Present status and future of crystalline silicon solar cells in Japan

Crystalline silicon solar cells show promise for further improvement of cell efficiency and cost reduction by developing process technologies for large-area, thin and high-efficiency cells and manufacturing technologies for cells and modules with high yield and high productivity.In this paper, Japanese activities on crystalline Si wafers and solar cells are presented. Based on our research results from crystalline Si materials and solar cells, key issues for further development of crystalline Si materials and solar cells will be discussed together with recent progress in the field. According to the Japanese PV2030 road map, by the year 2030 we will have to realize efficiencies of 22% for module and 25% for cell technologies into industrial mass production, to reduce the wafer thickness to 50–100 μm, and to reduce electricity cost from 50 Japanese Yen/kWh to 7 Yen/kWh in order to increase the market size by another 100–1000 times.     

Thin crystalline silicon solar cell bonded to sintered substrate with aluminum paste

Making thinner wafers is a simple way to reduce the production cost of silicon solar cells. However, thin wafers need to be supported mechanically in order to avoid the problem of breakage. Among the several possible supporting materials, silicon substrate made from the sintering of silicon powder, which is produced during the slicing process is the most favorable one because of its abundance and its similar thermal expansion coefficient with silicon wafers. For the bonding of the substrate and thin silicon wafers, aluminum paste is selected because of its compatibility with silicon and the possible BSF effect. Silicon solar cells of 150 μm with the sintered substrate on the back show 5.42% in solar cell conversion efficiency. Compared to commercial silicon cells, lower J_sc is obtained. This might be due to the poor conduction in the back layer of aluminum, which is absorbed into the supporting substrate during the annealing process.     

Thin crystalline silicon solar cells

A 50 μm thin layer of high quality crystalline silicon together with efficient light trapping and well passivated surfaces is in principle all that is required to achieve stable solar cell efficiencies in the 20% range. In the present work, we propose to obtain these layers by directly cutting 50 μm thin wafers from an ingot with novel cutting techniques. This development is discussed in the frame of a defect tolerant mass production scenario and aims at obtaining twice the amount of wafers as compared to present wire/slurry technology. The ability to process such mechanically flexible wafers into solar cells with standard laboratory equipment is experimentally verified.     

Industrial manufacturing of semitransparent crystalline silicon POWER solar cells

This paper gives an extract of the state of the art of the manufacturing of semitransparent crystalline silicon POWER solar cells in an industrial environment. A short introduction of the POWER devices concept (see Fig. 1) will be given followed by an insight in the applied production process. Finally, examples effecting the efficiency distribution in the cell production and their solutions are given. It is believed that the lessons we learned in optimising the manufacturing process and production line of transparent POWER solar cells can be helpful for the increasing activities in the direction of thin wafers as well as novel solar cell devices.     

New concepts for high-efficiency silicon solar cells

This paper gives an overview about recent activities in the industrial application of high-efficiency monocrystalline silicon solar cells. It also presents the latest results achieved at Fraunhofer ISE, especially a new patented process for the formation of back-contact points on dielectrically passivated cells called laser-fired contacts and its application to thin wafers.     

Sheet resistance uniformity in drive-in step for different multi-crystalline silicon wafer dispositions

In this work, we present a study of emitters realized using different configurations of the silicon wafers in the quartz boat. The phosphorous liquid source is sprayed onto p-type multi-crystalline silicon substrates and the drive-in is made at high temperature in a muffle furnace. Three different configurations of the wafers in the boat are tested: separated, back to back and compact block of wafers. A fourth configuration is also used in source-receptor mode. The emitter phosphorous concentration profile is obtained by SIMS analysis. The resulting emitters are characterized by sheet resistance measurements and a comparison is made between the wafers within the same batch and from one batch to another. The uniformity and the standard deviation of the sheet resistance are calculated in each case. The emitter sheet resistance mapping of the wafer set in the middle of the boat for a given process gives a mean R_sq 14.66 Ω/sq with a standard deviation of 1.76% and uniformity of 18.7%. Standard deviations of 2.116% and 1.559% are obtained for wafers in the batch when using the spaced and compact configurations, respectively. The standard deviation is reduced to 0.68% when the wafers are used in source/receptor mode. A comparison is also made between wafers with different dilution of phosphorous source in ethanol.From these results we can conclude that the compact configuration offers better uniformity and lower standard deviation. Furthermore, when combined with the source-receptor configuration these parameters are significantly improved.This study allows the experimenter to identify the technological parameters of the solar cell emitter manufacturing and target precisely the desired values of the sheet resistance while limiting the number of rejected wafers.     

颗粒硅带多晶硅薄膜太阳电池的研制

以工业硅粉为原料制备出颗粒硅带（SSP），对颗粒硅带表面形态进行了分析。以SSP为衬底，采用快速热化学气相沉积（RTCVD）法生长多晶硅薄膜，并以此制作出效率为2．93％的颗粒硅带多晶硅薄膜太阳电池，这在国内属首先。并报道了对以SSP为衬底的多晶硅薄膜太阳电池的初步研究结果，同时讨论了该类电源的结构、工艺特点和改进措施。     

Development of low-cost silicon crystal growth techniques for terrestrial photovoltaic solar energy conversion

Single crystal silicon solar cells are potential elements of large scale solar energy conversion systems. Current costs of these cells are too high at least in part because current production methods require single crystal wafers obtained by slicing cylindrical single crystal ingots. This paper reviews a U.S. research program aimed at reducing the cost of silicon cells by developing new methods of growing silicon ribbons and sheets from which high efficiency solar cells can be fabricated. The paper also describes novel techniques for lower cost processes for ingot growth and wafer slicing which are included in this research and development program.     

Annual available radiation for fixed and tracking collectors

Single crystal silicon solar cells are potential elements of large scale solar energy conversion systems. Current costs of these cells are too high at least in part because current production methods require single crystal wafers obtained by slicing cylindrical single crystal ingots. This paper reviews a U.S. research program aimed at reducing the cost of silicon cells by developing new methods of growing silicon ribbons and sheets from which high efficiency solar cells can be fabricated. The paper also describes novel techniques for lower cost processes for ingot growth and wafer slicing which are included in this research and development program.     

3D modelling of a reverse cell made with improved multicrystalline silicon wafers

The spectral response, short-circuit photocurrent and conversion efficiency of a reverse cell made with multicrystalline silicon wafers have been computed taking into account different values of base thickness, grain size, grain boundary recombination velocity, front and back surface recombination velocities and minority carrier diffusion length in the grains. The results are compared to those of a conventional multicrystalline cell computed under the same conditions. It is shown that the reverse cell structure, which simplifies the technological problems, particularly those related to the conventional emitter and front grid, could be a good alternative solution in the case of improved thin wafers.     

Application of phosphorus diffusion gettering process on upgraded metallurgical grade Si wafers and solar cells

Although phosphorus (P) diffusion gettering process has been wildly used to improve the performance of Si solar cells in photovoltaic technology, it is a new attempt to apply P diffusion gettering process to upgraded metallurgical grade silicon (UMG-Si) wafers with the purity of 99.999%. In this paper, improvements on the electrical properties of UMG-Si wafers and solar cells were investigated with the application of P diffusion gettering process. To enhance the improvements, the gettering parameters were optimized on the aspects of gettering temperature, gettering duration and POCl₃ flow rate, respectively. As we expected, the electrical properties of both multicrystalline Si (multi-Si) and monocrystalline Si (mono-Si) wafers were significantly improved. The average minority carrier lifetime increased from 0.35 μs to nearly about 2.7 μs for multi-Si wafers and from 4.21 μs to 5.75 μs for mono-Si wafers, respectively. Accordingly, the average conversion efficiency of the UMG-Si solar cells increased from 5.69% to 7.03% for multi-Si solar cells (without surface texturization) and from 13.55% to 14.55% for mono-Si solar cells, respectively. The impurity concentrations of as-grown and P-gettered UMG-Si wafers were determined quantitively so that the mechanism of P diffusion gettering process on UMG-Si wafers and solar cells could be further understood. The results show that application of P diffusion gettering process has a great potential to improve the electrical properties of UMG-Si wafers and thus the conversion efficiencies of UMG-Si solar cells.     

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.     

Drastic reduction in surface recombination velocity of crystalline silicon by surface treatment using catalytically-generated radicals

A method of reducing surface recombination velocities (SRVs) of crystalline silicon (c-Si) wafers is presented for the case when c-Si surfaces are passivated by amorphous Si (a-Si) thin films. It is demonstrated that the surface treatment of c-Si wafers prior to a-Si deposition, using hydrogen atoms generated by catalytic reaction of hydrogen gas with heated catalyzer, lowers SRV effectively, and that SRV is drastically reduced to less than 3 cm/s when a small amount of doping impurity is added during atomic hydrogen treatment.     

A new energy efficient, environment friendly and high productive texturization process of industrial multicrystalline silicon solar cells

A new texturization process based on a uniform, isotropic and slow removal of silicon, using a composition of sodium hydroxide (NaOH) and sodium hypochlorite (NaOCl) solution at an elevated temperature is developed recently for multicrystalline silicon solar cells. This process is applied in optimized condition in regular industrial production line and it immediately replaces the old popular industrial process of texturization using a combination of NaOH solution, alcoholic NaOH solution and hydrochloric acid solution in different steps at a higher temperature. Also the gain in solar cell efficiency at global AM1.5 spectrum, 1 SUN intensity condition is nearly 10% in final value. In addition, it has become finally an energy efficient and environment friendly texturization process for large area multicrystalline silicon solar cells for commercial use. In this paper the cost effectiveness and environment friendly aspects of the proposed process have been studied in detail along with the surface texture analysis of wafers with SEM and AFM micrographs to substantiate the reasons behind the above facts.     

Formation and distribution of silicon carbide (SiC) precipitates in industrial directional solidification of mc-Si ingots

Abstract

Silicon carbide inclusions in multicrystalline (polycrystalline) silicon ingots affect the cutting process and quality of silicon wafers. The higher density of SiC inclusions relative to the silicon melt suggests that they should sink, but inclusions were observed at the top, middle and bottom of industrial ingots. More inclusions were observed at the top relative to the middle and bottom of the ingot. Small SiC inclusions were found at the bottom and reticular SiC inclusions at the top of the ingot, suggesting that inclusion growth may occur during growth of the ingot. A mechanism to explain the formation and distribution of SiC in industrial silicon directionally solidified ingots, based on the thermodynamics of SiC, is proposed together with strategies to reduce carbon contamination and improve ingot quality.     

Mono- and tri-crystalline Si for PV application

Crystalline silicon wafers are by far the dominant absorber materials for today's production of solar cells and modules due to their good price/performance relation and their proven environmental stability. These wafers are mainly produced either by a solar-optimized Czochralski (Cz)-growth method yielding crystalline silicon with low defect density (c-Si) or by a directional solidification or a ribbon growth method yielding large grained multi-crystalline (mc-Si) wafers with higher defect density. To further improve the price/performance relation of Cz solar cells, tri-crystalline silicon (tri-Si) is being developed as a high-quality wafer material that combines both the high diffusion length of minority carriers of up to 1300 μm of c-Si and the productivity of mc-Si. More than 1000 μm LID free diffusion length could be reached with specially doped tri-crystals. Due to an increased mechanical stability tri-Si allows both quasi-continuous pulling and thin slicing with higher mechanical yields. This paper reviews the structural, electronic, and mechanical properties of tri-crystalline silicon wafers with respect to c-Si wafers for solar applications. Actual non-textured solar cells processed with a simple cost effective fabrication process exhibit the same cell efficiencies up to 15.9% for both tri-silicon and mono-silicon wafers. With an improved process, up to 18% cell efficiency can be obtained with textured mono-Si.     

Growth and properties of SiGe multicrystals with microscopic compositional distribution for high-efficiency solar cells

The growth technique and physical properties of SiGe multicrystals with microscopic compositional distribution are demonstrated for new high-efficiency solar cells in which the wavelength dependence of the absorption coefficient can be freely designed by controlling the compositional distribution in the SiGe multicrystals. This growth technique is suitable for the practical casting method, and it is made up of melt growth of SiGe multicrystals with wide and microscopic distribution of the composition from Si to Ge all over the crystals. It is studied how much widely the microscopic compositional distribution in SiGe multicrystals grown from binary Si–Ge melts can be controlled by the melt composition and the cooling process. The range of the microscopic compositional distribution becomes wider as the starting Si concentration in the growth melt becomes larger. SiGe multicrystals with various microscopic compositional distribution can be freely controlled by optimizing the melt composition and the cooling process. The wavelength dependence of the absorption coefficient of such SiGe multicrystals can also be freely designed. Using the experimentally determined absorption coefficient of a SiGe crystal with microscopic compositional distribution, the short circuit photo-current of solar cells was calculated and it is demonstrated that the short circuit photo-current can be much larger for SiGe with microscopic compositional distribution than for SiGe with uniform composition. Si thin film can be easily grown on such a SiGe multicrystal and the Si/SiGe heterostructure can be obtained. These results show that SiGe multicrystals with microscopic compositional distribution are hopeful for new high-efficiency solar cell applications by using the practical casting method.     

Global simulation of a silicon Czochralski furnace in an axial magnetic field

Control of melt flow in crystal growth process by application of the magnetic field is a practical technique for silicon single crystals. In order to understand the influence of axial magnetic field on the silicon melt flow and oxygen transport in a silicon Czochralski (Cz) furnace, a set of global numerical simulations was conducted using the finite-element method for the magnetic field strength from 0 to 0.3 T, the crystal rotation rates from 0 to 30 rpm and the crucible counter-rotation rates from 0 to −15 rpm. It was assumed that the flow was axisymmetric laminar in both the melt and the gas, the melt was incompressible and a constant temperature was imposed on the outer wall of the Cz furnace. The results indicate significantly different flow patterns, thermal and oxygen concentration fields in the melt pool when a uniform axial magnetic field is applied.     

Antireflective porous layer formation on multicrystalline silicon by metal particle enhanced HF etching

Antireflection of silicon (Si) surface is one key technology for the manufacture of efficient solar cells. Metal particle enhanced HF etching is applied to produce uniform antireflecting porous layer on multicrystalline Si wafers that cannot be uniformly texturized by anisotropic etching with an alkaline solution. Fine platinum (Pt) particles are deposited on multicrystalline n-Si wafers by electroless displacement reaction in a hexachloroplatinic acid solution containing HF. Both macroporous and luminescent microporous layers are uniformly formed by immersing the Pt-particle-deposited multicrystalline Si wafers in a HF solution. The reflectance of the wafers is reduced from 30% to 6% by the formation of porous layer. The photocurrent density of photoelectrochemical solar cells using porous multicrystalline n-Si has a 25% higher value than non-porous Si cells.     

Laser enhanced gettering of silicon substrates

One challenge to the use of lightly-doped, high efficiency emitters on multicrystalline silicon wafers is the poor gettering efficiency of the diffusion processes used to fabricate them. With the photovoltaic industry highly reliant on heavily doped phosphorus diffusions as a source of gettering, the transition to selective emitter structures would require new alternative methods of impurity extraction. In this paper, a novel laser based method for gettering is investigated for its impact on commercially available silicon wafers used in the manufacturing of solar cells. Direct comparisons between laser enhanced gettering (LasEG) and lightly-doped emitter diffusion gettering demonstrate a 45% absolute improvement in bulk minority carrier lifetime when using the laser process. Although grain boundaries can be effective gettering sites in multicrystalline wafers, laser processing can substantially improve the performance of both grain boundary sites and intra-grain regions. This improvement is correlated with a factor of 6 further decrease in interstitial iron concentrations. The removal of such impurities from multicrystalline wafers using the laser process can result in intra-grain enhancements in implied open-circuit voltage of up to 40 mV. In instances where specific dopant profiles are required for a diffusion on one surface of a solar cell, and the diffusion process does not enable effective gettering, LasEG may enable improved gettering during the diffusion process.