogeneous distribution of CdSNPs; (2) the synergetic effects between CdS particles and TiO₂NTs, viz., the potential gradient at the interface between CdSNPs and TiO₂NTs.