Boron removal from silicon by hydrogen assistant during the electromagnetic directional solidification of AlSi alloys

Boron (B) removal from silicon (Si) by using an Ar-20% H₂ gas mixture during the AlSi solvent refining was investigated. Electromagnetic directional solidification was employed to enrich the primary Si crystals in the melt and simultaneously drive the produced B_xH_y gas species to migrate out of the Si enrichment zone. Thermodynamic analysis shows that the formation of B_xH_y gas species by the reaction of dissolved boron [B] and dissolved hydrogen [H] in AlSi melt is feasible. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) analysis confirmed that the impurity carbon (C), oxygen (O), and B adhered to the wall of the gas cavity, indicating that B removal can be attributed to the migration of gas species. As the flow time of Ar-20% H₂ gas mixture increased, the B removal fraction significantly increased, and a maximum value of 96.3% for B removal fraction was achieved when the flow time was 150 min. Finally, an overall process for producing solar grade silicon (SoG-Si) from metallurgical grade silicon (MG-Si) with the combination of ArH₂ refining in AlSi solvent and vacuum directional solidification was proposed.     

Hydrogen production of bio-oil steam reforming combining heat recovery of blast furnace slag: Thermodynamic analysis

Hydrogen production via steam reforming of bio-oil combining heat recovery of blast furnace slag was investigated via thermodynamic analysis in this paper. The addition of blast furnace slag just had a slight enhancement for hydrogen production from the steam reforming process of bio-oil at low temperature, and had almost no thermodynamic effect (either promotion or restraint) for the steam reforming reaction equilibrium at high temperature where higher H₂ yield were obtained, no matter how much blast furnace slag was added. However, different masses of blast furnace slag as heat carrier supply different amounts of heat, so the optimal blast furnace slag addition was performed via energy balance. If the sensible heats of the reformed gas and the slag after steam reforming reactions were unrecycled, the required mass of blast furnace slag was over 30 times of bio-oil mass, while the required slag mass was just 11.5 times of bio-oil mass if the sensible heats after the steam reforming reactions were recycled. For the latter, about 0.144 Nm³ H₂ per kg blast furnace slag was obtained at the reforming temperature of 700–750 °C and the steam/carbon mole ratio of 6.     

A simple process to remove boron from metallurgical grade silicon

It is necessary to develop solar grade (SoG) silicon for the photovoltaic industry. A desirable approach is to upgrade metallurgical grade (MG) silicon. The most problematic impurities to remove from MG silicon are B and P. A simple process to remove B from MG silicon has been developed by refining MG silicon in the molten state followed by directional solidification. With this approach, B has been reduced to 0.3 ppma, P to <10 ppma and all other impurities to <0.1 ppma using commercially available, as-received MG silicon. It remains to develop a similar P reduction process so that SoG silicon production from MG silicon can be commercialized. The B-removal process was applied to B overdoped electronic grade silicon, and the resulting material was used for crystal growth. Test solar cells of 12.5–13.4% (1 cm²) efficiency were produced.     

The brand‐new metallization patterning processes for plated solar cells

This paper discusses two brand‐new patterning methods for solar cell front metallization by using a layer of amorphous silicon (a‐Si) and the laser processed patterning process. These methods have the advantages of simplicity, rapidity, and low cost for the mass production of plated solar cells and also have the potential to overcome the shortcomings of the existing complex processes for Ni/Cu plated cells. In this paper, we reveal the processes and show the metallization performance. The patterning results were disclosed and had the line width of about 45 µm in our experiment. The specific contact resistivity (ρ_c) between plated Ni and silicon wafer exceeded the order of 10^?4 Ω cm². In addition, the patterning mechanisms are also proposed and discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

High temperature oxidation of ZrC-20%MoSi2 in air for future solar receivers

This article reports on the study of the oxidation of ZrC-20 vol% MoSi₂ in the temperature range 1800-2400 K in air, in order to partially reproduce the operating conditions of a high-temperature receiver for concentrated solar radiation. Such receivers are used in solar tower power plants, this technology being likely to grow in scale in the future due to environmental concerns. A thermodynamic calculation showed the existence of a limit temperature at about 1600 K, above which CO formation is significantly increased. During oxidation experiments carried out in a solar furnace, Bubble Burst Events appeared around 2000 K. The formation of these bubbles was accompanied by an increase in oxidation damage for the material. It was assumed that these bubbles formed because of the surface melting of samples in addition to an increased release of CO. However ZrC was found to undergo less oxidation damage than SiC under same conditions, as demonstrated in this study. Two different ZrC surface states were studied, but no major differences were observed in terms of oxidation behavior. Results of the thermodynamic calculation and characterization of the oxide layer let us think that the addition of such a high amount of MoSi₂ was detrimental to the oxidation behavior above 1800 K, because of its dissociation and its role in the surface melting.     

The infrared processing in multicrystalline silicon solar cell low-cost technology

New directions in photovoltaics depend very often on financial possibilities and new equipment. In this paper, we present the modification of a standard screen-printing technology by using an infrared (IR) furnace for forming a n⁺/p structure with phosphorus-doped silica paste on 100 cm² multicrystalline silicon wafers. The solar cells were fabricated on 300 μm thick 1 Ω cm p-type multicrystalline Bayer silicon. The average results for 100 cm² multicrystalline silicon solar cells are: I_sc=2589 mA, V_oc=599 mV, FF=0.74, E_ff=11.5%. The cross-sections of the contacts metallized in the IR furnace, as determined by scanning electron microscopy, and the phosphorus profile measured by an electrochemical profiler are shown. IR processing offers many advantages, such as a small overall thermal budget, low power and time consumption, in terms of a cost-effective technology for the continuous preparation of solar cells.     

Development of an emitter for industrial silicon solar cells using the doped oxide solid source diffusion technique

The aim of this paper is to demonstrate for the first time the feasibility of fabricating large-area screen-printed monocrystalline silicon solar cells using the Doped Oxide Solid Source (DOSS) diffusion technique. This process was applied to form the n⁺p emitter junction from highly doped sources prepared in a POCl₃ ambient. The diffusions were performed under a pure nitrogen flow in the temperature range 900–1050°C. In this investigation attention was devoted to the influence of the source doping level on the fill factor. The solar cells were fabricated on industrial quality 4-inch Cz wafers using a simple processing sequence incorporating screen-printed contacts and a TiO₂ antireflection coating deposited by spin-on. Fill factors as high as 79% were obtained. The potential benefit of retaining for passivation purposes the thin residual oxide grown during phosphorus diffusion was evaluated. These first experiments led to a cell efficiency close to 10%.     

Large-area high efficiency single crystalline silicon solar cells

This paper reports on a 100 cm² single crystalline silicon solar cell with a conversion efficiency of 19.44% (J_sc = 37.65 mA/cm², V_oc = 638 mV, FF = 0.809). The cell structure is as simple as only applying the textured surface, oxide passivation, and back surface field by the screen printing method. The comparison between cell performances of the CZ (Czochralski) and FZ (Floating zone) silicon substrates was investigated. The higher efficiency cells were obtained for the FZ substrate rather than the CZ substrate. The influence of the phosphorus concentration of the emitter on the cell efficiency has also been investigated. A good result was obtained when the surface concentration of phosphorus was 3 × 10²⁰ cm⁻³ and the junction depth was about 0.6 μm.     

Optimization of thermal processing and device design for high-efficiency c-Si solar cells

To improve the cell performance of single-crystal silicon solar cells, the process conditions have been optimized by monitoring the bulk lifetime after each thermal step in the cell fabrication process. The emitter geometry, i.e., front and rear contact size and pitch were optimized, and the cells were fabricated through a set of environmentally considered processes, especially for surface treatment, oxidation, diffusion, and electrode fabrication. Conversion efficiency of 22.3% in a 4 cm² cell, and 22.6% in a 1 cm² cell, was attained, respectively, with structural features of SiO₂ single-AR, “inverted-pyramid” fron texture, point-contact with line-emitter for front electrodes, and locally diffused BSF for rear contacts.     

Fenton degradation of 4-chlorophenol contaminated water promoted by solar irradiation

The degradation of 4-chlorophenol (4-CP) contaminated water by Fenton process with or without solar irradiation assistance were investigated. It was found that the COD degradation and mineralization efficiency of 4-CP were more than 90% when a 30 min treatment of solar photo-Fenton oxidation process was applied and under an optimum [H₂O₂]₀/[Fe²⁺]₀ ratio of 40, the COD degradation and mineralization efficiency increased 65% as compared to Fenton oxidation. Meanwhile, the AOS values increased from −0.33 to 2.13 in solar photo-Fenton process while no significant improvement for AOS values was found in Fenton process, implying a higher degree of oxidation for 4-CP in solar photo-Fenton process. In addition, increasing the intensity of solar irradiation seemed to be beneficial for treatment of 4-CP contaminated water. Formation of chloride ion as a result of mineralization of organically bounded chlorine was identified during the treatment of 4-CP solution. Near-stoichiometric accumulation of chlorine was observed during the degradation of 4-CP in both Fenton and solar photo-Fenton processes. However, accumulation rate of chloride ions were much faster in solar photo-Fenton process. The degradation of 4-CP was found to obey a pseudo-first-order reaction kinetics. As compared to Fenton process, the presence of solar light in photo-Fenton process increases the reaction rate by a factor of 6.5 and 15.8 for COD and TOC degradation, respectively. In other words, during the treatment of 4-CP contaminated water, solar photo-Fenton process possesses notably higher mineralization efficiency in a relatively short radiation time as compared to Fenton process, and could enhance the degradation treatment of refractory organic wastewater such as 4-CP in a cost-effective approach.     

High-efficiency μc-Si/c-Si heterojunction solar cells

P-type microcrystalline silicon (μc-Si (p)) on n-type crystalline silicon (c-Si(n)) heterojunction solar cells is investigated. Thin boron-doped μc-Si layers are deposited by plasma-enhanced chemical vapor deposition on CZ-Si and the V_oc of μc-Si/c-Si heterojunction solar cells is higher than that produced by a conventional thermal diffusion process. Under the appropriate conditions, the structure of thin μc-Si films on (1 0 0), (1 1 0), and (1 1 1) CZ-Si is ordered, so high V_oc of 0.579 V is achieved for 2×2 cm² μc-Si/multi-crystalline silicon (mc-Si) solar cells. The epitaxial-like growth is important in the fabrication of high-efficiency μc-Si/mc-Si heterojunction solar cells.     

Potential cost reduction of buried-contact solar cells through the use of titanium dioxide thin films

This paper explores the potential of applying titanium dioxide (TiO₂) thin films to the buried-contact (BC) solar cell. The aim is to develop a lower-cost BC technology that can be applied to multicrystalline silicon (mc-Si) wafers, the predominant substrate of the photovoltaics (PV) industry. The original BC solar cell used a thick, thermally grown, silicon dioxide (SiO₂) layer as the front surface dielectric coating. Upon commercialisation of the BC technology, BP Solar replaced this layer with silicon nitride (Si₃N₄), which exhibits improved optical properties. It is anticipated that production costs can be further reduced by using a low temperature deposited front surface dielectric coating, such as TiO₂, thereby reducing the number of lengthy high temperature processing steps, and developing a process such that it can be applied to mc-Si wafers. TiO₂ is chosen because of its optimal optical properties for glass-encapsulated silicon solar cells and familiarity of PV manufacturers with this material. The results presented resolve the issue of surface passivation with TiO₂ and demonstrate that TiO₂/SiO₂ stacks, achieved during a brief high-temperature oxidation process after TiO₂ thin film deposition, are compatible with high-efficiency solar cells. However, TiO₂ cannot perform all the necessary functions of the thick SiO₂ or Si₃N₄ layer, due to its inability to act as a phosphorus diffusion barrier. In light of these results, three alternate BC solar cell fabrication sequences are presented, and an initial conversion efficiency of 11.5% has been achieved from the first batch of solar cells in a non-optimised processes.     

Performance improvements of crystalline silicon by iterative gettering process for short duration and with the use of porous silicon as sacrificial layer

In this work, we demonstrate that an efficient purification method of silicon wafers where iterative sequences were used. Each sequence consists of forming porous silicon (PS) on both sides of the samples, followed by thermal annealing in an infrared furnace under N₂/SiCl₄ ambient. Improvements of the electronic parameters were obtained by optimizing the heat treatments temperatures and the number and duration of the iteration sequences. Best results were obtained for temperatures below 980 °C and for three sequences of 20 min each one. After three sequences the mobility of the majority carrier improved from 94 cm² V⁻¹ s⁻¹ (for untreated wafer) to about 374 cm² V⁻¹ s⁻¹. The observed results were explained taking into account the transport properties of the impurities in the porous media and their concentration at the walls at each iteration. It was found that short iterative sequences give almost the same results than one long sequence duration. Silicon solar cells based on iterative gettered silicon wafers exhibit an increase in the short-circuit current and the open-circuit voltage. This fact seems to be important to ameliorate solar grade silicon (SGS) based solar cells performances.     

Purification of metallurgical grade silicon by a solar process

The purification of upgraded metallurgical silicon by extraction of boron and phosphorus was experimentally demonstrated using concentrated solar radiation in the temperature range 1550–1700 °C. The process operated with a flow of Ar at reduced pressure (0.05 atm) for elimination of P, and with a flow of H₂O for elimination of B. Impurity content decreased by a factor of 3 after a 50-min solar treatment, yielding Si samples with final average content of 2.1 ppm_w B and 3.2 ppm_w P.     

The effects of the band gap and defects in silicon nitride on the carrier lifetime and the transmittance in c-Si solar cells

In this paper, silicon nitride thin films with different silane and ammonia gas ratios were deposited and characterized for the antireflection and passivation layer of high efficiency single crystalline silicon solar cells. An increase in the transmittance and a recombination decrease using an effective antireflection and passivation layer can be enhanced by an optimized SiN_x film in order to attain higher solar cell efficiencies. As the flow rate of the ammonia gas increased, the refractive index decreased and the band gap increased. Consequently, the transmittance increased due to the higher band gap and the decrease of the defect states, which existed for the 1.68 and 1.80 eV in the SiN_x films. The interface trap density found in silicon can be reduced down to 1.0×10¹⁰ cm⁻² eV⁻¹ for the SiN_x layer deposited under the optimized silane to ammonia gas ratio. Reduction in the carrier lifetime of the SiN_x films deposited using a higher NH₃/SiH₄ flow ratio was caused by the increase of the interface traps and the defect states in/on the interface between the SiN_x and the silicon wafer. Silicon and nitrogen rich films are not suitable for generating both higher carrier lifetimes and transmittance. An improvement in the single c-Si solar cell parameters was observed for the cells with an optimal SiN_x layer, as compared to those with non-optimal SiN_x layers. These results indicate that the band gap and the defect states of the SiN_x films should be carefully controlled in order to obtain the maximum efficiency for c-Si solar cells.     

Phosphorus-doped silicon quantum dots for all-silicon quantum dot tandem solar cells

Doping of Si quantum dots is important in the field of Si quantum dots-based solar cells. Structural, optical and electrical properties of Si QDs formed as multilayers in a SiO₂ matrix with various phosphorus (P) concentrations introduced during the sputtering process were investigated for its potential application in all-silicon quantum dot tandem solar cells. The formation of Si quantum dots was confirmed by transmission electron microscopy. The addition of phosphorus was observed to modify Si crystallization, though the phosphorus concentration was found to have little effect on quantum dot size. Secondary ion mass spectroscopy results indicate minimal phosphorus diffusion from Si QDs layers to adjacent SiO₂ layers during high-temperature annealing. Resistivity is significantly decreased by phosphorus doping. Resistivity of slightly phosphorus-doped (0.1 at% P) films is seven orders of magnitude lower than that of intrinsic films. Dark resistivity and activation energy measurements indicate the existence of an optimal phosphorus concentration. The photoluminescence intensity increases with the phosphorus concentration, indicating a tendency towards radiative recombination in the doped films. These results can provide optimal condition for future Si quantum dots-based solar cells.     

The effect of rear surface polishing to the performance of thin crystalline silicon solar cells

As the thickness of crystalline silicon solar cells decreases, light loss cannot be avoided due to the absorption limit in long wavelength light. Internal rear side reflection can be enhanced by polishing the rear surface. The rear polishing processes are performed before the texturing and before and after doping the emitter layer to optimize the solar cell fabrication process sequences. All cells made by rear surface polishing showed improved light trapping in long wavelength region (900-1100 nm) compared to that in the conventional cells. However, silicon solar cells fabricated by rear polishing before and after doping have similar (35.5 mA/cm²) or lower (35.26 mA/cm²) short circuit current density compared to the cells produced by the conventional process (35.59 mA/cm²) due to pore damage to the anti-reflection layer and the surface of the emitter layer during rear polishing. This surface damage was effectively prevented adapting the rear surface polishing before the front surface texturing, which led to increasing the current density from 35.59 to 36.29 mA/cm².     

A study of electrical uniformity for monolithic polycrystalline silicon solar cells

The aim of this work is to investigate the electrical uniformity of monolithic polycrystalline silicon solar cells prepared by various process techniques. By a series of experiments such as P and Al impurity gettering and silicon nitride passivation, a new conclusion is that the application of P and Al gettering as well as silicon nitride passivation enhances the electrical uniformity of small area solar cells diced from the same polycrystalline silicon solar cells, even if impurity gettering is not effective when the dislocation density is above a threshold value of about 10⁶ cm⁻². The experiments give us some hints that when we cut large area polycrystalline silicon solar cells into small pieces needed for application, we should modify production process slightly.     

CO2 capture using carbide slag modified by propionic acid in calcium looping process for hydrogen production

Lime enhanced gasification (LEGS) process based on calcium looping in which CaO is employed as CO₂ sorbent is an emerging technology for hydrogen production and CO₂ capture. In this work, carbide slag which was an industrial solid waste was utilized as CO₂ sorbent in hydrogen production process. Modification of carbide slag by propionic acid was proposed to improve its reactivity. The CO₂ capture behavior of raw and modified carbide slags was investigated in a dual fixed-bed reactor (DFR) and a thermo-gravimetric analyzer (TGA). The results show that modification of carbide slag by propionic acid enhances its CO₂ capture capacity in the multiple calcination/carbonation cycles. The favorable carbonation temperature and calcination temperature for modified carbide slag are 680–700 °C and 850–950 °C, respectively. Prolonged carbonation treatment is beneficial to CO₂ capture of raw and modified carbide slags. The prolonged carbonation for 9 h in the 21st cycle increases the conversions of raw and modified carbide slags in this cycle. And then the carbonation conversions of the two sorbents were also improved in the subsequent cycles. Calcined modified carbide slag shows more porous microstructure compared with calcined raw one for the same number of cycles. Modification of carbide slag by propionic acid increases the surface area, pore volume and pore area. In addition, the volume and area of the pores in 20–100 nm in diameter were improved, which had been proved to be more effective to capture CO₂. The microstructure of calcined modified carbide slag favors its higher CO₂ capture capacity in the multiple calcination/carbonation cycles.     

Unusual photocapacitance properties of a mono-crystalline silicon solar cell for optoelectronic applications

The current-voltage characteristics of mono-crystalline solar cell device under dark and illumination of 100 mW/m² (AM1.5) were measured. The efficiency of the studied device under AM1.5 was found to be 14.22%±0.2 compared with the company standards. The capacitance properties of mono-crystalline silicon solar cell device were investigated under dark and illumination conditions. The studied mono-crystalline silicon solar cell exhibits an unusual photocapacitance ranging from 50.4 to 4585 nF under dark and 100 mW/m² (AM1.5) of white light, respectively. The drastic increase in the capacitance of the solar cell is due to the space charge polarization induced by the increasing number of photogenerated carriers. The photocapacitance mechanism of the solar cell was interpreted by modified Goswami and Goswami (MGG) model. The relative capacitance C_ph/C_d (the ratio between the capacitance under illumination to the capacitance under dark) and the relative resistance R_ph/R_d (the ratio between the resistance under illumination to the resistance under dark) as a function of the applied frequency at different illuminations were interpreted. The values of the interface state density N_ss and interface capacitance C_ss are increased with the increasing illumination intensities. The prepared mono-silicon solar cell device is a good candidate for photocapacitive and photoresistive sensors in modern electronic and optoelectronic devices.