技术领域technical field
本发明涉及感光化学技术领域，尤其涉及一种刻蚀辅助剂及其制备方法和应用方法。The invention relates to the technical field of photosensitive chemistry, in particular to an etching auxiliary agent, a preparation method and an application method thereof.
背景技术Background technique
继硅基PERC和TOPcon太阳能电池以后，硅基异质结(HJT)太阳能电池近几年来受到越来越多的关注。其具有结构对称性、低温工艺、高开路电压、高转换效率以及良好的稳定性诸多优势，是下一代光伏技术的有力竞争者。异质结电池的工艺流程包括双面清洗和表面织构化，以及通过PECVD方法在正面依次沉积5-10nm的本征非晶Si层和5-10nm的p型非晶Si，以形成p-n结。After silicon-based PERC and TOPcon solar cells, silicon-based heterojunction (HJT) solar cells have received more and more attention in recent years. It has the advantages of structural symmetry, low temperature process, high open circuit voltage, high conversion efficiency and good stability, and is a strong competitor for the next generation of photovoltaic technology. The process flow of heterojunction cells includes double-sided cleaning and surface texturing, and sequentially depositing a 5-10nm intrinsic amorphous Si layer and a 5-10nm p-type amorphous Si layer on the front side by PECVD method to form a p-n junction .
异质结电池的设计核心在于晶体硅衬底与非晶硅组成了异质结结构，因此关于这种异质结结构的界面钝化起着尤为关键的作用。高质量的界面钝化可以有效降低载流子的复合，提高少子寿命，最终提高电池的效率。在表面织构化工艺之后，硅衬底上形成了致密的金字塔型陷光结构。传统晶体硅电池采用氮化硅薄膜进行钝化，但氮化硅薄膜厚度在80-100nm，因此只需将金字塔陷光结构的尺寸控制在1-2um即可有很好的薄膜沉积质量和钝化效果。但是1-2um的金字塔陷光结构却不适用于异质结电池，主要有两点原因：第一是非晶硅薄膜的厚度在5-10nm，由于应力的作用，很难在小绒面结构上有良好的覆盖性，甚至会在塔尖和塔底处产生较多裂纹；第二是如今各大厂商都在尝试在非晶硅上使用掺杂微晶工艺，微晶的晶粒尺寸会到达微米级别，甚至会超过部分相邻金字塔结构之间的距离，很难有良好的薄膜沉积质量和覆盖性。The core of the design of heterojunction cells is that the crystalline silicon substrate and amorphous silicon form a heterojunction structure, so the interface passivation of this heterojunction structure plays a particularly critical role. High-quality interface passivation can effectively reduce the recombination of carriers, increase the minority carrier lifetime, and ultimately improve the efficiency of the battery. After the surface texturing process, a dense pyramid-shaped light-trapping structure is formed on the silicon substrate. Traditional crystalline silicon cells use silicon nitride film for passivation, but the thickness of silicon nitride film is 80-100nm, so it is only necessary to control the size of the pyramid light-trapping structure at 1-2um to have good film deposition quality and passivation. effect. However, the 1-2um pyramid light-trapping structure is not suitable for heterojunction cells. There are two main reasons: the first is that the thickness of the amorphous silicon film is 5-10nm. It has good coverage, and even produces more cracks at the top and bottom of the tower; the second is that major manufacturers are now trying to use doped microcrystal technology on amorphous silicon, and the grain size of the microcrystal will reach At the micron level, it even exceeds the distance between some adjacent pyramid structures, making it difficult to have good film deposition quality and coverage.
因此，在目前的异质结表面织构化工艺中，亟需提高金字塔结构的尺寸。目前市面上主流的单晶硅织构化添加剂制备得到的金字塔结构普遍在2um及以下，不能够满足硅基异质结太阳能电池的要求。Therefore, in the current heterojunction surface texturing process, it is urgent to increase the size of the pyramid structure. At present, the pyramid structure prepared by the mainstream monocrystalline silicon texturing additives on the market is generally 2um or below, which cannot meet the requirements of silicon-based heterojunction solar cells.
发明内容Contents of the invention
本发明的目的在于提供一种刻蚀辅助剂及其制备方法和应用方法，用于克服现有表面织构化添加剂无法得到较大金字塔结构的问题。The object of the present invention is to provide an etching auxiliary agent and its preparation method and application method, which are used to overcome the problem that the existing surface texturing additives cannot obtain larger pyramid structures.
为了实现上述目的，本发明提供如下技术方案：In order to achieve the above object, the present invention provides the following technical solutions:
一种刻蚀辅助剂，包括以下组分：0.1-2.0wt％亚甲基双萘磺酸钠、0.1-2.0wt％绒面催化剂、0.005-0.05wt％脱泡剂、0.001-0.05wt％外观修饰剂、0.1-2.0wt％反应调节剂，余量为去离子水。An etching auxiliary agent, comprising the following components: 0.1-2.0wt% sodium methylene bis-naphthalene sulfonate, 0.1-2.0wt% suede catalyst, 0.005-0.05wt% defoaming agent, 0.001-0.05wt% appearance Modifier, 0.1-2.0wt% reaction modifier, and the balance is deionized water.
有益技术效果：本发明提供的刻蚀辅助剂包含以下组分：0.1-2.0wt％亚甲基双萘磺酸钠、0.1-2.0wt％绒面催化剂、0.005-0.05wt％脱泡剂、0.001-0.05wt％外观修饰剂、0.1-2.0wt％反应调节剂，余量为去离子水。本发明以亚甲基双萘磺酸钠为主要作用成分，配合使用绒面催化剂、脱泡剂、外观修饰剂和反应调节剂，在进行单晶硅表面刻蚀的过程中保证反应持续、稳定、均匀进行，最终得到的单晶硅表面形成了底座边长在3-5um的金字塔结构形貌。其中，本发明中的亚甲基双萘磺酸钠主要用于促进反应进行并产生较大的金字塔结构；本发明添加的绒面催化剂可以提高金字塔结构的密度，保证其致密性；由于碱性溶液(KOH)在刻蚀过程中会产生氢气，由于表面张力的作用，气泡会聚集在硅片表面，导致反应无法正常进行，本发明通过添加脱泡剂，消除了硅表面的产生的气泡，保证了反应持续的进行；通过添加外观修饰剂使硅片表面各处的反应比较均匀，且保证刻蚀完的硅片外观均匀，满足工业生产需求；另外，本发明还添加了反应调节剂，主要作用是与其他组分协同作用，调节反应速率，保证刻蚀程度的可控性，可以根据需要获得所需的表面形貌。本发明请求保护的刻蚀辅助剂在辅助刻蚀过程中可以保证反应持续、稳定、均匀进行，最终得到的单晶硅表面形成了底座边长在3-5um的金字塔结构形貌，远超当前能形成的金字塔结构大小，可以实现异质结结构的高质量界面钝化，对于推动异质结太阳能电池产业化具有重要意义。Beneficial technical effects: the etching auxiliary agent provided by the invention comprises the following components: 0.1-2.0wt% sodium methylene bis-naphthalene sulfonate, 0.1-2.0wt% suede catalyst, 0.005-0.05wt% defoamer, 0.001 - 0.05wt% appearance modifier, 0.1-2.0wt% reaction regulator, and the balance is deionized water. The present invention uses sodium methylene bis-naphthalene sulfonate as the main active ingredient, and cooperates with a suede catalyst, a defoamer, an appearance modifier and a reaction regulator to ensure continuous and stable reaction during the process of etching the surface of single crystal silicon , evenly, and the surface of the finally obtained monocrystalline silicon forms a pyramid structure with a base side length of 3-5um. Wherein, sodium methylene bis-naphthalene sulfonate in the present invention is mainly used to promote the reaction and produce a larger pyramid structure; the suede catalyst added in the present invention can improve the density of the pyramid structure and ensure its compactness; The solution (KOH) will generate hydrogen during the etching process. Due to the effect of surface tension, the bubbles will gather on the surface of the silicon wafer, causing the reaction to fail to proceed normally. The present invention eliminates the bubbles generated on the silicon surface by adding a defoaming agent. It ensures that the reaction continues; by adding an appearance modifier, the reaction on the surface of the silicon wafer is relatively uniform, and the appearance of the etched silicon wafer is guaranteed to be uniform, which meets the needs of industrial production; in addition, the present invention also adds a reaction regulator, The main function is to cooperate with other components to adjust the reaction rate, ensure the controllability of the etching degree, and obtain the desired surface morphology as required. The etching auxiliary agent claimed in the present invention can ensure continuous, stable and uniform reaction during the auxiliary etching process, and finally the surface of the obtained single crystal silicon forms a pyramid structure with a base side length of 3-5um, which is far beyond the current The size of the pyramid structure that can be formed can realize high-quality interface passivation of the heterojunction structure, which is of great significance for promoting the industrialization of heterojunction solar cells.
附图说明Description of drawings
图1是实施例1中制得样品的表面形貌SEM图；Fig. 1 is the surface topography SEM figure of sample obtained in embodiment 1;
图2是实施例2中制得样品的表面形貌SEM图；Fig. 2 is the surface topography SEM figure of sample obtained in embodiment 2;
图3是对比例4中制得样品(现有技术)的表面形貌SEM图。Fig. 3 is the SEM image of the surface morphology of the sample (prior art) prepared in Comparative Example 4.
具体实施方式Detailed ways
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
本发明提供一种刻蚀辅助剂，包括以下组分：0.1-2.0wt％亚甲基双萘磺酸钠、0.1-2.0wt％绒面催化剂、0.005-0.05wt％脱泡剂、0.001-0.05wt％外观修饰剂、0.1-2.0wt％反应调节剂，余量为去离子水。The invention provides an etching auxiliary agent, which comprises the following components: 0.1-2.0wt% sodium methylene bis-naphthalene sulfonate, 0.1-2.0wt% suede catalyst, 0.005-0.05wt% defoaming agent, 0.001-0.05 wt% appearance modifier, 0.1-2.0 wt% reaction modifier, and the balance is deionized water.
在本发明中，所述刻蚀辅助剂优选包括以下组分：0.5-1.0wt％亚甲基双萘磺酸钠、0.5-1.0wt％绒面催化剂、0.01-0.02wt％脱泡剂、0.01-0.03wt％外观修饰剂、0.8-1.2wt％反应调节剂，余量为去离子水。In the present invention, the etching aid preferably includes the following components: 0.5-1.0wt% sodium methylene bis-naphthalene sulfonate, 0.5-1.0wt% suede catalyst, 0.01-0.02wt% defoamer, 0.01 - 0.03wt% appearance modifier, 0.8-1.2wt% reaction regulator, and the balance is deionized water.
在本发明中，所述刻蚀辅助剂更优选包括以下组分：0.8wt％亚甲基双萘磺酸钠、0.8wt％绒面催化剂、0.015wt％脱泡剂、0.02wt％外观修饰剂、0.10wt％反应调节剂，余量为去离子水。In the present invention, the etching aid more preferably includes the following components: 0.8wt% sodium methylene bis-naphthalene sulfonate, 0.8wt% suede catalyst, 0.015wt% defoaming agent, 0.02wt% appearance modifier , 0.10wt% reaction modifier, and the balance is deionized water.
在本发明中，所述亚甲基双萘磺酸钠的来源并无特殊要求，采用市售产品即可。应当理解的是，所述亚甲基双萘磺酸钠可以有效促进刻蚀反应的进行，并有助于获得较大的金字塔型陷光结构。In the present invention, there is no special requirement on the source of the sodium methylene bis-naphthalene sulfonate, and commercially available products can be used. It should be understood that the sodium methylene bis-naphthalene sulfonate can effectively promote the etching reaction and help to obtain a larger pyramid-shaped light-trapping structure.
在本发明中，所述亚甲基双萘磺酸钠的含量优选为0.1-2.0wt％，更优选为0.5-1.0wt％，最优选为0.8wt％。In the present invention, the content of the sodium methylene bis-naphthalene sulfonate is preferably 0.1-2.0 wt%, more preferably 0.5-1.0 wt%, most preferably 0.8 wt%.
在本发明中，所述绒面催化剂优选为聚环氧琥珀酸、烷基糖苷、十二烷基硫酸钠或十二烷基苯磺酸钠中的一种；更优选为聚环氧琥珀酸。本发明对所述绒面催化剂的分子量并无特殊要求，采用本领域常规使用的即可。本发明对所述绒面催化剂的来源并无特殊要求，采用市售产品即可。应当理解的是，本发明中绒面催化剂的作用是提高金字塔结构的密度，保证致密性。In the present invention, the suede catalyst is preferably one of polyepoxysuccinic acid, alkyl glucoside, sodium dodecyl sulfate or sodium dodecylbenzenesulfonate; more preferably polyepoxysuccinic acid . In the present invention, there is no special requirement on the molecular weight of the textured catalyst, which can be conventionally used in this field. The present invention has no special requirements on the source of the textured catalyst, and commercially available products can be used. It should be understood that the function of the textured catalyst in the present invention is to increase the density of the pyramid structure and ensure compactness.
在本发明中，所述绒面催化剂的含量优选为0.1-2.0wt％，更优选为0.5-1.0wt％，最优选为0.8wt％。In the present invention, the content of the texture catalyst is preferably 0.1-2.0 wt%, more preferably 0.5-1.0 wt%, most preferably 0.8 wt%.
在本发明中，所述脱泡剂优选为环糊精、羟乙基纤维素、羟丙甲基纤维素、阿拉伯胶、瓜尔胶或黄原胶中的一种；更优选为环糊精。本发明对所述脱泡剂的分子量并无特殊要求，采用本领域常规使用的即可。本发明对所述脱泡剂的来源并无特殊要求，采用市售产品即可。应当理解的是，由于碱性溶液(KOH)在刻蚀过程中会产生氢气，由于表面张力的作用，气泡会聚集在硅片表面，导致反应无法正常进行，通过添加脱泡剂，消除了硅表面的产生的气泡，保证了反应持续的进行。In the present invention, the defoaming agent is preferably one of cyclodextrin, hydroxyethylcellulose, hydroxypropylmethylcellulose, gum arabic, guar gum or xanthan gum; more preferably cyclodextrin . The present invention has no special requirements on the molecular weight of the defoaming agent, which can be conventionally used in this field. The present invention has no special requirements on the source of the defoaming agent, and commercially available products can be used. It should be understood that since the alkaline solution (KOH) will generate hydrogen gas during the etching process, bubbles will gather on the surface of the silicon wafer due to the effect of surface tension, causing the reaction to fail to proceed normally. By adding a defoaming agent, the silicon The air bubbles generated on the surface ensure that the reaction continues.
在本发明中，所述脱泡剂的含量优选为0.005-0.05wt％，更优选为0.01-0.02wt％，最优选为0.015wt％。In the present invention, the content of the defoaming agent is preferably 0.005-0.05wt%, more preferably 0.01-0.02wt%, most preferably 0.015wt%.
在本发明中，所述外观修饰剂优选为聚乙二醇、二乙二醇甲醚、二乙二醇丁醚、三缩乙二醇丁醚或四缩乙二醇丁醚中的一种；更优选为聚乙二醇。特别的，所述聚乙二醇优选为聚乙二醇200、聚乙二醇400、聚乙二醇600、聚乙二醇800和聚乙二醇1000。当选定聚乙二醇作为外观修饰剂时，本发明中聚乙二醇分子量越小，则效果越好。本发明对所述外观修饰剂的来源并无特殊要求，采用市售产品即可。应当理解的是，通过添加外观修饰剂，使得硅片表面各处的反应比较均匀，且保证硅片外观没有问题。In the present invention, the appearance modifier is preferably one of polyethylene glycol, diethylene glycol methyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether or tetraethylene glycol butyl ether ; More preferably polyethylene glycol. In particular, the polyethylene glycol is preferably polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800 and polyethylene glycol 1000. When polyethylene glycol is selected as the appearance modifier, the smaller the molecular weight of polyethylene glycol in the present invention, the better the effect. The present invention has no special requirements on the source of the appearance modifier, and commercially available products can be used. It should be understood that by adding the appearance modifier, the reaction on the surface of the silicon wafer is relatively uniform, and the appearance of the silicon wafer is guaranteed to be correct.
在本发明中，所述外观修饰剂的含量优选为0.001-0.05wt％，更优选为0.01-0.03wt％，最优选为0.02wt％。In the present invention, the content of the appearance modifier is preferably 0.001-0.05 wt%, more preferably 0.01-0.03 wt%, most preferably 0.02 wt%.
在本发明中，反应调节剂优选为为无机钠盐和/或有机钠盐；所述无机钠盐可以选择为碳酸钠和/或硅酸钠，所述有机钠盐可以选择为三聚磷酸钠，柠檬酸钠，乳酸钠和酒石酸钠中的一种或两种。所述反应调节剂更优选为碳酸钠和硅酸钠。本发明对所述反应调节剂的来源并无特殊要求，采用市售产品即可。应当理解的是，本发明中反应调节剂的主要作用是调节反应速率，保证刻蚀程度的可控性，从而可以根据需要获得所需的表面形貌。In the present invention, the reaction regulator is preferably an inorganic sodium salt and/or an organic sodium salt; the inorganic sodium salt can be selected as sodium carbonate and/or sodium silicate, and the organic sodium salt can be selected as sodium tripolyphosphate , one or both of sodium citrate, sodium lactate and sodium tartrate. The reaction regulator is more preferably sodium carbonate and sodium silicate. The present invention has no special requirements on the source of the reaction modifier, and commercially available products can be used. It should be understood that the main function of the reaction regulator in the present invention is to adjust the reaction rate and ensure the controllability of the etching degree, so that the desired surface morphology can be obtained as required.
在本发明中，所述反应调节剂的含量优选为0.1-2.0wt％％，更优选为0.8-1.2wt％，最优选为0.10wt％。In the present invention, the content of the reaction regulator is preferably 0.1-2.0 wt%, more preferably 0.8-1.2 wt%, most preferably 0.10 wt%.
在本发明中，之所以采用去离子水，是为了避免非去离子水中存在的化合物离子与刻蚀液或者硅表面发生反应，导致刻蚀反应不准确。一般来讲，去离子水要求电阻小于等于1.0MΩ。In the present invention, the reason why deionized water is used is to avoid the reaction of compound ions in non-deionized water with etching solution or silicon surface, resulting in inaccurate etching reaction. Generally speaking, deionized water requires resistance less than or equal to 1.0MΩ.
本发明还提供一种刻蚀辅助剂的制备方法，用于制备上述的刻蚀辅助剂，包括以下步骤：The present invention also provides a method for preparing an etching auxiliary agent, which is used to prepare the above etching auxiliary agent, comprising the following steps:
将0.1-2.0wt％亚甲基双萘磺酸钠、0.1-2.0wt％绒面催化剂、0.005-0.05wt％脱泡剂、0.001-0.05wt％外观修饰剂、0.1-2.0wt％反应调节剂，依次加入去离子水中，期间不断进行搅拌，即得所述刻蚀辅助剂。0.1-2.0wt% sodium methylene bis-naphthalene sulfonate, 0.1-2.0wt% suede catalyst, 0.005-0.05wt% defoamer, 0.001-0.05wt% appearance modifier, 0.1-2.0wt% reaction regulator , sequentially added to deionized water, during which the stirring was continued to obtain the etching auxiliary agent.
在本发明中，所述五种辅助剂组分添加至去离子水的过程有顺序要求，优选按照亚甲基双萘磺酸钠、绒面催化剂、脱泡剂、外观修饰剂、调节剂的顺序添加。In the present invention, the process of adding the five auxiliary components to deionized water has order requirements, preferably according to the order of sodium methylene bis-naphthalene sulfonate, suede catalyst, defoamer, appearance modifier, regulator added sequentially.
在本发明中，所述相邻组分添加之间优选间隔一定时间添加；所述间隔时间优选为1-2min，更优选为1.5min。应当理解的是，所述在相邻组分之间相隔一定时间，是为了给与组分溶解的时间，将组分充分溶解。In the present invention, it is preferable to add a certain time interval between the addition of the adjacent components; the interval time is preferably 1-2 min, more preferably 1.5 min. It should be understood that the interval between adjacent components for a certain period of time is to allow time for the components to dissolve and fully dissolve the components.
在本发明中，所述组分添加时还包括搅拌操作；所述搅拌优选以500-600rpm的速率进行，更优选为550rpm。In the present invention, the addition of the components also includes a stirring operation; the stirring is preferably performed at a rate of 500-600 rpm, more preferably 550 rpm.
在本发明中，将最后的反应调节剂添加至水中后，即可得到所述刻蚀辅助剂；优选的，在将最后的反应调节剂添加至水中后，还可继续进行搅拌5-10min。In the present invention, the etching auxiliary agent can be obtained after adding the last reaction regulator into the water; preferably, after adding the last reaction regulator into the water, the stirring can be continued for 5-10 min.
本发明还提供一种刻蚀辅助剂的应用方法，包括：将所述刻蚀辅助剂加入到KOH溶液中，搅拌均匀制成刻蚀液；将单晶硅放入所述刻蚀液中刻蚀得到刻蚀后的单晶硅。The present invention also provides an application method of an etching auxiliary agent, comprising: adding the etching auxiliary agent into a KOH solution, stirring evenly to make an etching solution; putting single crystal silicon into the etching solution to etch The etched single crystal silicon is obtained by etching.
在本发明中，所述蚀辅助剂和KOH溶液的质量比优选为(1.0-5.0)：100；更优选为2.5:100；所述KOH溶液的浓度优选为0.5-2.0wt％；更优选为1wt％；所述搅拌的速率优选为500-600rpm；更优选为550rpm。In the present invention, the mass ratio of the corrosion aid and the KOH solution is preferably (1.0-5.0):100; more preferably 2.5:100; the concentration of the KOH solution is preferably 0.5-2.0wt%; more preferably 1 wt%; the stirring rate is preferably 500-600 rpm; more preferably 550 rpm.
在本发明中，所述刻蚀优选在70-80℃条件下进行，更优选为75℃；所述刻蚀的时间优选为900-1500s，更优选为1200s。In the present invention, the etching is preferably performed at 70-80°C, more preferably 75°C; the etching time is preferably 900-1500s, more preferably 1200s.
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.
在本发明中，下述实施例及对比例中的原料如无特殊说明，均为市售试剂。In the present invention, the raw materials in the following examples and comparative examples are all commercially available reagents unless otherwise specified.
实施例1Example 1
本实施例刻蚀辅助剂包括以下组分：10g亚甲基双萘磺酸钠、10g聚环氧琥珀酸、0.5g环糊精、0.1g聚乙二醇200、5g硅酸钠、5g碳酸钠和969.4g去离子水。The etching auxiliary agent in this embodiment includes the following components: 10g sodium methylene bis-naphthalene sulfonate, 10g polyepoxysuccinic acid, 0.5g cyclodextrin, 0.1g polyethylene glycol 200, 5g sodium silicate, 5g carbonic acid Sodium and 969.4g deionized water.
刻蚀辅助剂的制备方法：The preparation method of etching auxiliary agent:
(1)按照原料配比，将亚甲基双萘磺酸钠、聚环氧琥珀酸、环糊精、聚乙二醇、硅酸钠、碳酸钠，按照时间间隔1.5min依次加入到去离子水中，在550rpm搅拌条件下配置成1L的刻蚀辅助剂；(1) According to the ratio of raw materials, add sodium methylene bis-naphthalene sulfonate, polyepoxysuccinic acid, cyclodextrin, polyethylene glycol, sodium silicate, and sodium carbonate to the deionized In water, under the stirring condition of 550rpm, prepare 1L of etching auxiliary agent;
(2)将刻蚀辅助剂加入到40LKOH溶液(1wt％)中，在550rpm搅拌条件下配置成刻蚀液；(2) Add the etching auxiliary agent to 40L KOH solution (1wt%), and configure it as an etching solution under the stirring condition of 550rpm;
(3)将刻蚀液加热到70℃，将单晶硅片放入刻蚀液中反应1200s，得到的产品表面形貌如图1所示，金字塔底座边长在3-5微米(如图1)(注：由于刻蚀得到的金字塔结构并不是均一大小的，因此这里的金字塔底座边长是一个范围值，意思是形成的80％以上的金字塔结构底座边长都在3-5微米的范围内)。(3) Heat the etching solution to 70°C, put the monocrystalline silicon wafer into the etching solution and react for 1200s. 1) (Note: Since the pyramid structure obtained by etching is not uniform in size, the side length of the pyramid base here is a range value, which means that more than 80% of the formed pyramid structure base side lengths are in the range of 3-5 microns within the range).
实施例2Example 2
本实施例刻蚀辅助剂包括以下组分：20g亚甲基双萘磺酸钠、20g烷基糖苷、0.5g羟乙基纤维素、0.5g二乙二醇甲醚、20g三聚磷酸钠和939g去离子水。The etching auxiliary agent of this embodiment comprises the following components: 20g sodium methylene bis-naphthalene sulfonate, 20g alkyl glucoside, 0.5g hydroxyethyl cellulose, 0.5g diethylene glycol methyl ether, 20g sodium tripolyphosphate and 939g deionized water.
刻蚀辅助剂的制备方法：The preparation method of etching auxiliary agent:
(1)按照原料配比，将亚甲基双萘磺酸钠、聚环氧琥珀酸、环糊精、聚乙二醇、硅酸钠、碳酸钠，按照时间间隔2.0min依次加入到去离子水中，在6000rpm搅拌条件下配置成1L的刻蚀辅助剂；(1) According to the ratio of raw materials, add sodium methylene bis-naphthalene sulfonate, polyepoxysuccinic acid, cyclodextrin, polyethylene glycol, sodium silicate, and sodium carbonate to the deionized In water, under the stirring condition of 6000rpm, make 1L of etching auxiliary agent;
(2)将刻蚀辅助剂加入到40LKOH溶液(1.5wt％)中，在500rpm搅拌条件下配置成刻蚀液；(2) Add the etching auxiliary agent to 40L KOH solution (1.5wt%), and configure it as an etching solution under the stirring condition of 500rpm;
(3)将刻蚀液加热到75℃，将单晶硅片放入刻蚀液中反应1500s，得到的产品表面形貌如图2所示，金字塔底座边长在3-5微米(如图2)。(3) Heat the etching solution to 75°C, put the monocrystalline silicon wafer into the etching solution and react for 1500s. 2).
实施例3Example 3
本实施例刻蚀辅助剂包括以下组分：8g亚甲基双萘磺酸钠、8g十二烷基硫酸钠、0.15g羟丙甲基纤维、0.2g聚乙二醇400、1g柠檬酸钠和982.65g去离子水。The etching auxiliary agent in this embodiment includes the following components: 8g sodium methylene bis-naphthalene sulfonate, 8g sodium lauryl sulfate, 0.15g hydroxypropyl methylcellulose, 0.2g polyethylene glycol 400, 1g sodium citrate and 982.65g deionized water.
刻蚀辅助剂的制备方法：The preparation method of etching auxiliary agent:
(1)按照原料配比，将亚甲基双萘磺酸钠、十二烷基硫酸钠、羟丙甲基纤维、聚乙二醇400、硅酸钠、碳酸钠，按照时间间隔1min依次加入到去离子水中，在500rpm搅拌条件下配置成1L的刻蚀辅助剂；(1) According to the ratio of raw materials, add sodium methylene bis-naphthalene sulfonate, sodium lauryl sulfate, hydroxypropyl methylcellulose, polyethylene glycol 400, sodium silicate, and sodium carbonate in sequence at intervals of 1 minute Into deionized water, under the stirring condition of 500rpm, make 1L of etching auxiliary agent;
(2)将刻蚀辅助剂加入到20LKOH溶液(0.5wt％)中，在600rpm搅拌条件下配置成刻蚀液；(2) Add the etching auxiliary agent to 20L KOH solution (0.5wt%), and configure it as an etching solution under the stirring condition of 600rpm;
(3)将刻蚀液加热到75℃，将单晶硅片放入刻蚀液中反应900s，得到的产品表面形貌中的金字塔底座边长在3-4微米。(3) Heat the etching solution to 75° C., put the monocrystalline silicon wafer into the etching solution and react for 900 s, and the side length of the pyramid base in the surface morphology of the obtained product is 3-4 microns.
实施例4Example 4
本实施例刻蚀辅助剂包括以下组分：10g亚甲基双萘磺酸钠、5g十二烷基苯磺酸钠、0.1g瓜尔胶、0.3g三缩乙二醇丁醚、4g乳酸钠、4g酒石酸钠和976.6g去离子水。The etching auxiliary agent in this embodiment includes the following components: 10g sodium methylene bis-naphthalene sulfonate, 5g sodium dodecylbenzenesulfonate, 0.1g guar gum, 0.3g triethylene glycol butyl ether, 4g sodium lactate , 4g sodium tartrate and 976.6g deionized water.
刻蚀辅助剂的制备方法：The preparation method of etching auxiliary agent:
(1)按照原料配比，将亚甲基双萘磺酸钠、聚环氧琥珀酸、环糊精、聚乙二醇、硅酸钠、碳酸钠，按照时间间隔2min依次加入到去离子水中，在600rpm搅拌条件下配置成1L的刻蚀辅助剂；(1) According to the ratio of raw materials, add sodium methylene bis-naphthalene sulfonate, polyepoxysuccinic acid, cyclodextrin, polyethylene glycol, sodium silicate, and sodium carbonate into deionized water in sequence at intervals of 2 minutes , under 600rpm stirring condition, configured as 1L etching auxiliary agent;
(2)将刻蚀辅助剂加入到100LKOH溶液(2.0wt％)中，在600rpm搅拌条件下配置成刻蚀液；(2) Add the etching auxiliary agent to 100L KOH solution (2.0wt%), and configure it as an etching solution under the stirring condition of 600rpm;
(3)将刻蚀液加热到80℃，将单晶硅片放入刻蚀液中反应1500s，得到的产品表面形貌中的金字塔底座边长在3-4微米。(3) Heat the etching solution to 80° C., put the monocrystalline silicon wafer into the etching solution and react for 1500 s, and the side length of the pyramid base in the obtained product surface morphology is 3-4 microns.
实施例5Example 5
本实施例刻蚀辅助剂包括以下组分：5g亚甲基双萘磺酸钠、10g聚环氧琥珀酸、0.2g阿拉伯胶、0.1g聚乙二醇1000、12g乳酸钠和972.7g去离子水。The etching aid in this embodiment includes the following components: 5g sodium methylene bis-naphthalene sulfonate, 10g polyepoxysuccinic acid, 0.2g gum arabic, 0.1g polyethylene glycol 1000, 12g sodium lactate and 972.7g deionized water .
刻蚀辅助剂的制备方法：The preparation method of etching auxiliary agent:
(1)按照原料配比，将亚甲基双萘磺酸钠、聚环氧琥珀酸、环糊精、聚乙二醇、硅酸钠、碳酸钠，按照时间间隔2min依次加入到去离子水中，在500rpm搅拌条件下配置成1L的刻蚀辅助剂；(1) According to the ratio of raw materials, add sodium methylene bis-naphthalene sulfonate, polyepoxysuccinic acid, cyclodextrin, polyethylene glycol, sodium silicate, and sodium carbonate into deionized water in sequence at intervals of 2 minutes , under the stirring condition of 500rpm, it is configured as 1L etching auxiliary agent;
(2)将刻蚀辅助剂加入到100LKOH溶液(2.0wt％)中，在550rpm搅拌条件下配置成刻蚀液；(2) Add the etching auxiliary agent to 100L KOH solution (2.0wt%), and configure it as an etching solution under the stirring condition of 550rpm;
(3)将刻蚀液加热到80℃，将单晶硅片放入刻蚀液中反应1500s，得到的产品表面形貌中的金字塔底座边长均在3-4微米。(3) Heat the etching solution to 80° C., put the monocrystalline silicon wafer into the etching solution and react for 1500 s, and the side length of the pyramid base in the surface morphology of the obtained product is all 3-4 microns.
实施例6Example 6
本实施例刻蚀辅助剂包括以下组分：7g亚甲基双萘磺酸钠、8.5g聚环氧琥珀酸、0.14g黄原胶、0.21g四缩乙二醇丁醚、9g乳酸钠和975.15g去离子水。The etching auxiliary agent in this embodiment includes the following components: 7g sodium methylene bis-naphthalene sulfonate, 8.5g polyepoxysuccinic acid, 0.14g xanthan gum, 0.21g tetraethylene glycol butyl ether, 9g sodium lactate and 975.15 g deionized water.
刻蚀辅助剂的制备方法：The preparation method of etching auxiliary agent:
(1)按照原料配比，将亚甲基双萘磺酸钠、聚环氧琥珀酸、环糊精、聚乙二醇、硅酸钠、碳酸钠，按照时间间隔1min依次加入到去离子水中，在600rpm搅拌条件下配置成1L的刻蚀辅助剂；(1) According to the ratio of raw materials, add sodium methylene bis-naphthalene sulfonate, polyepoxysuccinic acid, cyclodextrin, polyethylene glycol, sodium silicate, and sodium carbonate into deionized water in sequence at intervals of 1 min , under 600rpm stirring condition, configured as 1L etching auxiliary agent;
(2)将刻蚀辅助剂加入到100LKOH溶液(2.0wt％)中，在500rpm搅拌条件下配置成刻蚀液；(2) Add the etching auxiliary agent to 100L KOH solution (2.0wt%), and configure it as an etching solution under the stirring condition of 500rpm;
(3)将刻蚀液加热到75℃，将单晶硅片放入刻蚀液中反应1200s，得到的产品表面形貌中的金字塔底座边长均在3-4微米。(3) Heat the etching solution to 75° C., put the monocrystalline silicon wafer into the etching solution and react for 1200 s, and the side length of the pyramid base in the obtained product surface morphology is all 3-4 microns.
实施例7Example 7
本实施例刻蚀辅助剂包括以下组分：9g亚甲基双萘磺酸钠、8g聚环氧琥珀酸、0.17g黄原胶、0.25g二乙二醇丁醚、10g乳酸钠和972.58g去离子水。The etching auxiliary agent in this embodiment includes the following components: 9g sodium methylene bis-naphthalene sulfonate, 8g polyepoxysuccinic acid, 0.17g xanthan gum, 0.25g diethylene glycol butyl ether, 10g sodium lactate and 972.58g ionized water.
刻蚀辅助剂的制备方法：The preparation method of etching auxiliary agent:
(1)按照原料配比，将亚甲基双萘磺酸钠、聚环氧琥珀酸、环糊精、聚乙二醇、硅酸钠、碳酸钠，按照时间间隔1.5min依次加入到去离子水中，在550rpm搅拌条件下配置成1L的刻蚀辅助剂；(1) According to the ratio of raw materials, add sodium methylene bis-naphthalene sulfonate, polyepoxysuccinic acid, cyclodextrin, polyethylene glycol, sodium silicate, and sodium carbonate to the deionized In water, under the stirring condition of 550rpm, prepare 1L of etching auxiliary agent;
(2)将刻蚀辅助剂加入到100LKOH溶液(2.0wt％)中，在600rpm搅拌条件下配置成刻蚀液；(2) Add the etching auxiliary agent to 100L KOH solution (2.0wt%), and configure it as an etching solution under the stirring condition of 600rpm;
(3)将刻蚀液加热到70℃，将单晶硅片放入刻蚀液中反应900s，得到的产品表面形貌中的金字塔底座边长均在3-4微米。(3) Heat the etching solution to 70° C., put the monocrystalline silicon wafer into the etching solution and react for 900 s, and the side length of the pyramid base in the surface morphology of the obtained product is all 3-4 microns.
对比例1Comparative example 1
与实施例1相比，本实施例将实施例1中的亚甲基双萘磺酸钠等量替换为聚醚(现有技术中刻蚀辅助剂的有效成分)，其他条件不变，得到的产品表面形成零星的金字塔结构，但不致密，不符合实际生产需求。Compared with Example 1, in this example, the sodium methylene bis-naphthalene sulfonate equivalent in Example 1 is replaced by polyether (the active ingredient of the etching auxiliary agent in the prior art), and other conditions remain unchanged, and the obtained The sporadic pyramid structure is formed on the surface of the product, but it is not dense and does not meet the actual production needs.
对比例2Comparative example 2
与实施例1相比，本实施例将实施例1中的碳酸钠和硅酸钠等量替换为去离子水，其他条件不变，得到的产品表面形貌中的金字塔底座边长均在2微米以下，原因为反应调节剂碳酸钠和硅酸钠可以有效提高金字塔大小。Compared with Example 1, the present embodiment replaces the sodium carbonate and sodium silicate equivalents in Example 1 with deionized water, and other conditions are constant, and the pyramid base side lengths in the surface morphology of the obtained product are all within 2 Below the micron, the reason is that the reaction regulator sodium carbonate and sodium silicate can effectively increase the pyramid size.
对比例3Comparative example 3
与实施例1相比，本实施例将实施例1中的聚环氧琥珀酸(绒面催化剂)等量替换为自来水，其他条件不变，得到的产品表面形貌中的金字塔底座边长均在1-3微米，且表面致密性不强。Compared with Example 1, the polyepoxysuccinic acid (velvet catalyst) in Example 1 is replaced by tap water in the same amount in this example, and other conditions are constant, and the side lengths of the pyramid bases in the surface appearance of the obtained product are equal. At 1-3 microns, and the surface density is not strong.
对比例4Comparative example 4
与实施例1相比，本实施例将实施例1中的本发明的刻蚀辅助剂替换为等量的市面上主流的添加剂(现有技术，此对比例使用CN111117623A所述的刻蚀辅助剂)，得到的产品形貌边长2微米以下(如图3)。Compared with Example 1, this embodiment replaces the etching auxiliary agent of the present invention in Example 1 with an equivalent amount of additives on the market (prior art, this comparative example uses the etching auxiliary agent described in CN111117623A ), the obtained product morphology has a side length of less than 2 microns (as shown in Figure 3).
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。The above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Anyone skilled in the art can easily think of changes or substitutions within the technical scope disclosed in the present invention. Should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.
| Application Number | Priority Date | Filing Date | Title |
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| CN202310301123.8ACN116536050A (en) | 2023-03-24 | 2023-03-24 | A kind of etching auxiliary agent and its preparation method and application method |
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| CN202310301123.8ACN116536050A (en) | 2023-03-24 | 2023-03-24 | A kind of etching auxiliary agent and its preparation method and application method |
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| CN116536050Atrue CN116536050A (en) | 2023-08-04 |
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| CN110396725A (en)* | 2019-07-10 | 2019-11-01 | 天津爱旭太阳能科技有限公司 | Texturing additive for monocrystalline silicon wafer and its application |
| KR102368778B1 (en)* | 2021-10-19 | 2022-03-02 | (주)호진플라텍 | The texturing solution for single crystal silicon wafers |
| CN114481332A (en)* | 2022-01-27 | 2022-05-13 | 江苏捷捷半导体新材料有限公司 | Low-weight-loss monocrystalline silicon piece texturing additive, preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106087068A (en)* | 2016-07-08 | 2016-11-09 | 合肥中南光电有限公司 | A kind of amino of chitosan sulfonic acid monocrystaline silicon solar cell sheet surface texture liquid and preparation method thereof |
| CN110396725A (en)* | 2019-07-10 | 2019-11-01 | 天津爱旭太阳能科技有限公司 | Texturing additive for monocrystalline silicon wafer and its application |
| KR102368778B1 (en)* | 2021-10-19 | 2022-03-02 | (주)호진플라텍 | The texturing solution for single crystal silicon wafers |
| CN114481332A (en)* | 2022-01-27 | 2022-05-13 | 江苏捷捷半导体新材料有限公司 | Low-weight-loss monocrystalline silicon piece texturing additive, preparation method and application thereof |
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