Solar photocatalytic degradation of gaseous formaldehyde by sol–gel TiO2 thin film for enhancement of indoor air quality

Solar photocatalytic degradation of formaldehyde in the gaseous phase has been investigated. The tested photoreactor is made of a borosilicate glass tube with the inner surface coated with a sol–gel TiO₂ thin film. In a pseudo-first-order Langmuir–Hinshelwood (L–H) model, the maximum reaction rate constant obtained is 0.148 min⁻¹ under an exposure to sunlight with solar UVA irradiance of 1.56 mW/cm². The solar photolysis effect is found to be negligible. It is also found that the sol–gel TiO₂ thin film has a lower apparent photonic efficiency of solar photocatalysis than a Degussa P25 TiO₂ coating. However, for the photonic efficiency taking into account the absorbed and scattered photons only and, in other words, excluding the transmitted photons, the thin film has a higher value. Based on a total of 28 measured data, an empirical-correlation equation has been developed to express the reactant residue with respect to the solar UVA irradiance and exposure time. A reasonable agreement between the correlation and experimental data is obtained. The findings of this investigation can be applied to design optimization of a honeycomb photoreactor made up of TiO₂-coated glass tubes or polygonal cells.     

Effects of illumination and Co γ-ray irradiation on the electrical characteristics of porous silicon solar cells

A new approach for hybrid metal–insulator–semiconductor (MIS) Si solar cells is adopted by Institute of Fundamental Problems for High Technology, Ukrainian Academy of Sciences. In order to interpret the effect of illumination and ⁶⁰Co γ-ray radiation dose on the electrical characteristics of solar cells are studied at room temperature. Before the solar cells are subjected to stressed irradiation six different illumination levels of forward and reverse bias I–V measurements are carried out at room temperature. The solar cells are irradiated with ⁶⁰Co γ-ray source irradiation, with a dose rate of 2.12 kGy/h and an over dose range from 0 to 500 kGy. Experimental results shows that both the values of capacitance and conductance increase with increasing illumination levels and give the peaks at high illumination levels. γ-ray irradiation induces an increase in the barrier heights Φ_b(C–V) which are obtained from reverse-bias C–V measurements, whereas barrier heights Φ_b(I–V) which are deducted from forward-bias I–V measurements remain essentially constant. This negligible change of Φ_b(I–V) is attributed to the low barrier height (BH) in regions associated with the surface termination of dislocations. Both the I–V and C–V characteristics indicate that the total-dose radiation hardness of the Si solar cells cannot be neglected according to illumination levels.     

Performance of solar driven methanol–water combined ejector–absorption cycle in the Athens area

The performance of a solar driven CH₄O-H₂O combined ejector– absorption unit, operating in conjunction with intermediate temperature solar collectors in Athens, is predicted along the five months (May–September) in case of the unit working as heat pump in an industrial area. The operation of the unit and the related thermodynamics are simulated by suitable computer codes and the required local climatological data are determined by statistical processings over a considerable number of years. It is found that the heat gain factor varies in the range from 2.1330 to 2.4481 for the above period of time. The maximum HGF of about 2.4481 is obtained in July at 14.25 hrs with corresponding specific heat gain power 915 W/m². The maximum Q_gain of about 1086 W/m² is obtained in June at 12.54 hrs with corresponding HGF 2.3572. Also the maximum value of HGF was estimated by correlation of three temperatures: generator temperature (85.0°C–97.2°C), condenser temperature (43.3°C–47.6°C) and evaporator temperature (12.6°C–25.4°C).     

Organic solar cells consisting of stacked amine–thiophene copolymer and 3,4,9,10-perylenetetracarboxyl-bis-benzimidazole layers

Organic solar cells were fabricated using a new amine–bithiophene copolymer as an electron donor layer and 3,4,9,10-perylenetetracarboxyl-bis-benzimidazole (PV) as an electron acceptor layer. The amine–thiophene copolymer, poly{(9,9-dioctylfluorene-2,7-diyl)-co-[N,N′-bis(4-tert-butylphenyl)benzidine-N,N′-bis(phenylene-4,4′-diyl)]-co-(2,2′-bithiophene-5,5′-diyl)} (PF8-TPD-T2), had a glass transition temperature (T_g) at about 77 °C, and exhibited liquid crystalline states and a high hole mobility. The rigid bithiophene units in the polymer chain are probably responsible for the formation of the liquid crystalline states and the high hole mobility. A solar cell made of the PF8-TPD-T2 copolymer and PV layers showed a photocurrent density of 0.99 mA/cm², an open-circuit voltage of 0.61 V, and an energy conversion efficiency of 0.332%. The photocurrent of the solar cells was generated at both the copolymer and PV layers, and the copolymer layer was the main contributor to photocurrent when the thickness of the polymer was about 17 nm. After annealing the solar cells at temperatures well above the glass transition temperature (T_g) of the copolymer, the photocurrent action spectra of the solar cells were broadened and the performance was improved. The changes were mostly due to the increased contribution of the PV layer to the photocurrent by the annealing.     

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.     

Preparation of Cu(In,Ga)Se2 thin films from Cu–Se/In–Ga–Se precursors for high-efficiency solar cells

Improved preparation process of a device quality Cu(In,Ga)Se₂ (CIGS) thin film was proposed for production of CIGS solar cells. In–Ga–Se layer were deposited on Mo-coated soda-lime glass, and then the layer was exposed to Cu and Se fluxes to form Cu–Se/In–Ga–Se precursor film at substrate temperature of over 200°C. The precursor film was annealed in Se flux at substrate temperature of over 500°C to obtain high-quality CIGS film. The solar cell with a MgF₂/ITO/ZnO/CdS/CIGS/Mo/glass structure showed an efficiency of 17.5% (V_oc=0.634 V, J_sc=36.4 mA/cm², FF=0.756).     

Optimal optical generation profiles in a-Si:H p–i–n solar cells

The dependence of the maximum power output P_M and short-circuit current J_SC on the form (relative variation with position) of the optical generation rate profile in an a-Si:H p–i–n solar cell has been investigated computationally. It was found that there was an optimal form for the generation profile, and that P_M increased from 4.64 to 5.29 mWcm⁻², an increase of about 14%, when this optimal generation profile was used in the simulation. Optimal doping of the i-layer of the cell with phosphorous led to a P_M of 5.60 mWcm⁻², and when the optimal generation profile for this P-profiled cell was found, it yielded a P_M of 7.86 mWcm⁻², an increase of about 40%. This suggests that the combination of P-profiling and optimal generation could lead to significant improvements in cell performance. Moreover, it was found that for both cells the form of the optimal generation profile could be associated with the position of the peak in the external quantum efficiency, obtained from the spectral response. The possibility of using band-gap grading to achieve an optimal generation rate profile has been suggested.     

Light soaking effect in a-Si:H based n–i–p and p–i–n solar cells

Hydrogenated amorphous silicon solar cells have been realised in both a p–i–n configuration on a Corning glass substrate as well as in a n–i–p configuration on stainless-steel substrate. The performance degradation of the two kinds of cell under solar illumination has been examined for a 140 h period. During degradation, the two devices were kept under load in the maximum power condition that is normally used in a solar plant. The performance of the Corning glass deposited device exhibited a higher rate of degradation with respect to the other cell. A discussion on the possible reasons for this behaviour is given.     

Effect of illumination intensity and temperature on the I–V characteristics of n-C/p-Si heterojunction

Krishna et al. (Sol. Energy Mater. Sol. Cells 65 (2001) 163) have recently developed an heterojunction n-C/p-Si in order to achieve low cost and high-efficiency carbon solar cell. It has been shown that for this structure, the maximum quantum efficiency (25%) appears at wavelength λ (600 nm). In this paper, the dependence of I–V characteristics of this heterojunction solar cell on illumination intensity and temperature has been systematically investigated. An estimation of the stability of the solar cell with temperature has been made in terms of the temperature coefficient of I_sc and V_oc. The intensity variation study has been used to estimate the series resistance R_s of the solar cell.The effect of illumination intensity on I–V of n-C/p-Si heterojunction is more complex because the carrier lifetime and the carrier mobility of amorphous carbon are small and also because drift of carriers by built-in electric field plays an important role in these cells. Therefore, the conventional analytical expression for I–V characteristic is not applicable to such solar cells. These structures will not obey the principle of superposition of illuminated and dark current. The experimental results have been analysed by developing empirical relation for I–V.The temperature sensitivity parameters α, the change in I_sc and β, the change in V_oc per degree centigrade have been computed and are found to be 0.087 mA/°C and 1 mV/°C, respectively. This suggests that the heterojunction n-C/p-Si has good temperature tolerance. The value of series resistance has been estimated from the family of I–V curves at various intensities. The R_s is found to be ≈12 Ω, which is on the higher side from the point of view of photovoltaic application.     

Metastable volume changes of hydrogenated amorphous silicon and silicon–germanium alloys produced by exposure to light

Exposure of hydrogenated amorphous silicon, a-Si:H, to light produces large-scale structural changes and increases the density of dangling Si bond defects acting as efficient carrier recombination centers. The latter is the well-studied Staebler–Wronski effect (SWE). All light-induced changes are metastable and disappear after annealing to approximately 200°C. This review focuses on one of the large-scale changes, namely that of the macroscopic density of the material. In all device quality materials, the initial stress is compressive with values typically in the range of 10⁸–10⁹ Pa. Exposure to light produces additional compressive stress, which can exceed 2×10⁷ Pa. The observed change of stress is due to a change of the volume of the unsupported material and not of its elastic modulus. The relative volume change, ΔV/V, at 300 K becomes detectable at values in excess of about 10⁻⁶ after only a few photons per Si atom have been absorbed. ΔV/V saturates above 10⁻³, under high-intensity light after an average of more than 10⁶ photons per Si atom have been absorbed. ΔV/V initially grows with t^0.50±0.04 under CW illumination producing carrier generation rate G in the range of 10²¹ to a few 10²³ cm⁻³ s⁻¹. The approach to saturation is well fitted by a stretched exponential function with stretch exponent close to 0.5. ΔV/V is approximately proportional to G. The fastest and largest photo-expansion has been observed in the so-called “edge material” between the amorphous and microcrystalline state, produced by plasma enhanced CVD from increasingly diluted silane/hydrogen gas mixtures. The quantum efficiency of volume expansion has been observed to increase with the photon energy of the light in contrast to the SWE. No volume increase is observed in Ge rich a-Si_1−xGe_x:H alloys and in hydrogenated microcrystalline material. Photo-expansion and the SWE show marked difference in spatial extend in the network, different evolution in time and different wavelength dependence. Hence, the two effects appear to be independent even though both involve hydrogen.     

Promising window layer of thin film Si solar cell with p–i–n structure prepared by using SiH2Cl2

The fabrication process for a-Si:H solar cells with p–i–n structure contains a problem of damage to the SnO₂ substrate particularly at higher process temperatures. We have reported that the suppression of darkening and wide optical gap (E_opt) are obtained by using SiH₂Cl₂ instead of SiH₄ as a source gas (Mater. Res. Soc. Symp. Proc. 609 (2000), in press). In this paper, p-type a-Si:H:(Cl) was investigated. Comparable E_opt and dark conductivity (σ_dark) to those of conventional a-SiC:H were obtained. Solar cells using this a-Si:H:(Cl) show higher current density (J_sc) and higher collection efficiency in all wavelength regions as compared to a p-layer not using chlorine processes. The newly developed p-layer has been applied to solar cells with p–i–n structure fabricated at higher substrate temperatures (T_s). Although the a-Si:H material deposited at higher substrate temperatures has been reported as being more stable against light soaking (21st IEEE PVSC Proceeding, Florida, USA, 1990, p. 1656), the high temperature processing is difficult to apply to the a-Si:H p–i–n structure because of the significant darkening of SnO₂ at higher T_s. With an a-Si:H:(Cl) buffer layer, a-Si:H solar cells can be fabricated at higher T_s (300°C) with reasonable cell performance. The best stabilized efficiency was 7.5% obtained at a T_s of 250°C.     

Concentrator silicon solar cells from silicon industry rejects

Two types of silicon (Si) substrates (40 n-type with uniform base doping and 40 n/n⁺ epitaxial wafers) from the silicon industry rejects were chosen as the starting material for low-cost concentrator solar cells. They were divided into four groups, each consisting of 20 substrates: 10 are n/n⁺ and 10 are n substrates, and the solar cells were prepared for different diffusion times (45, 60, 75 and 90 min). The fabricated solar cells on n/n⁺ substrates (prepared with a diffusion time of 75 min) showed better parameters. In order to improve their performances, particularly the fill factor, 20 new solar cells on n/n⁺ substrates were fabricated using the same procedure (the diffusion time was 75 min)—but with four new front contact patterns. Investigation of current–voltage (I–V) characteristics under AM 1.5 showed that the parameters of these 20 new solar cells have improved in comparison to previous solar cells' parameters, and were as follows: open-circuit voltage (V_OC=0.57 V); short circuit current (I_SC=910 mA), and efficiency (η=9.1%). Their fill factor has increased about 33%. The I–V characteristics of these solar cells were also investigated under different concentration ratios (X), and they exhibited the following parameters (under X=100 suns): V_OC=0.62 V and I_SC=36 A.     

The obstructed diffusion of the I3 ion in mesoscopic TiO2 membranes

The diffusional permeability of I⁻₃ ion in acetonitrile in free standing TiO₂ membrane with a porosity of 55% was examined. The apparent diffusion coefficient, D_app at 25°C of the ion was found to be 3.4×10⁻⁶ cm^{2 −1}, an order of magnitude smaller than the free diffusion at the same temperature. The temperature dependency of D_app was measured in the range 0–30°C and analysed in terms of the Walden product. The diffusional activation energy was found to be 13.5 kJ/mol. The parameters of interest for the efficiency of mesoscopic wet solar cells are discussed. A back of an envelope calculation shows that although the obstructed diffusion coefficient of the I⁻₃ ion was an order of magnitude smaller than the free diffusion the diffusional flux is still sufficient to meet a current density of 50 mA cm⁻². At incident photon flux of 1 kW m⁻² and at a photopotential of 0.6 V this would correspond to a solar energy efficiency of approximately 30%.     

Studies on the temperature dependence of I–V and C–V characteristics of electron irradiated silicon photo-detectors

The current transport mechanisms of n⁺–p silicon (Si) photo-detectors in different temperature and bias regions before and after irradiation with a dose of 350 kGy has been investigated and presented in this article. Temperature-dependent dark current–voltage (I–V) studies under forward and reverse bias were carried out for this purpose. In the temperature range studied, the dark current contribution in the low bias range is believed to be due to the generation-recombination of minority carriers in the space-charge region. Electron irradiation does not seem to have altered the dark current conduction mechanism. Capacitance–voltage (C–V) at various temperatures was measured to identify the presence of deep levels in the device.     

Solar cells using iodine-doped polythiophene–porphyrin polymer films

Wet-type organic solar cells containing 5,10,15,20-3-tetrathienylporphyrin (TThP) and polythiophene (PTh) films were fabricated. The TThP/PTh film was prepared on indium-tin-oxide (ITO) glass using an electrochemical polymerization method in an n-Bu₄NPF₆/CH₂Cl₂ solution. It was found that a small amount of iodine doping of the film improved the incident photon-to-electron conversion efficiency (IPCE) of a solar cell consisting of a TThP/PTh film and an aqueous electrolyte. A HOMO level measurement suggested that a modified HOMO level of the low iodine-doped TThP/PTh film allowed a fast electron transfer from PTh to a porphyrin moiety. To obtain further improvement, a sandwich-type solar cell using a 5% (w/w) aqueous solution of acetonitrile containing 0.05 M iodine and 0.5 M lithium iodide as an electrolyte was then fabricated. The solar cell absorbed light in the 300–800 nm wavelength range, converting this to a cathodic photocurrent with a maximum IPCE of 32% at 430 nm under irradiation of 5.0×10¹⁴ photon cm⁻² s⁻¹. This value is about 10 times higher than that of the solar cells using an aqueous electrolyte. The total energy conversion efficiency (η) of the solar cell under simulated sunlight reached 0.12% for 2.59 mW cm⁻² at AM1.5 and 0.05% for 100 mW cm⁻² at air mass 1.5.     

Optical and electrochemical characteristics of sol–gel deposited iron oxide films

Homogenous, crack free iron oxide films are prepared by the sol–gel spin coating technique from a solution of iron iso-propoxide and isopropanol. The films were characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-visible (UV–Vis) spectroscopy and cyclic voltammetry (CV). XRD of the films showed that they had an amorphous structure. The optical constants refractive index (n) and extinction coefficient (k) were measured by scanning spectrometer in the wavelength range of 390–990 nm. The n and k values were found n =2.3±0.01 and k =0.2±0.002 at 650 nm. The electrochemical behavior investigated in 0.5 M LiClO₄ propylene carbonate (PC) electrolyte-CV examinations showed good rechargeability of the Li⁺/e⁻ insertion extraction process beyond 300 cycles. Spectroelectrochemistry showed that these films exhibit weak cathodic coloration in the spectral range of 350–800 nm.     

Thermodynamic analysis of monomethylamine–water solutions in a single-stage solar absorption refrigeration cycle at low generator temperatures

A theoretical analysis of the coefficient of performance COP was undertaken to examine the efficiency characteristics of the monomethylamine–water solutions for a single-stage absorption refrigeration machine, using low generator temperatures (60–80°C), which allows the use of flat plate solar collectors. The thermodynamic analysis considers both, basic and refined cycles. The refined absorption cycle included a sensible heat recover exchanger (that is a solution heat exchanger). The thermal coefficients of performance COP_h for the basis cycle and COP_SHE for the refined cycle were calculated using the enthalpies at various combinations, at the operating temperatures and concentrations. The flow ratio F_R has been calculated as additional optimization parameter. Due to the relative low pressure and the high coefficients of performance, the monomethylamine–water solutions present interesting properties for their application in solar absorption cycles at moderate condenser and absorber temperatures (25–35°C), with temperatures in the evaporator from −10°C to 10°C which are highly usable for food product preservation and for air conditioning in rural areas.     

Sol–gel deposition and optical characterization of multilayered SiO2/Ti1−xSixO2 coatings on solar collector glasses

Thin films of silicon oxide and silicon titanium mixed oxides are deposited on solar collector glazing in a sol–gel dip-coating process based on alcoxide precursors. Spectrophotometry is used to characterize the relation of film thickness and withdrawal speed for the precursor solutions, and to determine the refractive index of individual layers of the mixed oxides. The inferred dispersion relations n(λ) are compared to the predictions of effective medium theories. Based on the knowledge of the optical properties of individual layers, multilayer interference stacks are designed. Multilayered samples of superior quality are deposited by sol–gel dip-coating in a particle-free environment. The final optical performance of the multilayer stacks are characterized in terms of the visible reflectance R_VIS, CIE color coordinates, and the solar transmission T_sol. Values of up to 2.4 have been attained for the energy efficiency of the colored reflection M=R_VIS/(100%-T_sol). The produced coatings combine a bright colored reflection with an acceptable solar transmittance, and are thus well suited for the application in colored glazed thermal solar collectors. This novel type of colored glazing opens up new perspectives for the architectural integration of thermal solar collectors, e.g. as solar active glass facades.     

A numerical model of p–n junctions bordering on surfaces

Many solar cell structures contain regions where the emitter p–n junction borders on the surface. If the surface is not well passivated, a large amount of recombination occurs in such regions. This type of recombination is influenced by the electrostatics of both the p–n junction and the surface, and hence it is different from the commonly described recombination phenomena occurring in the p–n junction within the bulk. We developed a two-dimensional model for the recombination mechanisms occurring in emitter p–n junctions bordering on surfaces. The model is validated by reproducing the experimental I–V curves of specially designed silicon solar cells. It is shown under which circumstances a poor surface passivation, near where the p–n junction borders on the surface, reduces the fill factor and the open-circuit voltage. The model can be applied to many other types of solar cells.     

n–p Junction formation in p-type silicon by hydrogen ion implantation

Hydrogen ion implantations at an energy of 250 keV and a dose of 3×10¹⁶ cm⁻² were applied to float zone, Czochralski grown silicon wafers and to multicrystalline samples. It was found that after annealing at 350°C<T<550°C for 1 h a n–p junction is formed and a photovoltaic behaviour is observed. Spectral responses show that the photocurrent in the near infrared part of the spectrum is comparable to that given by a standard silicon solar cell. The depth of the junction is about 2 μm and C–V measurements show that the junction is graduated. Hydrogen plasma immersion leads to similar results. The conversion of p- to n-type silicon is explained by the formation of shallow donor levels associated to a high concentration of hydrogen.