硅片及其太阳电池的光衰规律研究

采用氙灯模拟太阳光源,将光强调至1000 W/m2,研究常规太阳能级单晶硅片、多晶硅片和物理提纯硅片的原片、去损减薄片、热氧化钝化片、双面镀氮化硅(SiN x:H)膜钝化片、碘酒钝化片以及太阳电池的光衰规律.利用WT-2000少子寿命测试仪以及太阳电池I-V特性测试仪分别对硅片的少子寿命和太阳电池的I-V特性参数随光照时间的变化进行了测试.结果表明:所有硅片以及太阳电池在光照的最初60 min内衰减很快随后衰减变慢,180 min之后光衰速率变得很小,几乎趋于零.     

Light‐induced degradation and regeneration of multicrystalline silicon Al‐BSF and PERC solar cells

Light‐induced degradation (LID) is a well‐known problem faced by p‐type Czochralski (Cz) monocrystalline silicon (mono‐Si) wafer solar cells. In mono‐Si material, the physical mechanism has been traced to the formation of recombination active boron‐oxygen (B–O) complexes, which can be permanently deactivated through a regeneration process. In recent years, LID has also been identified to be a significant problem for multicrystalline silicon (multi‐Si) wafer solar cells, but the exact physical mechanism is still unknown. In this work, we study the effect of LID in two different solar cell structures, aluminium back‐surface‐field (Al‐BSF) and aluminium local back‐surface‐field (Al‐LBSF or PERC (passivated emitter and rear cell)) multi‐Si solar cells. The large‐area (156 mm × 156 mm) multi‐Si solar cells are light soaked under constant 1‐sun illumination at elevated temperatures of 90 °C. Our study shows that, in general, PERC multi‐Si solar cells degrade faster and to a greater extent than Al‐BSF multi‐Si solar cells. The total degradation and regeneration can occur within ～320 hours for PERC cells and within ～200 hours for Al‐BSF cells, which is much faster than the timescales previously reported for PERC cells. An important finding of this work is that Al‐BSF solar cells can also achieve almost complete regeneration, which has not been reported before. The maximum degradation in Al‐BSF cells is shown to reduce from 2% (relative) to an average of 1.5% (relative) with heavier phosphorus diffusion.     

Electrical properties of purified solar grade silicon substrates using a combination of porous silicon and SiCl4

This work investigates the photo-thermal treatment of solar grade (SG) silicon to reduce impurities to a low level suitable for high efficiency low-cost solar cells application. It describes experiment carried out by using a tungsten lamps furnace (rapid thermal processing, RTP) to purify solar grade silicon wafers using a combination of porous silicon (PS) and silicon tetrachloride. This process enables to attract the impurities towards the porous layer where they react with SiCl₄ to form metallic chlorides. The gettering effect was studied using the Hall Effect and the Van Der Pauw methods to measure the resistivity, the majority carrier concentration and mobility. We have obtained a significant improvement of the majority carrier mobility after such thermo-chemical treatment. The gettering efficiency is also evaluated by the relative increase of the minority carrier diffusion length L, measured by the light beam induced current (LBIC) technique.     

High-efficiency core–shell solar cell array from Si wafer

High-efficiency micro core–shell solar cell (μ-CSSC) arrays are fabricated from Si wafer by using traditional lithography and phosphorus diffusion. The p–n junction depth is around 450 nm, indicating that it forms core–shell structure in micropillars by using phosphorus diffusion. The μ-CSSC arrays have high minority carrier lifetime of 23 μs and long diffusion length of ～150 μm. The best power efficiency of the μ-CSSC reaches to 9.2%. It is a convenient method for fabricating Si μ-CSSC arrays in wafer scale for future applications.     

低温退火磷吸杂工艺对低少子寿命铸造多晶硅电性能的影响

本文针对低少子寿命铸造多晶硅片进行试验, 通过一种将多温度梯度磷扩散吸杂工艺与低温退火工艺结合的新型低温退火吸杂工艺, 去除低少子寿命多晶硅片中影响其电性能的Fe杂质及部分晶体缺陷, 提高低少子寿命多晶硅所生产的太阳电池各项电性能. 通过低温退火磷扩散吸杂工艺与其他磷扩散吸杂工艺的比较, 证明了低温退火吸杂工艺具有更好的磷吸杂和修复晶体缺陷的作用. IV-measurement发现经过低温退火工艺处理后的低少子寿命多晶硅, 制备的太阳电池光电转换效率比其他实验组高0.2%, 表明该工艺能有效地提高低少子寿命多晶硅太阳电池各项电性能参数及电池质量. 本研究结果表明新型低温退火磷吸杂工艺可将低少子寿命硅片应用于大规模太阳电池生产中, 提高铸造多晶硅材料在太阳能领域的利用率, 节约铸造多晶硅的生产成本. 关键词： 低温退火 磷吸杂 低少子寿命多晶硅 太阳电池     

Ion implanted induced giant gettering of gold in silicon

Abstract

Ion implanted induced giant gettering of Gold in Silicon has been investigated by using ?111? Si wafer implanted with 10¹⁶ Ar⁺ ions/cm² at 280 keV. Some conditions of the appearance of giant gettering of Au in Si have been establi shed at different temperatures i.e. 500°C and 900°C: (i) annealing in vacuum, (ii) an “infinite” source of Au from a preannealed Au-Si film deposited by sputtering. On the basis of the experimental results a simple thermodinamic model explaining the giant gettering involving the mechanism of a liquid Au-Si phase has been developed.     

Low‐Temperature Saw Damage Gettering to Improve Minority Carrier Lifetime in Multicrystalline Silicon

The minority carrier lifetime in multicrystalline silicon ? a material used in the majority of today's manufactured solar cells ? is limited by defects within the material, including metallic impurities which are relatively mobile at low temperatures (≤700 °C). Addition of an optimised thermal process which can facilitate impurity diffusion to the saw damage at the wafer surfaces can result in permanent removal of the impurities when the saw damage is etched away. We demonstrate that this saw damage gettering is effective at 500 to 700 °C and, when combined with subsequent low‐temperature processing, lifetimes are improved by a factor of more than four relative to the as‐grown state. The simple method has the potential to be a low thermal budget process for the improvement of low‐lifetime “red zone” wafers.

     

New optical features to enhance solar cell performance based on porous silicon surfaces

Electrochemical etching is used to fabricate porous silicon (PS) surfaces for both sides of the Si wafer. The effect of PS on performance of Si solar cells is investigated and the reflected mirrors are manipulated to enhance solar cell efficiency. The process is promising for solar cell manufacturing due to its simplicity, lower cost and suitability for mass production. The PS surface has discrete pores and short-branched pores on the polished wafer side. In contrast, the etched backside of the wafer has smaller pore size, with random pores. PS formed on both sides has lower reflectivity value compared with results in other works. Solar cell efficiency is increased to 15.4% with PS formed on both sides compared with the unetched sample and other results. Using empirical models, the optical properties of the refractive index and the optical dielectric constant are investigated. The porous surface texturing properties could enhance and increase the conversion efficiency of porous Si solar cells. The obtained results are in agreement with experimental and other data.     

Improved performance of solar cell based on porous silicon surfaces

Porous silicon (PS) surfaces were fabricated by electrochemical etching for both sides of the Si wafer. The objective of the present study is to investigate the PS effect on performance of silicon solar cells. Moreover, enhancement of solar cell efficiency can be obtained by manipulating of the reflected mirrors, and the process is very promising for solar cells manufacturing due to its simplicity, lower cost and suitability for mass production. The surface of PS is observed to have been discrete pores with smooth walls, and with short branches pores for the polished wafer side. In contrast, the etched backside of the wafer was observed to have bigger pore size than the etched polished side, and pores on the surface are in random location. PS formed on the both sides has lower reflectivity value in comparison to the other researcher group. The increase in efficiency of solar cell fabricated with PS formed on both sides of the wafer were extremely observed in comparison to one side PS and bulk silicon solar cells respectively. Solar cell fabricated shows that the conversion efficiency increased to 14.5% in comparison to unetched sample. The porous surface texturing properties could enhance and increased the conversion efficiency of silicon solar cells, these results also showed that the efficiency with this procedure is more promising in comparison to other solar cells, which are fabricated under similar conditions.     

Photographic diagnosis of crystalline silicon solar cells utilizing electroluminescence

The photographic surveying of electroluminescence (EL) under forward bias was proved to be a powerful diagnostic tool for investigating not only the material properties but also process induced deficiencies visually in silicon (Si) solar cells. Under forward bias condition, solar cells emit infrared light (wavelength around 1000 to 1200 nm) whose intensity reflects the number of minority carriers in base layers. Thus, all the causes that affect the carrier density can be detected, i.e., the minority carrier diffusion length (or in other words, lifetime), recombination velocity at surfaces and interfaces, etc. (intrinsic material properties), and wafer breakage and electrode breakdown, etc. (extrinsic defects). The EL intensity distribution can be captured by Si CCD camera in less than 1 s, and the detection area simply depends upon the optical lens system suitable to the wide range of 1 cm–1.5 m. This fast and precise technique is superior to the conventional scanning method such as the laser beam induced current (LBIC) method. The EL images are displayed as grayscale, which leads to the difficulty of distinguishing the sorts of those deficient areas. Since the intrinsic deficiency is more sensitive to temperature than the extrinsic deficiency, the change in solar cell temperature can offer the difference in EL intensity contrasts. These effects upon the measurement temperature can be applied to categorize the types of deficiency in the crystalline Si solar cell.     

A new approach to determine accurately minority-carrier lifetime

Electron or proton irradiations introduce recombination centers, which tend to affect solar cell parameters by reducing the minority-carrier lifetime (MCLT). Because this MCLT plays a fundamental role in the performance degradation of solar cells, in this work we present a new approach that allows us to get accurate values of MCLT. The relationship between MCLT in p-region and n-region both before and after irradiation has been determined by the new method. The validity and accuracy of this approach are justified by the fact that the degradation parameters that fit the experimental data are the same for both short-circuit current and the open-circuit voltages. This method is applied to the p⁺/n-InGaP solar cell under 1 MeV electron irradiation.     

Characteristics of silicon solar cell emitter with a reduced diffused phosphorus inactive layer

The diffusion of phosphorus using a phosphorous oxychloride (POCl₃) source in silicon has been used widely in crystalline silicon solar cells. The thermal diffusion process in the furnace consists of two steps: pre-deposition and drive-in. The phosphorous doping profile via thermal diffusion often exhibits high concentrations in the surface-near emitter, which result in a recombination increase. This layer, called the dead layer, should be inhibited in order to fabricate high efficiency silicon solar cells. In this paper, the amount of the POCl₃ flow rate was varied during the pre-deposition process in order to minimize the dead layer, and the characteristics of the phosphosilicate glass (PSG) and emitter were analyzed. From the secondary ion mass spectroscopy (SIMS) and electrochemical capacitance–voltage profiler (ECV) measurements, the emitter formed using a POCl₃ flow rate of 1000 sccm contained the least amount of inactive dopant and resulted in reasonable performance in the silicon solar cell. As the POCl₃ flow rate increased, the doped silicon wafer included electrically inactive P near the surface, which functions as a defect degrading the electrical performance of the emitter. As a result of this, the removal of the dead layer containing the inactive P was attempted through dipping the doped wafer in a HF solution. After this process, the emitter saturation current density and implied V_oc were improved. The completed solar cells and their external quantum efficiencies at a short wavelength also demonstrated improved performance. A quantitative analysis of the emitter can provide a deeper understanding of methods to improve the electrical characteristics of the silicon solar cell.     

X-ray topography study of monocrystalline silicon wafers diffused with phosphorus by different methods

To reduce the cost of the emitter diffusion process, there has been increasing interest to substitute the standard process of batch POCl₃ emitter diffusion used in the silicon solar-cell manufacturing industry with in-line diffusion processes such as the spray-on and screen-printing process. For this reason, it is essential to study and compare the processes of different diffusion methods from the point of view of the crystalline quality of the final wafers. X-ray transmission topography was employed to characterize the possible precipitates and other microdefects generated in Czochralski-grown silicon (Cz Si) during the emitter diffusion process carried out by screen-printing, spray-on and the standard process, in which the emitter was provided by a liquid (POCl₃) source. The results indicate that the phosphorus diffusion process influences the crystalline quality of the wafers and the efficiency of the external gettering process that takes place during phosphorus diffusion depends on the diffusion method employed.     

21.63% industrial screen‐printed multicrystalline Si solar cell

In this paper, we demonstrate industrially feasible large‐area solar cells achieving energy conversion efficiency up to 21.63% on p‐type boron doped multicrystalline Si wafers. Advanced light trapping, passivation and hydrogenation technology are used to achieve excellent light absorption with very low surface recombination velocity. The bulk lifetime of the multi‐crystalline Si wafers used for the fabrication exceeds 500 μs after optimized gettering and hydrogenation processes. The high bulk lifetime and excellent surface passivation enable V_oc to exceed 670 mV. The metallization process is carried out by screen printing and firing in a conventional belt furnace. Detailed performance parameters and quantum efficiency of the cells will be illustrated in the paper. In addition, free energy loss analysis and cell simulation are also performed using the control parameters measured during cell fabrication processes.     

Gettering of metallic impurities in photovoltaic silicon

 This work addresses the issue of structural defect-metallic impurity interactions in photovoltaic silicon and their effect on minority carrier diffusion length values. Aluminium and phosphorus segregation gettering studies were performed on photovoltaic silicon in order to gain insight into these interactions and quantify the effect of gettering on solar cell performance. Integrated circuit grade silicon was also studied for comparative purposes. Additionally, a novel rapid thermal annealing technique, designed to dissolve metallic impurity precipitates, and Deep Level Transient Spectroscopy were utilized to determine the as-grown impurity concentration in both grades of materials. Significant differences in gettering responses between the two grades of silicon are observed. Gettering treatments greatly improve I.C. grade silicon with a specific gettering temperature providing the optimal response. Photovoltaic grade silicon does not respond as well to the gettering treatments and, in some cases, the material degrades at higher gettering temperatures. The degradation is primarily observed in dislocated regions of multicrystalline photovoltaic silicon. Additionally, these dislocated regions were found to possess the highest as-grown metallic impurity concentration of all the materials studied. The dislocation-free photovoltaic silicon has a higher diffusion length relative to dislocated silicon but could not be improved by the gettering methods employed in this study. A model is presented to describe these phenomena where the high concentration of metallic impurities at dislocations produce relatively low minority carrier diffusion lengths as well as the degrading response with higher gettering temperatures while microdefects create an upper limit to the photovoltaic grade material’s diffusion length. Received: 21 June 1996/Accepted: 2 September 1996     

Ni reactions with surfaces: dependence of gettering efficiencies for Ni on crystal-growth conditions, back-side-gettering techniques, oxygen precipitates and thermal treatments

We have performed measurements on the gettering efficiencies for Ni in different silicon wafers. Gettering efficiencies were measured of wafers grown by different crystal-growth techniques, such as Czochralski-grown (CZ) and floating zone (FZ), as well as wafers containing crystal-originated particles (COPs) of different size and density. Lightly boron doped CZ wafers covered with an epitaxial layer were also evaluated. In another set of experiments, we compared different back-side-gettering techniques, like poly-silicon, stacking faults and He-implanted back sides and the dependence of back-side gettering on cooling rate and contamination level. Internal surfaces of oxygen precipitates were also investigated. The gettering test started with a reproducible spin-on contamination in the range around 10¹² atoms/cm² and was followed by a thermal treatment to redistribute the Ni impurity in the wafer. Subsequently, wafers were analyzed for their surface and bulk contamination by a novel layer-by-layer etching, stratigraphical technique in combination with inductively coupled plasma mass spectrometry. No detectable gettering effect of COPs was found. FZ wafers differed remarkably in their gettering behavior from CZ wafers, obviously due to differences in aggregated self-point defects. Most remarkably, the deposition process of an epitaxial layer changed the gettering behavior of p/p- wafers. Comparing the gettering efficiencies of different back sides, an extraordinarily high gettering efficiency of He-implanted voids can be anticipated, which was higher than the gettering efficiency of poly-silicon and stacking faults. High cooling rates at the end of the drive-in cycle and low contamination levels lowered the gettering efficiencies of back-side-gettering techniques, suggesting a diffusion-limited gettering process. Based on the dependence of the gettering efficiencies on different drive-in cycles, a surface reaction as a mechanistic initiation of the drive-in must be assumed. Oxygen precipitates exhibited a high gettering effect for Ni contamination. All experimental results are interpreted by available active surfaces in the gettering phases. Received: 30 May 2001 / Accepted: 16 June 2001 / Published online: 30 August 2001     

晶硅太阳电池中Fe-B对与少子寿命、陷阱浓度及内量子效率的相关性

以太阳电池级直拉单晶硅片为材料,利用瞬态微波反射光电导衰减仪研究了硅片分别经过单、双面扩散后Fe-B对与少子寿命τ、陷阱浓度及制备成电池的内量子效率（IQE）的相关性.对于单面扩散后的样品,Fe-B对浓度分布在较大程度上决定了少子寿命分布;对于双面扩散后的样品,Fe-B对浓度显著降低（在135×10¹¹ cm^-3左右）,已不及其他杂质和缺陷对少子寿命的影响.结合瞬态微波衰减信号和陷阱模型,对单、双面吸杂前后硅片的陷阱浓度进行数值计算,发现经过扩散 关键词： 少子寿命 陷阱浓度 内量子效率 Fe-B对     

High efficiency screen-printed n-type silicon solar cell using co-diffusion of APCVD boron emitter and POCl3 back surface field

We present the fabrication and analysis of Passivated Emitter and Rear Totally Diffused (PERT) solar cells on n-type silicon using a co-diffusion process. In a single high temperature step, a BSG/SiO_x stack deposited by APCVD and a POCl₃ back surface field diffuse into the wafer to form the boron doped emitter and phosphorus doped back surface field. The SiO_x layer on top of BSG acts as a masking layer to prevent cross-doping of phosphorus as well as a blocking layer for boron out-diffusion. This resulted in an initial sheet resistance of 76 Ω/□ with good uniformity and a final p⁺ emitter sheet resistance of 97 Ω/□ after boron rich layer removal. Additionally, bulk lifetime was investigated before and after the high temperature step that resulted in an increase from 1.2 ms to 1.5 ms due to a POCl₃ gettering effect. A peak cell efficiency of 20.3% was achieved and each recombination component in terms of saturation current density was calculated and analyzed to understand the cell for further efficiency enhancement.     

调制激光致硅晶圆载流子辐射扫描成像试验研究

建立了调制激光诱发硅晶圆少数载流子密度波一维模型, 仿真分析了少数载流子输运参数对调制激光诱发载流子辐射信号频域响应的影响. 利用调制激光诱发载流子辐射扫描成像系统对含有表面划痕的硅晶圆进行了扫描成像试验研究. 通过少数载流子密度波模型与多参数拟合方法反求得到了扫描区域的输运参数二维分布图. 该方法得到的少数载流子寿命与利用传统光电导方法测量的少数载流子寿命结果相符; 分析了划痕对载流子输运参数造成的影响, 与光电导方法比较, 该方法可以测量不同位置的全部载流子输运参数且分辨率高.     

Hybrid process for texturization of diamond wire sawn multicrystalline silicon solar cell

Acid texture is difficult for diamond wire sawn (DWS) multicrystalline silicon (mc‐Si) wafer owing to the inhomogeneous distribution of damage layer on the surface. In this article, metal‐assisted chemical etching (MACE) has been selected for introducing a porous seeding layer to induce acid texturing etching. SEM results show that the oval pit structures coverage get obvious improvement even on the smooth areas. Owing to the further improved light absorption ability by second MACE and nanostructure rebuilding (NSR) process, nanostructured DWS mc‐Si solar cell has exhibited a conversion efficiency of 17.96%, which is 0.45% higher than that of DWS wafer with simple acid texture process. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)