Silicon tubes by a closed molten zone: a characterisation study

We report on the characterisation of silicon tubes recrystallised by closed molten zone, a technique developed as a step to a possible process for thin silicon sheet production. The tube faces are quite flat and have a smooth surface. For the electrical characterisation, samples were cut from the tube faces and simple photovoltaic solar cells were formed. The average diffusion length of minority carriers was found, from spectral response, to be around 100 μm. Low-resolution LBIC measurements showed lower diffusion lengths (around 40 μm) in the regions close to the tube edges. This behaviour was correlated to measurements of residual thermal stresses using infrared photoelasticity. Measurements of the changes of spectral response with increasing bias light intensity reveal an increase in the effective diffusion length, a known effect that is interpreted in terms of a density of trapping states.     

Influence of electrode on electrical conduction of ZincPhthalocyanine (ZnPc) thin films

The electrical conduction properties of ZincPhthalocyanine (ZnPc) thin films have been studied using copper, silver and aluminium electrodes. The sandwich structures were prepared by the thermal evaporation method. The I–V characteristics were investigated to identify the dominant charge transport mechanism in the films. Among all possible mechanisms, it was observed that the data fits well to the SCLC type of conduction in the Al/ZnPc/Al and Schottky type of conduction prevails in the Ag/ZnPc/Ag and Cu/ZnPc/Cu devices. The trap levels and its dependence of structure have been studied and results are discussed. The charge transport phenomenon in the ZnPc films seems to depend highly on the electrode material and temperature. The carrier mobility increases with increasing temperature whereas the density of trapped holes decreases with increasing temperature. The barrier height also decreases with increase in temperature. The influence of the temperature on the electrical parameters such as saturation current density (J_s), barrier height (Φ_b), density of states in the valence band edge N_d (m⁻³), the position of the Fermi level E_F (eV), ionized acceptor atom density N_e (m⁻³), activation energy ΔΦ (eV), mobilities of hole (μ₀) and the concentration of free holes in the valence band (n₀) have been discussed in detail.     

Effect of spatial variation of incident radiation on spectral response of a large area silicon solar cell and the cell parameters determined from it

Effect of spatial variation of incident monochromatic light on spectral response of an n⁺–p–p⁺ silicon solar cell and determination of diffusion length of minority carriers (L_b) in the base region and the thickness of the apparent dead layer (x_d) in the n⁺ emitter from the spectral response have been investigated. Spectral response of a few 10 cm diameter and 10×10 cm² pseudo-square silicon solar cells was measured with the help of a standard silicon solar cell of 2×2 cm² area in 400–1100 nm wavelength range. Different areas (4, 9, 16, 25 and total area 78.6 or 96 cm²) were exposed. The effect of the radial variation of incident radiation was determined quantitatively by defining a parameter f₁ as the ratio of the average intensity falling on the reference cell to that on the exposed area of the test cell. The value of f₁ varied between 1 and 1.15 (1.25) as the exposed area of the cell varied from 4 cm² to 78.6 (96) cm² indicating that the spatial inhomogeneity of intensity increased with the increase in the exposed cell area. Short-circuit current densities, J_sc, computed from spectral response data for AM1.5 spectrum were less compared to the directly measured values by a factor which was nearly equal to f₁. However, radial variation of intensity does not affect the determination of diffusion length of minority carriers in the base region (by the long wavelength spectral response, LWSR method using the measured spectral response data in 0.85<λ<1.05 μm range) and the thickness of the dead layer (by the method of Singh et al. using the data of 0.45<λ<0.65 μm range) significantly.     

An analytical study of the porosity effect on dye-sensitized solar cell performance

The porosity in a dye-sensitized solar cell (DSSC) can affect light absorption and electron diffusion that govern the overall electrical current–voltage (I–V) characteristics. In this research, two methods, namely, constant overlap and variable overlap, were developed to determine the connectivity of dye-sensitized TiO₂ particles in high and low porosity levels, respectively. In turn, the light absorption coefficient α and the electron diffusion coefficient D were analytically derived in terms of the porosity P. Subsequently, the electron diffusion differential equation involving α and D was solved for the I–V output as a function of P. A parametric analysis showed that the optimal porosity was equal to 0.41 for maximum I–V output. The analytical results agree well with experimental data reported in the literature. Besides DSSC, the analytical model can be applied to predict the performance of solid-state DSSC as well as dye-sensitized photoelectrochemical cells applied to hydrogen production and water purification.     

Improvement of hydrogen production with expression of lba gene in chloroplast of Chlamydomonas reinhardtii

An ORF cDNA fragment of one of leghemoglobin genes, lba was cloned from Glycine max and transferred into chloroplasts of Chlamydomonas reinhardtii. More rapidly O₂ consumption, lower O₂ content and higher H₂ output were monitored in the transgenic algal cultures than those in WT cultures either in S-free or S-containing medium. Maximum expression of lba in the transgenic algae consisted with the time when minimal O₂ contents and maximal H₂ evolution occurred. The highest H₂ production achieved in sulfur-free medium for both algal cultures. When restoring sulfate in the medium, H₂ production in the transgenic algal cultures kept steadily around 130–145 μl per bottle while that in WT cultures decreased gradually from 98 μl per bottle at 12.5 μM sulfate to 40 μl per bottle at 100 μM sulfate. The results indicated that heteroexpression of lehemoglaobin genes in chloroplasts of green algae improved H₂ yield by decreasing O₂ content in the medium. This protein had potential to be used in improvement of H₂ production in green algae.     

Influence of hydrogen passivation on majority and minority charge carrier mobilities in ribbon silicon

Multicrystalline silicon materials and ribbons in particular contain a higher amount of defects as compared to monocrystalline silicon, which have to be passivated during solar cell processing in order to reach satisfactory cell efficiencies. Within the solar cell process, this is usually carried out via the deposition of a hydrogen-rich SiN_x layer and a following firing step. During passivation, the electronic properties of the materials (conductivity, mobility) can change which might have an influence on the optimised parameters like emitter sheet resistance and grid geometry. This paper deals with the impact of hydrogen passivation on the electronic properties of majority and minority charge carriers in ribbon silicon materials. Majority charge carrier mobilities resulting from Hall measurements are strongly increasing after hydrogenation especially at temperatures below 300 K. Even at room temperature, changes in mobility up to a factor of 2 have been observed. For the determination of minority charge carrier mobilities in processed solar cells, a new method is presented based on spatially resolved internal quantum efficiency and lifetime measurements. It allows the calculation of mapped mobilities especially in materials showing small diffusion lengths. The same reductions in mobility of a factor 2–3 as compared to monocrystalline silicon for both majority and minority charge carriers could be detected in RGS silicon.     

Repeated production of hydrogen by sulfate re-addition in sulfur deprived culture of Chlamydomonas reinhardtii

Biological hydrogen production by the green alga, Chlamydomonas reinhardtii can be induced in conditions of sulfur deprivation. In this study, we investigated the repeated and enhanced hydrogen production afforded by the re-addition of sulfate with monitoring of pH and concentration of chlorophyll and sulfate. Without adjustment of the pH, the optimal concentration of re-added sulfate was 30 μM for the hydrogen production. By the re-addition of 30 μM of sulfate and the adjustment of the pH during 4 cycles of repeated production, we obtained the maximum amount of 789 ml H₂ l⁻¹ culture, which is 3.4 times higher than that of one batch production without adjustment of pH, 236 ml H₂ l⁻¹ culture. This means that the enhancement of the hydrogen production can be achieved by the careful control of the sulfate re-addition and pH adjustment in the sulfur deprived culture.     

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.     

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%.     

An EQCM study for a novel aromatic poly(amine-imide) electrochromic thin film

A new aromatic poly(amine-imide) electrochromic thin film synthesized with N,N-bis(4-aminophenyl)-N′,N′-diphenyl-1,4-phenylenediamine and 3,3′,4,4′-benzo-phenonetetra carboxylic dianhydride, abbreviated as poly(PD-BCD), was studied. The poly(PD-BCD) thin-film electrode has been characterized by cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM). As the polymer chain acquires positive charge during the oxidation of poly(PD-BCD) to its radical cation state or dication state, the anions would insert into the polymer matrix in order to neutralize the charge. However, when the electrodes were cycled in electrolytes containing different cations, including 0.1 M LiClO₄/acetonitrile (ACN), 0.1 M NaClO₄/ACN and 0.1 M TBAClO₄/ACN, the experimental results revealed two mechanisms for the redox reaction. A plot of mass change (Δm) vs. accumulated charge (Q) gave a slope, from which the electrochromic mechanism can be extracted. The slopes of Δm–Q obtained from the CV–EQCM measurements in three electrolytes were different for the first redox stage, but the slopes were almost the same for the second redox stage. This means that, in addition to the involvement of anions, cations also play an important role in the first redox stage, however, the role of the cations is less in the second stage. Moreover, two reaction mechanisms for the two reaction stages of poly(PD-BCD) are proposed in this study.     

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.     

Determination of front surface recombination velocity of silicon solar cells using the short-wavelength spectral response

A method of determination of recombination velocity S_f of minority carriers at the front surface of an n⁺–p–p⁺(p⁺–n–n⁺) silicon solar cell in which the n⁺(p⁺) front emitter is made by diffusion of dopant impurity in the p(n) region is presented. This method uses the short-wavelength spectral response of the cell to determine S_f and is applicable if the front emitter of the cell has a linearly varying built-in field. It was applied to a p⁺–n–n⁺ solar cell that had a Gaussian distribution of the dopant impurity in the p⁺ front emitter up to a depth of 0.078 μm from the surface. Using the spectral response data of cell in 380 nm<λ< 500 nm range S_f was found to have a nearly constant value 6×10⁵ cm s⁻¹ in 400 nm<λ<460 nm range. Below and above this wavelength range the value of S_f was found to be slightly smaller. For comparison the value of S_f was also determined assuming the p⁺ region to be uniformly doped, and this value was found to be significantly smaller than based on the diffused emitter model. The analysis showed that for a diffused junction cell, the assumption that the front emitter is uniformly doped, ignores the presence of the built-in field in the emitter region and leads to overestimation of minority carrier recombination in the emitter. Consequently for a given contribution of the front emitter region to the spectral response of the cell, this assumption underestimates the front surface recombination and determines a smaller value of S_f. On the other hand, the present method can be expected to determine a realistic value of S_f independent of λ for most diffused junction silicon solar cells using the spectral response data in a suitable short-wavelength range since each such cell indeed has a built-in electric field in the emitter region.     

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.     

Characterization of multicrystalline silicon wafers by non-invasive measurements

Non-invasive transient photoconductance measurements of large grain multicrystalline silicon wafers (ρ=1 Ω cm) are presented. It is shown that the surfaces of untreated wafers can be characterized as infinite sinks for excess charge carriers. The value 24.5 cm² s⁻¹ for the minority carrier diffusion constant was determined in all samples. So in untreated wafers, surface recombination yields a known contribution to the decay time measured and the volume lifetime can be determined. Application of these measurements as a standard characterization of multicrystalline silicon wafers is discussed.     

Segregation phenomena in large-size cast multicrystalline Si ingots

In cast multicrystalline silicon ingots impurity concentrations vary along the ingot height due to segregation phenomena during the directional solidification. It is expected that these concentrations are the highest at the top of the ingot which solidifies last. The bottom of the ingot which solidifies first, and which is longer in contact with the crucible floor is contaminated by solid state diffusion. As a consequence, lifetime (τ_n) and diffusion length (L_n) of minority carriers are the highest in the central part of the ingot and decrease strongly in the top as well as at the bottom. However, the impurity concentration is so high at the extremities of the ingot that additional solid state segregation phenomena occur at extended defects, which extract impurities from the adjacent grains. That is revealed at grain boundaries (GBs) by τ_n and L_n scan maps and also by the variation of the mobility of the majority carriers which cross GBs.     

Triplet exciton diffusion and delayed interfacial charge separation in a Tio2/PdTPPC bilayer: Monte Carlo simulations

Nanosecond photoexcitation of a bilayer of smooth anatase TiO₂ coated with palladium tetrakis(4-carboxyphenyl)porphyrin (PdTPPC) results in a delayed, after-pulse growth of the conductivity over many microseconds as monitored by time-resolved microwave conductivity. This phenomenon is attributed to the slow diffusion of PdTPPC triplet excitons followed by electron injection into the TiO₂ conduction band. The temporal form and intensity dependence of this process have been simulated by Monte Carlo (MC) calculations of exciton diffusion and exciton–exciton annihilation. Good agreement between the experimental results and MC simulations are obtained using a triplet exciton diffusion coefficient D_E=8×10⁻¹¹ m²/s, exciton lifetime τ_E≥10 μs, effective triplet–triplet annihilation distance R_a=1.5 nm and interfacial electron injection efficiency φ_inj=0.44.     

Clear separation of seasonal effects on the performance of amorphous silicon solar modules by outdoor I/V-measurements

The causes of seasonal variations on the performance of an amorphous silicon solar module were clearly separated using long-term outdoors I(V)-measurements. We normalized the data to a standard temperature, by using measured temperature coefficients of the characteristic parameters of the I(V)-curve, rather then extrapolating the curve itself. The resulting data were interpreted using a new model containing an effective μτ-product in the i-layer of the device (Merten et al. 1997). This μτ-product is accessed by variable illumination measurements (VIM) of the I(V) characteristic, which can be easily performed outdoors, making use of the natural variation in the illumination levels. The effective μτ-product of the module remains constant throughout its second year of outdoor exposure. We conclude that the enhanced efficiency in summer is, therefore, mainly a spectral effect, and operating temperatures exceeding the winter value of 60°C do not further increase the module's performance.     

Review and comparison of equations relating bulk lifetime and surface recombination velocity to effective lifetime measured under flash lamp illumination

Photoconductance measurements are frequently used to determine the minority-carrier effective lifetime (τ_eff), from which the bulk lifetime (τ_b) and surface recombination velocity (S) must be extracted. The exact solution to the continuity equation is used to determine the conditions of validity for three approximate equations relating τ_eff to τ_b and S: the steady-state approximation, the transient approximation, and the widely used simple equation (1/τ_eff=1/τ_b+2S/W). We show that only the steady-state approximation matches the exact solution over the entire range of τ_eff, when the lamp time constant is 2.3 ms. When τ_eff>20 μs, all the equations give approximately the same result. However, when τ_eff<10 μs, only the steady-state equation is valid, while the error in the transient and simple equations may exceed 100%.     

Preliminary photovoltaic response from a polymer containing p-vinylenephenylene amine backbone

Optoelectronic properties from a novel polymer, poly(p-phenylene N-4-n-butylphenyl-N,N-bis-4-vinylenephenylamine) (PNB) have been investigated. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of the material were estimated to be −5.18 and −2.75 eV, respectively, measured with cyclic voltammetry. A single-layer device structure was prepared by spin-coating PNB thin films from a solution on top of an indium–tin oxide (ITO) substrate while aluminum was used as a top electrode. Current density–voltage (J–V) characteristic was measured which showed a typical rectifying behavior. Photovoltaic from a single-layered device was observed under a white arc lamp illumination. This was improved via a double-layer structure comprising vacuum evaporated copper phthalocyanine (CuPc) or N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C₁₃) as an additional layer. The open-circuit voltage, short-circuit current and hence the efficiency were improved in the double-layer devices. An ITO/PNB/PTCDI-C₁₃/Al device was estimated to have external quantum efficiency (EQE) around 1% at 330 nm. In a comparison of optical absorption and photocurrent spectra, it was demonstrated that the excitons could be separated and further, generated carriers drifting to the opposite electrodes more efficiently in the double-layer cells.     

Formation of ultrafast-switching viologen-anchored TiO2 electrochromic device by introducing Sb-doped SnO2 nanoparticles

Ultrafast-switching viologen-anchored TiO₂ electrochromic device (ECD) was developed by introducing Sb-doped SnO₂ (Sb_xSn_1−xO₂, ATO) as counter electrode (CE), and the switching behavior of the fabricated ECD was investigated as a function of Sb-doping concentration. About 9-nm-sized Sb_xSn_1−xO₂ (x=0–0.3) nanoparticles were synthesized by a solvothermal reaction of tin (IV) chloride and antimony (III) chloride at 240 °C, and employed to fabricate 2.4-μm-thick transparent CE. Working electrode (WE) was formed from the 7-nm-sized TiO₂ nanoparticle by a doctor blade method, and the thickness of the nanoporous TiO₂ electrode was 4.5 μm. The phosphonated viologen, bis(2-phosphonylethyl)-4,4′-bipyridinium dibromide, was then adsorbed on the prepared films for the construction of the ECD. The response time was strongly dependent on the doping concentration of Sb in ATO, and the fastest switching response was observed at 3 mol%. At this composition, the coloration time was 5.7 ms, and the bleaching time was 14.4 ms, which is regarded as one of the best results so far reported.