WO2023019934A1 - Texturing additive for rapid texturing, and application - Google Patents

Texturing additive for rapid texturing, and application Download PDF

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WO2023019934A1
WO2023019934A1 PCT/CN2022/081383 CN2022081383W WO2023019934A1 WO 2023019934 A1 WO2023019934 A1 WO 2023019934A1 CN 2022081383 W CN2022081383 W CN 2022081383W WO 2023019934 A1 WO2023019934 A1 WO 2023019934A1
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texturing
additive
sodium
rapid
solution
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Chinese (zh)
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周树伟
张丽娟
陈培良
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常州时创能源股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/08—Etching
    • C30B33/10—Etching in solutions or melts
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the field of photovoltaic technology, in particular to a texturing additive for rapid texturing and its application.
  • the manufacturing process of cells includes texturing, diffusion, etching, oxidation, coating, silk screen printing, sintering and other processes.
  • texturing is the first process. Challenged by the technical challenge of silicon wafer thinning. Texturing is to produce a "texture" on the surface of the silicon wafer by alkali etching to improve the absorption rate of the silicon wafer to sunlight, thereby improving the efficiency of the cell. As we all know, the higher the battery efficiency, the better the power generation income, which prompts manufacturers to constantly seek better texturing additives to assist alkali etching in the wet texturing process, and achieve the goal with the shortest texturing time. Lower corrosion depth and lower reflectivity, ie better surface "texture".
  • the silicon wafer needs to reach a certain corrosion depth to achieve the complete growth of the pyramid or It is the optimization of the suede surface.
  • the more suitable suede surface size that can be achieved by the existing texturing additives is 1.5 ⁇ 3um.
  • the object of the present invention is to propose a kind of texturing additive and its application for rapid texturing, the texturing additive can not only shorten the texturing time, but also can obtain the texturing sheet with low corrosion depth and low reflectivity.
  • a kind of texturing additive for rapid texturing comprising the following components in mass percent: 0.5% to 10% nucleating agent, 1% to 10% texturing catalyst, Surfactant 0.01% ⁇ 0.05%, defoaming agent 0.05% ⁇ 0.5%, the balance is deionized water.
  • the nucleating agent is selected from one or both of hydrolyzed polyacrylonitrile sodium salt and hydrolyzed polyacrylonitrile ammonium salt.
  • the suede catalyst is choline or choline hydroxide.
  • the surfactant is selected from sodium lauryl sulfate, sodium tetradecyl sulfate, sodium cetyl sulfate, sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, One or more of sodium hexaalkylbenzene sulfonates.
  • the defoaming agent is selected from toluenediamine polyether polyols.
  • the viscosity of the defoaming agent is 1100-12000 mPa ⁇ s.
  • a rapid texturing liquid which contains an alkaline solution and the above-mentioned texturing additive, and the mass ratio of the texturing additive to the alkaline solution is 0.5-2.5:100.
  • the alkaline solution is a 0.2-2wt% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
  • a rapid texturing method for monocrystalline silicon wafers using the above texturing liquid to texture the surface of monocrystalline silicon wafers.
  • the rapid texturing method of the above-mentioned monocrystalline silicon wafer comprises the following steps:
  • texture additives 0.5% to 10% of nucleating agent, 1% to 10% of texture catalyst, 0.01% to 0.05% of surfactant, 0.05% to 0.5% of The foaming agent is added to the remaining amount of deionized water, and mixed evenly to prepare a texturing additive;
  • step (3) Texturing: immerse the monocrystalline silicon wafer in the texturing solution prepared in step (2) for surface texturing, the texturing temperature is 75-85°C, and the texturing time is 240-290s.
  • the texturing additive of the present invention is hydrolyzed polyacrylonitrile sodium salt and hydrolyzed polyacrylonitrile ammonium salt as a nucleating agent, an anionic polymer obtained by alkaline hydrolysis of polyacrylonitrile waste, containing amide groups, Strong polar groups such as carboxyl and nitrile groups form strong hydrogen bonds with Si-H bonds on the surface of silicon wafers, which can be well adsorbed on the surface of silicon wafers, so they have good fleece performance and can form good fleece However, if the pyramid suede surface obtained from cashmere grows, it needs a larger corrosion depth.
  • the texture additive of the present invention has added texture catalyst choline or choline hydroxide, which contains active -OH in its molecule, has very strong basicity, and the positively charged N makes it It has a strong adsorption on the surface of the silicon wafer, so it has a synergistic effect with the alkali, promotes the combination of OH- and the surface of the silicon wafer, accelerates the corrosion reaction rate of the texturing process, and allows the reaction to completely grow and form the pyramid when the corrosion depth is small. Rather than staying in the growth process with high pyramid density but small texture, the reflectivity of the silicon wafer after texture is lower.
  • the texture catalyst choline or choline hydroxide is added to the texture additive of the present invention, the air bubbles on the surface of the silicon wafer will be generated faster, so the requirement for the removal rate of the air bubbles is higher.
  • the invention selects the toluene diamine polyether polyol with a viscosity of 1100-12000mPa ⁇ s as the defoaming agent, which has very low surface tension and promotes the rapid removal of the bubbles on the surface of the silicon chip.
  • the defoamer itself has a good defoaming ability, so that the basic appearance problems such as air bubble marks will not remain on the surface of the silicon wafer after texturing, there will still be poor uniformity, especially in the present invention. Low, the bubbles generated by the reaction on the surface of the silicon wafer are removed quickly, and the bubbles in the lower part will affect the surface of the upper part of the silicon wafer, so surfactants are required to be used together to optimize the texture appearance.
  • the surfactant of the present invention is selected from sodium lauryl sulfate, sodium tetradecyl sulfate, sodium cetyl sulfate, sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, hexadecane
  • sodium dodecylbenzenesulfonate as an appearance blending agent, also has the effect of supplementing cashmere, which is due to the sulfate group or sodium dodecylbenzenesulfonate in sodium dodecyl sulfate, etc.
  • nucleating agent has a certain polarity and adsorption, and can cooperate with nucleating agent to produce cashmere, so that the stability of cashmere production is better. Moreover, a small amount of surfactant is adsorbed on the surface of the silicon wafer, which promotes a more uniform distribution of the nucleating agent, so that a good appearance can be obtained even at a high corrosion rate.
  • the present invention has the following advantages:
  • the texturing additive of the present invention can shorten the texturing time to 240s;
  • Fig. 1 is the appearance of suede obtained in Example 1 of the present invention.
  • the parts by mass percentage 5 parts of hydrolyzed polyacrylonitrile ammonium salt, 2 parts of choline, 0.01 part of sodium dodecylsulfate, 0.015 part of sodium dodecylbenzenesulfonate, and 0.15 part of toluene with a viscosity of 8000 mPa s Diamine polyether polyol and 92.825 parts of deionized water are mixed and stirred evenly to make the texturing additive; then add the texturing additive, sodium hydroxide and deionized water in the texturing tank according to the mass ratio of 0.7:1:100, and stir Evenly prepare the texturing solution; then put the silicon chip into the texturing, the texturing temperature is 80°C, and the reaction time is 290s.
  • the texturing additive (the texturing additive disclosed in Chinese patent CN111501105A), sodium hydroxide and deionized water in sequence, stir evenly to make the texturing liquid; then put Texture the silicon wafers, the texturing temperature is 80°C, and the reaction time is 300s.
  • the textured sheets obtained in Examples 1-4 and Comparative Examples are weighed, the depth of corrosion is calculated, and the reflectivity test is carried out.
  • the reflectivity tester adopts NXT Helios-rc reflectivity tester, the test results are shown in Table 1.
  • Example 1 1.51 9.64%
  • Example 2 1.55 9.67%
  • Example 3 1.59 9.55%
  • Example 4 1.56 9.43% comparative example 2.50 9.00%

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Abstract

A texturing additive for rapid texturing, and an application. The texturing additive comprises the following components in percentage by mass: 0.5%-10% of a nucleating agent, 1%-10% of a texturing catalyst, 0.01%-0.05% of a surfactant, 0.05%-0.5% of a defoaming agent, and the balance of deionized water. The texturing additive can shorten the texturing time to 240 s; compared with existing texturing additives requiring a single-sided corrosion depth of 2.5 μm, when the single-sided corrosion depth of this texturing additive reaches 1.5 μm, complete growth of pyramids can be achieved, a texture size of 2 μm can be obtained, and a good effect on reducing the reflectivity is provided.

Description

一种用于快速制绒的制绒添加剂及应用A kind of texturing additive for fast texturing and its application 技术领域technical field
本发明涉及光伏技术领域，具体涉及一种用于快速制绒的制绒添加剂及应用。The invention relates to the field of photovoltaic technology, in particular to a texturing additive for rapid texturing and its application.
背景技术Background technique
随着光伏行业的飞速发展，不论是上游的硅料和硅片，还是中游的电池片，亦或是下游的组件都进行了大规模的扩产，其中电池片的扩产速度惊人，致使上游的硅片出现了供不应求的现象。电池片制造商为了摊薄成本，整个光伏行业内部开始出现薄片化的趋势，目前有些制造商已经开始使用厚度为140um的硅片，因此可以预见在不久的将来，薄片将成为行业的标配，甚至可能出现更薄的硅片用于光伏电池片。With the rapid development of the photovoltaic industry, whether it is upstream silicon materials and silicon wafers, midstream cells, or downstream components, large-scale expansions have been carried out. The expansion speed of cells is astonishing, causing upstream Silicon wafers are in short supply. In order to reduce the cost of cell manufacturers, the whole photovoltaic industry has begun to show a thinning trend. At present, some manufacturers have begun to use silicon wafers with a thickness of 140um. Thinner silicon wafers may emerge for use in photovoltaic cells.
电池片的制造环节包括制绒、扩散、刻蚀、氧化、镀膜、丝印、烧结等多个工序，为了尽可能使硅片在整个制造环节中的重量减少最低，制绒作为第一道工序将受到硅片薄片化的技术挑战。制绒是在硅片表面通过碱刻蚀产生“织构”,提高硅片对太阳光的吸收率，从而提高电池效率。众所周知，越高的电池效率会得到越好的发电收益，这促使各制造商在湿法制绒过程中，不断地寻求更好的制绒添加剂来辅助碱刻蚀，以最短的制绒时间来达到更低的腐蚀深度以及更低的反射率，即更好的表面“织构”。The manufacturing process of cells includes texturing, diffusion, etching, oxidation, coating, silk screen printing, sintering and other processes. In order to minimize the weight reduction of silicon wafers in the entire manufacturing process, texturing is the first process. Challenged by the technical challenge of silicon wafer thinning. Texturing is to produce a "texture" on the surface of the silicon wafer by alkali etching to improve the absorption rate of the silicon wafer to sunlight, thereby improving the efficiency of the cell. As we all know, the higher the battery efficiency, the better the power generation income, which prompts manufacturers to constantly seek better texturing additives to assist alkali etching in the wet texturing process, and achieve the goal with the shortest texturing time. Lower corrosion depth and lower reflectivity, ie better surface "texture".
在湿法制绒过程中，由于制绒添加剂受到硅片与碱的反应速率、绒面金字塔生长的速率以及化学品耗量的限制，因此硅片需要达到一定的腐蚀深度才能实现金字塔的完全生长或是绒面的最优化，现有制绒添加剂能够实现的较合适的绒面尺寸为1.5~3um，即使有些制绒添加剂在较短时间内可实现快速制绒，比如中国专利CN111501105A，但需要有一定量的腐蚀深度，低于这个腐蚀深度通常会出现金字塔生长不完全，致使绒面尺寸过小（小于1um）以及反射率偏高的问题。因而，需要开发出一种能在极低腐蚀深度条件下实现快速制绒，并且绒面尺寸合适、反射率低的制绒添加剂，为行业的发展助力。In the wet texturing process, since the texturing additives are limited by the reaction rate of the silicon wafer and alkali, the growth rate of the textured pyramid and the consumption of chemicals, the silicon wafer needs to reach a certain corrosion depth to achieve the complete growth of the pyramid or It is the optimization of the suede surface. The more suitable suede surface size that can be achieved by the existing texturing additives is 1.5~3um. Even if some texturing additives can achieve rapid texturing in a short period of time, such as the Chinese patent CN111501105A, it needs a Quantitative corrosion depth, lower than this corrosion depth usually results in incomplete pyramid growth, resulting in problems of too small suede size (less than 1um) and high reflectivity. Therefore, it is necessary to develop a texturing additive that can realize rapid texturing under extremely low corrosion depth conditions, and has a suitable texture size and low reflectivity, so as to help the development of the industry.
技术解决方案technical solution
本发明的目的在于提出一种用于快速制绒的制绒添加剂及应用，该制绒添加剂不仅能够缩短制绒时间，而且能够获得低腐蚀深度及低反射率的制绒片。The object of the present invention is to propose a kind of texturing additive and its application for rapid texturing, the texturing additive can not only shorten the texturing time, but also can obtain the texturing sheet with low corrosion depth and low reflectivity.
根据本发明的第一个方面，提供一种用于快速制绒的制绒添加剂，包括如下质量百分比含量的各组分：成核剂0.5%～10%，绒面催化剂1%～10%，表面活性剂0.01%～0.05%，脱泡剂0.05%～0.5%，余量为去离子水。According to a first aspect of the present invention, there is provided a kind of texturing additive for rapid texturing, comprising the following components in mass percent: 0.5% to 10% nucleating agent, 1% to 10% texturing catalyst, Surfactant 0.01% ~ 0.05%, defoaming agent 0.05% ~ 0.5%, the balance is deionized water.
优选的，所述成核剂选自水解聚丙烯腈钠盐、水解聚丙烯腈铵盐中的一种或两种。Preferably, the nucleating agent is selected from one or both of hydrolyzed polyacrylonitrile sodium salt and hydrolyzed polyacrylonitrile ammonium salt.
优选的，所述绒面催化剂为胆碱或氢氧化胆碱。Preferably, the suede catalyst is choline or choline hydroxide.
优选的，所述表面活性剂选自十二烷基硫酸钠、十四烷基硫酸钠、十六烷基硫酸钠、十二烷基苯磺酸钠、十四烷基苯磺酸钠、十六烷基苯磺酸钠中的一种或多种。Preferably, the surfactant is selected from sodium lauryl sulfate, sodium tetradecyl sulfate, sodium cetyl sulfate, sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, One or more of sodium hexaalkylbenzene sulfonates.
优选的，所述脱泡剂选自甲苯二胺聚醚多元醇。Preferably, the defoaming agent is selected from toluenediamine polyether polyols.
优选的，所述脱泡剂的粘度为1100～12000mPa•s。Preferably, the viscosity of the defoaming agent is 1100-12000 mPa·s.
根据本发明的第二个方面，提供一种快速制绒的制绒液，其含有碱溶液和上述制绒添加剂，制绒添加剂与碱溶液的质量比为0.5～2.5:100。According to the second aspect of the present invention, there is provided a rapid texturing liquid, which contains an alkaline solution and the above-mentioned texturing additive, and the mass ratio of the texturing additive to the alkaline solution is 0.5-2.5:100.
优选的，所述碱溶液为0.2～2wt%的氢氧化钠水溶液或氢氧化钾水溶液。Preferably, the alkaline solution is a 0.2-2wt% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
根据本发明的第三个方面，提供一种单晶硅片的快速制绒方法，利用上述制绒液对单晶硅片进行表面制绒。According to the third aspect of the present invention, there is provided a rapid texturing method for monocrystalline silicon wafers, using the above texturing liquid to texture the surface of monocrystalline silicon wafers.
优选的，上述单晶硅片的快速制绒方法，包括如下步骤：Preferably, the rapid texturing method of the above-mentioned monocrystalline silicon wafer comprises the following steps:
（1）配制制绒添加剂：将质量百分比含量为0.5%～10%的成核剂，1%-10%的绒面催化剂，0.01%～0.05%的表面活性剂，0.05%～0.5%的脱泡剂加入到余量的去离子水中，混合均匀配制成制绒添加剂；(1) Preparation of texture additives: 0.5% to 10% of nucleating agent, 1% to 10% of texture catalyst, 0.01% to 0.05% of surfactant, 0.05% to 0.5% of The foaming agent is added to the remaining amount of deionized water, and mixed evenly to prepare a texturing additive;
（2）配制制绒液：将步骤（1）配制成的制绒添加剂加入到碱溶液中，混合均匀配制成制绒液；制绒添加剂与碱溶液的质量比为0.5～2.5:100；(2) Prepare the texturing liquid: add the texturing additive formulated in step (1) into the alkaline solution, mix well to prepare the texturing liquid; the mass ratio of the texturing additive to the alkaline solution is 0.5-2.5:100;
（3）制绒：将单晶硅片浸入步骤（2）制得的制绒液中进行表面制绒，制绒温度为75～85℃，制绒时间为240～290s。(3) Texturing: immerse the monocrystalline silicon wafer in the texturing solution prepared in step (2) for surface texturing, the texturing temperature is 75-85°C, and the texturing time is 240-290s.
本发明的制绒添加剂，作为成核剂的水解聚丙烯腈钠盐和水解聚丙烯腈铵盐，由聚丙烯腈废料，经碱性水解而得到的阴离子聚合物，分子链上含有酰胺基、羧基和腈基等强极性基团，与硅片表面的Si-H键形成强氢键作用，可以很好地吸附在硅片表面，因而具有良好的出绒性能，可形成良好的出绒基底，但是出绒得到的金字塔绒面若要长大则需要较大的腐蚀深度，即使通过提高碱用量来提高反应速率，此时腐蚀深度和绒面尺寸还是难以平衡，也就是难以在较低的腐蚀深度下得到正常尺寸的金字塔绒面。为了解决这一问题，本发明的制绒添加剂中加入了绒面催化剂胆碱或氢氧化胆碱，其分子中含有活性的-OH，具有很强的碱性，并且带正电荷的N使得其在硅片表面具有很强的吸附性，从而与碱产生协同作用，促使OH -与硅片表面结合，加速制绒腐蚀反应速率，让反应在腐蚀深度较小时也可以使金字塔完全长大成型，而不是停留在金字塔密度高但是绒面很小的长大过程中，因此制绒后的硅片反射率更低。 The texturing additive of the present invention is hydrolyzed polyacrylonitrile sodium salt and hydrolyzed polyacrylonitrile ammonium salt as a nucleating agent, an anionic polymer obtained by alkaline hydrolysis of polyacrylonitrile waste, containing amide groups, Strong polar groups such as carboxyl and nitrile groups form strong hydrogen bonds with Si-H bonds on the surface of silicon wafers, which can be well adsorbed on the surface of silicon wafers, so they have good fleece performance and can form good fleece However, if the pyramid suede surface obtained from cashmere grows, it needs a larger corrosion depth. Even if the reaction rate is increased by increasing the amount of alkali, it is still difficult to balance the corrosion depth and the suede surface size at this time, that is, it is difficult to achieve a lower corrosion rate. The pyramid suede of normal size is obtained under the corrosion depth. In order to solve this problem, the texture additive of the present invention has added texture catalyst choline or choline hydroxide, which contains active -OH in its molecule, has very strong basicity, and the positively charged N makes it It has a strong adsorption on the surface of the silicon wafer, so it has a synergistic effect with the alkali, promotes the combination of OH- and the surface of the silicon wafer, accelerates the corrosion reaction rate of the texturing process, and allows the reaction to completely grow and form the pyramid when the corrosion depth is small. Rather than staying in the growth process with high pyramid density but small texture, the reflectivity of the silicon wafer after texture is lower.
本发明制绒添加剂中加入绒面催化剂胆碱或氢氧化胆碱后，硅片表面的气泡产生的更快，因此对气泡的脱除速率要求更高。本发明选用粘度为1100～12000mPa•s的甲苯二胺聚醚多元醇作为脱泡剂，具有很低的表面张力，促使硅片表面的气泡可以快速脱除。虽然脱泡剂本身具有很好的脱泡能力，而使得制绒后的硅片表面不会残留气泡印等基础外观问题，但是仍然会有均匀性不好的情况出现，尤其本发明腐蚀深度较低，硅片表面反应生成的气泡脱除快，下部分的气泡会对上部分的硅片表面产生影响，因而需要表面活性剂配合使用优化制绒外观。After the texture catalyst choline or choline hydroxide is added to the texture additive of the present invention, the air bubbles on the surface of the silicon wafer will be generated faster, so the requirement for the removal rate of the air bubbles is higher. The invention selects the toluene diamine polyether polyol with a viscosity of 1100-12000mPa·s as the defoaming agent, which has very low surface tension and promotes the rapid removal of the bubbles on the surface of the silicon chip. Although the defoamer itself has a good defoaming ability, so that the basic appearance problems such as air bubble marks will not remain on the surface of the silicon wafer after texturing, there will still be poor uniformity, especially in the present invention. Low, the bubbles generated by the reaction on the surface of the silicon wafer are removed quickly, and the bubbles in the lower part will affect the surface of the upper part of the silicon wafer, so surfactants are required to be used together to optimize the texture appearance.
本发明的表面活性剂选自十二烷基硫酸钠、十四烷基硫酸钠、十六烷基硫酸钠、十二烷基苯磺酸钠、十四烷基苯磺酸钠、十六烷基苯磺酸钠中的一种或多种，作为外观调和剂的同时也具有补充出绒的作用，这是由于十二烷基硫酸钠等中的硫酸基或十二烷基苯磺酸钠等中的磺酸基团具有一定的极性和吸附性，可与成核剂配合出绒，使制绒稳定性更好。而且少量表面活性剂吸附在硅片表面，促使成核剂更加均匀的分布，从而在高腐蚀速率下也能得到很好的外观。The surfactant of the present invention is selected from sodium lauryl sulfate, sodium tetradecyl sulfate, sodium cetyl sulfate, sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, hexadecane One or more of sodium dodecylbenzenesulfonate, as an appearance blending agent, also has the effect of supplementing cashmere, which is due to the sulfate group or sodium dodecylbenzenesulfonate in sodium dodecyl sulfate, etc. The sulfonic acid group in etc. has a certain polarity and adsorption, and can cooperate with nucleating agent to produce cashmere, so that the stability of cashmere production is better. Moreover, a small amount of surfactant is adsorbed on the surface of the silicon wafer, which promotes a more uniform distribution of the nucleating agent, so that a good appearance can be obtained even at a high corrosion rate.
有益效果Beneficial effect
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
（1）本发明的制绒添加剂能够实现制绒时间缩短至240s；(1) The texturing additive of the present invention can shorten the texturing time to 240s;
（2）与现有制绒添加剂的单面腐蚀深度2.5um相比，本发明制绒添加剂的单面腐蚀深度达1.5um时便可以实现金字塔的完全生长，可获得2um的绒面尺寸，并具有良好的降低反射率的效果。(2) Compared with the single-sided corrosion depth of 2.5um of the existing texturing additive, when the single-sided corrosion depth of the texturing additive of the present invention reaches 1.5um, the complete growth of the pyramid can be realized, and a suede surface size of 2um can be obtained, and It has a good effect of reducing reflectivity.
附图说明Description of drawings
图1是本发明实施例1获得的绒面形貌。Fig. 1 is the appearance of suede obtained in Example 1 of the present invention.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
下面结合附图和实施例对本发明的技术方案作进一步的说明。The technical solution of the present invention will be further described below in conjunction with the drawings and embodiments.
实施例1Example 1
按照质量百分比份数，将5份水解聚丙烯腈钠盐，2份胆碱，0.02份十二烷基硫酸钠，0.15份粘度为12000mPa•s的甲苯二胺聚醚多元醇和92.83份去离子水混合搅拌均匀配成制绒添加剂；再在制绒槽体中按照质量比0.7:1.2:100依次加入制绒添加剂、氢氧化钠和去离子水，搅拌均匀配成制绒液；然后放入硅片进行制绒，制绒温度80℃，反应时间240s。According to the parts by mass, 5 parts of hydrolyzed polyacrylonitrile sodium salt, 2 parts of choline, 0.02 part of sodium lauryl sulfate, 0.15 part of toluene diamine polyether polyol with a viscosity of 12000 mPa·s and 92.83 parts of deionized water Mix and stir evenly to make the texturing additive; then add the texturing additive, sodium hydroxide and deionized water in sequence in the texturing tank according to the mass ratio of 0.7:1.2:100, stir evenly to make the texturing liquid; then put silicon The sheet is made into texture at a temperature of 80°C and a reaction time of 240s.
实施例2Example 2
按照质量百分比份数，将5份水解聚丙烯腈钠盐，8份胆碱，0.02份十二烷基硫酸钠，0.4份粘度为3500mPa•s的甲苯二胺聚醚多元醇和86.58份去离子水混合搅拌均匀配成制绒添加剂；再在制绒槽体中按照质量比0.7:0.4:100依次加入制绒添加剂、氢氧化钠和去离子水，搅拌均匀配成制绒液；然后放入硅片进行制绒，制绒温度80℃，反应时间240s。According to the parts by mass, 5 parts of hydrolyzed polyacrylonitrile sodium salt, 8 parts of choline, 0.02 part of sodium lauryl sulfate, 0.4 part of toluene diamine polyether polyol with a viscosity of 3500 mPa·s and 86.58 parts of deionized water Mix and stir evenly to make the texturing additive; then add the texturing additive, sodium hydroxide and deionized water in sequence according to the mass ratio of 0.7:0.4:100 in the texturing tank, stir evenly to make the texturing liquid; then put silicon The sheet is made into texture at a temperature of 80°C and a reaction time of 240s.
实施例3Example 3
按照质量百分比份数，将2.5份水解聚丙烯腈钠盐，2.5份水解聚丙烯腈铵盐，8份胆碱，0.025份十二烷基硫酸钠，0.4份粘度为3500mPa•s的甲苯二胺聚醚多元醇和86.575份去离子水混合搅拌均匀配成制绒添加剂；再在制绒槽体中按照质量比0.7:0.3:100依次加入制绒添加剂、氢氧化钠和去离子水，搅拌均匀配成制绒液；然后放入硅片进行制绒，制绒温度80℃，反应时间270s。According to the parts by mass, 2.5 parts of hydrolyzed polyacrylonitrile sodium salt, 2.5 parts of hydrolyzed polyacrylonitrile ammonium salt, 8 parts of choline, 0.025 part of sodium lauryl sulfate, and 0.4 part of toluene diamine with a viscosity of 3500 mPa s Polyether polyol and 86.575 parts of deionized water were mixed and stirred evenly to prepare the texturing additive; then the texturing additive, sodium hydroxide and deionized water were sequentially added into the texturing tank according to the mass ratio of 0.7:0.3:100, and stirred evenly to prepare Texture-making liquid; then put into silicon wafers for texturing, the texturing temperature is 80°C, and the reaction time is 270s.
实施例4Example 4
按照质量百分比份数，将5份水解聚丙烯腈铵盐，2份胆碱，0.01份十二烷基硫酸钠，0.015份十二烷基苯磺酸钠，0.15份粘度为8000mPa•s的甲苯二胺聚醚多元醇和92.825份去离子水混合搅拌均匀配成制绒添加剂；再在制绒槽体中按照质量比0.7:1:100依次加入制绒添加剂、氢氧化钠和去离子水，搅拌均匀配成制绒液；然后放入硅片进行制绒，制绒温度80℃，反应时间290s。According to the parts by mass percentage, 5 parts of hydrolyzed polyacrylonitrile ammonium salt, 2 parts of choline, 0.01 part of sodium dodecylsulfate, 0.015 part of sodium dodecylbenzenesulfonate, and 0.15 part of toluene with a viscosity of 8000 mPa s Diamine polyether polyol and 92.825 parts of deionized water are mixed and stirred evenly to make the texturing additive; then add the texturing additive, sodium hydroxide and deionized water in the texturing tank according to the mass ratio of 0.7:1:100, and stir Evenly prepare the texturing solution; then put the silicon chip into the texturing, the texturing temperature is 80°C, and the reaction time is 290s.
对比例comparative example
在制绒槽体中按照质量比为0.7:1.2:100依次加入制绒添加剂（中国专利CN111501105A公开的制绒添加剂）、氢氧化钠和去离子水，搅拌均匀配成制绒液；然后放入硅片进行制绒，制绒温度80℃，反应时间300s。In the texturing tank body, according to the mass ratio of 0.7:1.2:100, add the texturing additive (the texturing additive disclosed in Chinese patent CN111501105A), sodium hydroxide and deionized water in sequence, stir evenly to make the texturing liquid; then put Texture the silicon wafers, the texturing temperature is 80°C, and the reaction time is 300s.
对实施例1-4及对比例所得的制绒片进行称重，计算腐蚀深度，并进行反射率测试，反射率测试仪采用NXT Helios-rc反射率测试仪，测试结果如表1所示。The textured sheets obtained in Examples 1-4 and Comparative Examples are weighed, the depth of corrosion is calculated, and the reflectivity test is carried out. The reflectivity tester adopts NXT Helios-rc reflectivity tester, the test results are shown in Table 1.
表1 实施例1-4及对比例的腐蚀深度及反射率Table 1 Corrosion depth and reflectivity of Examples 1-4 and comparative examples
组别group 单面腐蚀深度（um）Corrosion depth on one side (um) 反射率Reflectivity
实施例1Example 1 1.511.51 9.64%9.64%
实施例2Example 2 1.551.55 9.67%9.67%
实施例3Example 3 1.591.59 9.55%9.55%
实施例4Example 4 1.561.56 9.43%9.43%
对比例comparative example 2.502.50 9.00%9.00%
从表1可以看出，本发明的制绒添加剂可获得明显的低腐蚀深度，同时具有良好的降反效果。从图1可以看出，金字塔绒面已经完全长大成型，绒面尺寸在2um左右，未出现非常小的未成型绒面。It can be seen from Table 1 that the texturing additive of the present invention can obtain obviously low corrosion depth, and at the same time has a good reflection-reducing effect. It can be seen from Figure 1 that the pyramid suede has been fully grown and formed, and the suede size is about 2um, and there is no very small unformed suede.

Claims (10)

  1. 一种用于快速制绒的制绒添加剂，其特征在于，包括如下质量百分比含量的各组分：成核剂0.5%～10%，绒面催化剂1%～10%，表面活性剂0.01%～0.05%，脱泡剂0.05%～0.5%，余量为去离子水。A texturing additive for rapid texturing, characterized in that it comprises the following components in mass percent: 0.5% to 10% of nucleating agent, 1% to 10% of texturing catalyst, and 0.01% to 10% of surfactant 0.05%, defoaming agent 0.05% ~ 0.5%, the balance is deionized water.
  2. 根据权利要求1所述的用于快速制绒的制绒添加剂，其特征在于，所述成核剂选自水解聚丙烯腈钠盐、水解聚丙烯腈铵盐中的一种或两种。The texturing additive for rapid texturing according to claim 1, wherein the nucleating agent is selected from one or both of hydrolyzed polyacrylonitrile sodium salt and hydrolyzed polyacrylonitrile ammonium salt.
  3. 根据权利要求1或2所述的用于快速制绒的制绒添加剂，其特征在于，所述绒面催化剂为胆碱或氢氧化胆碱。The texturing additive for rapid texturing according to claim 1 or 2, characterized in that, the texturing catalyst is choline or choline hydroxide.
  4. 根据权利要求3所述的用于快速制绒的制绒添加剂，其特征在于，所述表面活性剂选自十二烷基硫酸钠、十四烷基硫酸钠、十六烷基硫酸钠、十二烷基苯磺酸钠、十四烷基苯磺酸钠、十六烷基苯磺酸钠中的一种或多种。The texturing additive for fast texturing according to claim 3, is characterized in that, described tensio-active agent is selected from sodium lauryl sulfate, sodium tetradecyl sulfate, sodium cetyl sulfate, cetyl sodium sulfate, One or more of sodium dialkylbenzenesulfonate, sodium tetradecylbenzenesulfonate, and sodium hexadecylbenzenesulfonate.
  5. 根据权利要求1或4所述的用于快速制绒的制绒添加剂，其特征在于，所述脱泡剂选自甲苯二胺聚醚多元醇。The texturing additive for fast texturing according to claim 1 or 4, characterized in that, the defoaming agent is selected from toluenediamine polyether polyols.
  6. 根据权利要求5所述的用于快速制绒的制绒添加剂，其特征在于，所述脱泡剂的粘度为1100～12000mPa•s。The texturing additive for rapid texturing according to claim 5, characterized in that the viscosity of the defoaming agent is 1100-12000 mPa•s.
  7. 一种快速制绒的制绒液，其特征在于，其含有碱溶液和权利要求1-6中任一项所述的制绒添加剂，制绒添加剂与碱溶液的质量比为0.5～2.5:100。A texturing liquid for rapid texturing, characterized in that it contains an alkali solution and the texturing additive described in any one of claims 1-6, and the mass ratio of the texturing additive to the alkaline solution is 0.5 to 2.5:100 .
  8. 根据权利要求7所述的快速制绒的制绒液，其特征在于，所述碱溶液为0.2～2wt%的氢氧化钠水溶液或氢氧化钾水溶液。The texturing solution for rapid texturing according to claim 7, characterized in that the alkaline solution is 0.2-2 wt% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
  9. 单晶硅片的快速制绒方法，其特征在于，利用权利要求7或8所述的制绒液对单晶硅片进行表面制绒。The rapid texturing method of monocrystalline silicon wafers is characterized in that the surface texturing of monocrystalline silicon wafers is carried out using the texturing liquid described in claim 7 or 8.
  10. 根据权利要求9所述的单晶硅片的快速制绒方法，其特征在于，包括如下步骤：The rapid texturing method of monocrystalline silicon wafer according to claim 9, is characterized in that, comprises the steps:
    （1）配制制绒添加剂：将质量百分比含量为0.5%～10%的成核剂，1%-10%的绒面催化剂，0.01%～0.05%的表面活性剂，0.05%～0.5%的脱泡剂加入到余量的去离子水中，混合均匀配制成制绒添加剂；(1) Preparation of texture additives: 0.5% to 10% of nucleating agent, 1% to 10% of texture catalyst, 0.01% to 0.05% of surfactant, 0.05% to 0.5% of The foaming agent is added to the remaining amount of deionized water, and mixed evenly to prepare a texturing additive;
    （2）配制制绒液：将步骤（1）配制成的制绒添加剂加入到碱溶液中，混合均匀配制成制绒液；制绒添加剂与碱溶液的质量比为0.5～2.5:100；(2) Prepare the texturing liquid: add the texturing additive formulated in step (1) into the alkaline solution, mix well to prepare the texturing liquid; the mass ratio of the texturing additive to the alkaline solution is 0.5-2.5:100;
    （3）制绒：将单晶硅片浸入步骤（2）制得的制绒液中进行表面制绒，制绒温度为75～85℃，制绒时间为240～290s。(3) Texturing: immerse the monocrystalline silicon wafer in the texturing solution prepared in step (2) for surface texturing, the texturing temperature is 75-85°C, and the texturing time is 240-290s.
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CN104659156A (en) * 2015-03-03 2015-05-27 中节能太阳能科技（镇江）有限公司 Etching method of single crystalline silicon solar cell
CN112144122A (en) * 2020-10-21 2020-12-29 常州时创能源股份有限公司 Texturing additive and texturing liquid suitable for large-size monocrystalline silicon wafers and application
CN113668066A (en) * 2021-08-19 2021-11-19 常州时创能源股份有限公司 Texturing additive for rapid texturing and application

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