技术领域technical field
本发明涉及光伏领域，具体涉及一种硼掺杂选择性发射极的制备方法。The invention relates to the field of photovoltaics, in particular to a preparation method of a boron-doped selective emitter.
背景技术Background technique
由于具有少子寿命高、温度系数低以及无B-O复合导致的光热诱导衰减等优点，N型晶硅电池已成为新一代高效太阳能电池的重点发展方向，也越来越受到业界的关注。目前较为成熟的N型晶硅电池主要包括N-PERT、N-PERL、N-TOPCon和N-IBC等结构电池。Due to the advantages of high minority carrier lifetime, low temperature coefficient, and no photothermal induced attenuation caused by B-O recombination, N-type crystalline silicon cells have become the key development direction of a new generation of high-efficiency solar cells, and they have also attracted more and more attention from the industry. At present, the relatively mature N-type crystalline silicon cells mainly include N-PERT, N-PERL, N-TOPCon and N-IBC structural cells.
选择性发射极结构（Selective Emitter，简称SE）是通过在电极接触区域进行重掺杂，电极之间进行轻掺杂，实现对发射极区域的优化，这样便可降低金属电极和硅片之间的接触电阻，同时还能降低扩散层区域的载流子复合，增强电池的输出电压和电流，从而能显著提升电池效率。The Selective Emitter structure (SE) is to optimize the emitter region by heavily doping the electrode contact area and lightly doping between the electrodes, so that the gap between the metal electrode and the silicon wafer can be reduced. At the same time, it can reduce the carrier recombination in the diffusion layer region, and enhance the output voltage and current of the battery, thereby significantly improving the battery efficiency.
磷的SE结构目前已在工业生产中得以应用，但是硼SE结构还没有得到有效应用。目前行业中也有一些针对硼SE结构的制备方法，主要分为以下两大类：（1）通过掩膜法结合二次硼扩的方法制备硼SE结构，主要是通过在硅衬底预先长掩膜层，然后对局部区域进行刻蚀形成窗口，之后进行一次硼扩散形成重掺，去掉掩膜后再二次硼扩散形成轻掺杂，该方法过程相对较为复杂，生产成本较高，难以在工业化中得以应用；（2）激光SE法，主要是通过沉积或涂抹硼源后再通过局部区域的激光推进实现重掺，其他未打激光区域实现轻掺，进而实现SE结构，由于硼的扩散所需激活能较高，需要较高的激光能量才能足以使得硼进行有效推进，这个过程激光不可避免会对基底硅产生较大烧蚀损伤，既会影响绒面结构，同时带来复合损伤，影响电池效率提升。The SE structure of phosphorus has been used in industrial production, but the SE structure of boron has not been effectively used. At present, there are also some preparation methods for boron SE structure in the industry, which are mainly divided into the following two categories: (1) The boron SE structure is prepared by the mask method combined with the secondary boron expansion method, mainly by pre-long masking on the silicon substrate. Then, the local area is etched to form a window, and then a boron diffusion is carried out to form heavy doping. After removing the mask, a second boron diffusion is carried out to form a light doping. This method is relatively complicated, the production cost is high, and it is difficult to It can be applied in industrialization; (2) Laser SE method, mainly by depositing or smearing a boron source, and then realizing heavy doping through local area laser advancement, and light doping in other unlasered areas, thereby realizing SE structure, due to the diffusion of boron The required activation energy is high, and high laser energy is required to make boron effectively advance. In this process, the laser will inevitably cause large ablation damage to the base silicon, which will not only affect the textured structure, but also bring composite damage. Affect the improvement of battery efficiency.
发明内容SUMMARY OF THE INVENTION
为解决现有技术的缺陷，本发明的目的在于提供一种硼掺杂选择性发射极的制备方法，在制绒后的硅片表面沉积BSG（硼硅玻璃）层，然后在BSG层表面局部覆盖掩膜层，使掩膜层的覆盖区域与硅片表面的金属电极印刷区域一致，然后对硅片进行高温推进，然后将硅片上的BSG层和掩膜层去除。In order to solve the defects of the prior art, the purpose of the present invention is to provide a preparation method of a boron-doped selective emitter, depositing a BSG (borosilicate glass) layer on the surface of the silicon wafer after texturing, and then partially on the surface of the BSG layer. The mask layer is covered so that the covering area of the mask layer is consistent with the metal electrode printing area on the surface of the silicon wafer, and then the silicon wafer is advanced at a high temperature, and then the BSG layer and the mask layer on the silicon wafer are removed.
优选的，所述在制绒后的硅片表面沉积BSG层，包括如下步骤：将制绒后的硅片置于管式硼扩散炉中进行管式沉积和轻微推进，使硅片表面获得一层BSG层和较浅的硼结。Preferably, the deposition of the BSG layer on the surface of the textured silicon wafer includes the following steps: placing the textured silicon wafer in a tubular boron diffusion furnace for tubular deposition and slight advancement, so that the surface of the silicon wafer obtains a layer BSG layer and shallower boron junction.
优选的，所述掩膜层为SiNx层或SiOxNy层。Preferably, the mask layer is a SiNx layer or a SiOxNy layer.
优选的，所述在BSG层表面局部覆盖掩膜层，包括如下步骤：在BSG层表面局部区域丝网印刷SiNx浆料或SiOxNy浆料，在该局部区域形成SiNx层或SiOxNy层，该局部区域与硅片表面的金属电极印刷区域一致。Preferably, the partially covering the mask layer on the surface of the BSG layer includes the following steps: screen printing SiNx paste or SiOxNy paste in a local area on the surface of the BSG layer, and forming a SiNx layer or SiOxNy layer in the local area, the local area It is consistent with the metal electrode printing area on the surface of the silicon wafer.
优选的，采用链式扩散炉或管式扩散炉对硅片进行高温推进，链式扩散炉设置五个温区，硅片依次经过进炉区、升温区、恒温区、降温区和出炉区，恒温区的温度控制在900-1100℃，硅片在恒温区高温推进200-1000s。Preferably, a chain-type diffusion furnace or a tube-type diffusion furnace is used to advance the silicon wafers at high temperature. The chain-type diffusion furnace is provided with five temperature zones. The temperature of the constant temperature zone is controlled at 900-1100°C, and the silicon wafer is advanced in the constant temperature zone at a high temperature for 200-1000s.
优选的，采用管式扩散炉对硅片进行高温推进，高温推进时，管式扩散炉中通入氮气和氧气。Preferably, a tubular diffusion furnace is used to advance the silicon wafer at a high temperature, and nitrogen and oxygen are introduced into the tubular diffusion furnace during the high temperature advance.
优选的，管式扩散炉的温度控制在950-1050℃，高温推进的时间为600-3000s。Preferably, the temperature of the tubular diffusion furnace is controlled at 950-1050° C., and the high temperature advancing time is 600-3000s.
优选的，采用含有HF的清洗液将硅片上的BSG层和掩膜层清洗去除。Preferably, the BSG layer and the mask layer on the silicon wafer are cleaned and removed by using a cleaning solution containing HF.
本发明的优点和有益效果在于：提供一种硼掺杂选择性发射极的制备方法，在沉积BSG层后只需局部覆盖掩膜层，能在不去除BSG层的条件下高温推进即可制备SE结构。The advantages and beneficial effects of the present invention are as follows: a method for preparing a boron-doped selective emitter is provided, which only needs to partially cover the mask layer after depositing the BSG layer, and can be prepared by advancing at high temperature without removing the BSG layer. SE structure.
本发明通过选择性的在BSG层表面局部区域（即金属电极印刷区域，以下简称电极区）覆盖掩膜层，对后续高温推进时电极区的硼向环境气氛中扩散起到抑制作用。具体的：在高温推进的过程中，由于电极区覆盖有掩膜层（SiNx层或SiOxNy层），能抑制电极区硅表面和BSG层中的硼往环境气氛（空气）中扩散逸出，从而使电极区有更多的硼源往硅衬底中扩散，电极区获得的硼浓度较高且结深较深；由于非电极区没有覆盖掩膜层，高温推进过程中，非电极区硅表面和BSG层中的硼会大量往环境气氛中扩散逸出，非电极区获得的硼浓度较低和且结深较浅；利用电极区和非电极区的差异便能制备出选择性发射极。In the present invention, the mask layer is selectively covered in the local area of the surface of the BSG layer (ie, the metal electrode printing area, hereinafter referred to as the electrode area), so as to inhibit the diffusion of boron in the electrode area into the ambient atmosphere during subsequent high temperature advancement. Specifically: in the process of high temperature advancement, since the electrode area is covered with a mask layer (SiNx layer or SiOxNy layer), it can inhibit the diffusion and escape of boron in the silicon surface of the electrode area and the BSG layer into the ambient atmosphere (air), thereby The electrode area has more boron sources to diffuse into the silicon substrate, and the boron concentration obtained in the electrode area is higher and the junction depth is deeper; since the non-electrode area does not cover the mask layer, during the high temperature advancement process, the non-electrode area silicon surface A large amount of boron in the BSG and BSG layers will diffuse into the ambient atmosphere, and the boron concentration obtained in the non-electrode area is lower and the junction depth is shallower; the selective emitter can be prepared by using the difference between the electrode area and the non-electrode area.
若采用管式扩散炉进行高温推进，可向管式扩散炉通入一定比例的氮气和氧气，在有氧气的环境中，能促进非电极区BSG层中的硼往环境气氛中扩散。If a tubular diffusion furnace is used for high-temperature propulsion, a certain proportion of nitrogen and oxygen can be introduced into the tubular diffusion furnace. In an environment with oxygen, it can promote the diffusion of boron in the BSG layer of the non-electrode area into the ambient atmosphere.
本发明具有如下特点：The present invention has the following characteristics:
1、本发明工艺步骤少，成本低，沉积BSG层后只需在电极区覆盖掩膜层（SiNx层或SiOxNy层），在不去除BSG层的条件下高温推进即可制备SE结构。1. The present invention has few process steps and low cost. After depositing the BSG layer, it only needs to cover the mask layer (SiNx layer or SiOxNy layer) in the electrode area, and the SE structure can be prepared by advancing at high temperature without removing the BSG layer.
2、本发明可行性高，可以直接利用现有产业设备。2. The present invention has high feasibility and can directly utilize existing industrial equipment.
3、本发明可使用链式推进，相对管式能增加产能。3. The present invention can use chain type propulsion, which can increase the production capacity compared with the tubular type.
4、本发明应用前景广。4. The present invention has wide application prospects.
具体实施方式Detailed ways
下面结合实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。The specific embodiments of the present invention will be further described below with reference to the examples. The following examples are only used to illustrate the technical solutions of the present invention more clearly, and cannot be used to limit the protection scope of the present invention.
本发明提供一种硼掺杂选择性发射极的制备方法，在制绒后的硅片表面沉积BSG（硼硅玻璃）层，然后在BSG层表面局部区域（即金属电极印刷区域，以下简称电极区）覆盖掩膜层（SiNx层或SiOxNy层），使掩膜层的覆盖区域与硅片表面的金属电极印刷区域一致，然后对硅片进行高温推进，然后将硅片上的BSG层和掩膜层去除。The invention provides a method for preparing a boron-doped selective emitter. A BSG (borosilicate glass) layer is deposited on the surface of a textured silicon wafer, and then a local area on the surface of the BSG layer (ie, the metal electrode printing area, hereinafter referred to as electrode area) cover the mask layer (SiNx layer or SiOxNy layer), make the coverage area of the mask layer consistent with the metal electrode printing area on the surface of the silicon wafer, then push the silicon wafer at high temperature, and then put the BSG layer and mask on the silicon wafer. Film removal.
本发明的具体实施例如下：Specific embodiments of the present invention are as follows:
1）制绒：选取N型硅原片进行常规清洗和制绒；1) Texturing: select N-type silicon original sheets for routine cleaning and texturing;
2）在制绒后的硅片表面沉积BSG层：将制绒后的硅片置于管式硼扩散炉中进行管式沉积和轻微推进，使硅片表面获得一层BSG层和较浅的硼结；管式沉积和轻微推进完成后，硼掺杂的峰值浓度为2E20cm-3，硼结深度为100nm，BSG层的厚度为20nm，方阻为200欧左右；2) Deposit a BSG layer on the surface of the textured silicon wafer: place the textured silicon wafer in a tubular boron diffusion furnace for tubular deposition and slight advancement, so that a layer of BSG layer and a shallower surface of the silicon wafer are obtained. Boron junction; after the tubular deposition and slight advancement are completed, the peak concentration of boron doping is 2E20cm-3 , the depth of the boron junction is 100nm, the thickness of the BSG layer is 20nm, and the square resistance is about 200Ω;
3）在BSG层表面局部覆盖掩膜层（SiNx层或SiOxNy层）：3) Locally cover the surface of the BSG layer with a mask layer (SiNx layer or SiOxNy layer):
在BSG层表面局部区域丝网印刷SiNx浆料或SiOxNy浆料，在该局部区域形成SiNx层或SiOxNy层，该局部区域与硅片表面的金属电极印刷区域一致；丝网印刷的图形宽度为100um；SiNx paste or SiOxNy paste is screen-printed in a local area on the surface of the BSG layer, and a SiNx layer or SiOxNy layer is formed in this local area, which is consistent with the metal electrode printing area on the surface of the silicon wafer; the width of the screen-printed pattern is 100um ;
4）对硅片进行高温推进：4) High temperature advancement of silicon wafers:
采用链式扩散炉或管式扩散炉对硅片进行高温推进，链式扩散炉设置五个温区，传送带速为100cm/min，硅片依次经过进炉区、升温区、恒温区、降温区和出炉区，恒温区的温度控制在900-1100℃，硅片在恒温区高温推进200-1000s，高温推进完成后电极区方阻为80-100欧，非电极区域方阻为200-250欧；The chain diffusion furnace or tube diffusion furnace is used to advance the silicon wafer at high temperature. The chain diffusion furnace is set with five temperature zones, and the conveyor speed is 100cm/min. The silicon wafer passes through the furnace entry zone, heating zone, constant temperature zone, and cooling zone in turn The temperature of the constant temperature zone is controlled at 900-1100 ℃, and the silicon wafer is advanced in the constant temperature zone for 200-1000s. After the high temperature advancement is completed, the square resistance of the electrode area is 80-100 ohms, and the square resistance of the non-electrode area is 200-250 ohms. ;
或者，or,
采用管式扩散炉对硅片进行高温推进，管式扩散炉中通入氮气和氧气，气体流量为O2:N2=1:4，管式扩散炉的温度控制在950-1050℃，高温推进的时间为600-3000s；A tubular diffusion furnace is used to advance the silicon wafer at high temperature. Nitrogen and oxygen are introduced into the tubular diffusion furnace. The gas flow rate is O2 :N2 =1:4. The temperature of the tubular diffusion furnace is controlled at 950-1050 ℃. The advancing time is 600-3000s;
5）采用含有HF的清洗液将硅片上的BSG层和掩膜层清洗去除。5) Use a cleaning solution containing HF to clean and remove the BSG layer and mask layer on the silicon wafer.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the technical principles of the present invention, several improvements and modifications can be made. These improvements and modifications It should also be regarded as the protection scope of the present invention.
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| CN202110607719.1ACN113363334A (en) | 2021-06-01 | 2021-06-01 | Preparation method of boron-doped selective emitter |
| CN202210000228.5ACN114497242A (en) | 2021-06-01 | 2022-01-01 | Preparation method and application of boron-doped selective emitter |
| PCT/CN2022/119038WO2023124254A1 (en) | 2021-06-01 | 2022-09-15 | Preparation method for and use of boron-doped selective emitter |
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