WO2010025624A1 - Rinse solution for removal of plasm etching residues - Google Patents

Rinse solution for removal of plasm etching residues Download PDF

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Publication number
WO2010025624A1
WO2010025624A1 PCT/CN2009/001001 CN2009001001W WO2010025624A1 WO 2010025624 A1 WO2010025624 A1 WO 2010025624A1 CN 2009001001 W CN2009001001 W CN 2009001001W WO 2010025624 A1 WO2010025624 A1 WO 2010025624A1
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WO
WIPO (PCT)
Prior art keywords
cleaning solution
plasma etching
residue cleaning
etching residue
solution according
Prior art date
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PCT/CN2009/001001
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French (fr)
Chinese (zh)
Inventor
刘兵
彭洪修
于昊
Original Assignee
安集微电子科技(上海)有限公司
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Publication of WO2010025624A1 publication Critical patent/WO2010025624A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds

Definitions

  • the present invention relates to a cleaning liquid in a semiconductor manufacturing process, and in particular to a plasma etching residue cleaning liquid.
  • the application, exposure and imaging of the photoresist layer is a necessary process step for the pattern fabrication of the components.
  • the residue of the photoresist layer material needs to be completely removed before the next process step (i.e., after coating, imaging, ion implantation, and etching of the photoresist layer). Ion bombardment in the doping step hardens the photoresist layer polymer, thus making the photoresist layer less soluble and more difficult to remove.
  • this layer of photoresist film has been removed using a two-step process (dry ashing and wet etching).
  • the first step uses dry ashing to remove most of the photoresist layer (PR); the second step uses a plasma etch residue cleaning solution to perform the cleaning process to remove the remaining photoresist layer, the steps of which are generally preceded by plasma etching.
  • the etch residue cleaning solution is rinsed, then rinsed with solvent or deionized water, and finally rinsed with deionized water. In this process, only the residual photoresist layer polymer and inorganic matter can be removed, and the damage to the metal layer such as the aluminum layer cannot be attacked.
  • Typical plasma etching residue cleaning solutions in the prior art are as follows: amine cleaning solution, semi-aqueous amine based (non-hydroxylamine) cleaning solution and fluoride cleaning solution.
  • the first two types of cleaning fluids need to be cleaned at high temperatures, generally between 60 ° C and 80 ° C. These cleaning fluids are currently developed mainly by EKC and ACT, and occupy a large market.
  • Typical patents are US6319885, US5672577, US6030932 US6825156 and US5419779.
  • the metal aluminum has a high corrosion rate during washing, and is often rinsed with a solvent after cleaning the plasma etching residue.
  • the solvents used were mainly isopropanol and N-methylpyrrolidone.
  • the former is gradually eliminated in some semiconductor manufacturing companies due to its low flash point and volatility.
  • the latter has been used in many semiconductor manufacturing companies because of its high flash point and low volatilization.
  • the cleaning solution composition disclosed in US 6,828,289 comprises: an acidic buffer, an organic polar solvent, a fluorine-containing substance and water, and having a pH between 3 and 7, wherein the acidic buffer is composed of an organic carboxylic acid or a polybasic acid.
  • the corresponding ammonium salt composition has a composition ratio of between 10:1 and 1:10.
  • Fluorine-containing cleaning fluids are disclosed, for example, in US Pat.
  • a cleaning composition for a fluorine-containing substance which comprises a fluorine-containing substance, an inorganic or organic acid, a quaternary ammonium salt and an organic polar solvent, having a pH of from 7 to 11, is disclosed in US Pat. No. 5,972,862, the disclosure of which is problem.
  • the technical problem to be solved by the present invention is to overcome the conventional plasma etching residue cleaning
  • the temperature required for liquid cleaning is high. It needs to be rinsed with solvent after cleaning.
  • the metal etching rate is higher when rinsed with deionized water, the cleaning operation window is smaller, and the viscosity and surface tension of the cleaning solution are large. It can effectively remove the photoresist residue after plasma etching, and can effectively inhibit the corrosion of metal (especially aluminum) and non-metal, and has a large plasma cleaning residue cleaning liquid for cleaning and rinsing operation window.
  • the plasma etch residue cleaning solution of the present invention comprises a solvent, water, and fluoride, which further contains a star polymer containing a pigment affinity group.
  • the mass fraction of the star polymer containing the pigment-affinity group is preferably
  • the mass fraction of the solvent is preferably 20% ⁇ 85%; the mass fraction of water is preferably 10% ⁇ 70%;
  • the mass fraction of the fluoride is preferably from 0.1% to 30%.
  • the pigment affinity group refers to a group containing one or more elements of oxygen, nitrogen and sulfur, preferably a hydroxyl group, an amino group or a carboxyl group; It refers to a polymer that connects three or more molecular chains in a radial form centering on a symmetrical center in a molecule.
  • the type of the pigment affinity group contained in the star polymer containing the pigment-affinity group may be one or more kinds.
  • the star polymer containing the pigment-affinity group may be a homopolymer or a copolymer.
  • the polymerizable monomer forming the polymer preferably includes one or more of the following: an acrylic monomer containing a pigment affinity group, an acrylate monomer containing a pigment affinity group, and a pigment-containing affinity.
  • the pigment affinity group is preferably a hydroxyl group, an amino group or a carboxyl group.
  • the acrylic monomer is preferably acrylic acid or methacrylic acid; and the acrylate monomer is preferably methyl acrylate, methyl methacrylate, ethyl acrylate or ethyl methacrylate.
  • the acrylamide monomer is preferably acrylamide or methyl Acrylamide.
  • the monomer in the star polymer forming the pigment-containing affinity group may further contain He does not contain polymeric monomers of the pigment affinity group, such as other vinyl monomers, preferably ethylene, propylene or styrene.
  • the vinyl monomer means a polymerizable monomer containing a vinyl unit.
  • preferred star polymers containing pigment-affinity groups are polyacrylic acid star homopolymers, binary star copolymers of styrene and hydroxyethyl acrylate, methyl acrylate and hydroxyethyl acrylate.
  • the number average molecular weight of the star polymer containing the pigment-affinity group is preferably
  • the solvent is a conventional solvent in the plasma etching residue cleaning liquid, preferably selected from the group consisting of sulfoxide, sulfone, imidazolium, pyrrolidone, imidazolidinone, alcohol, ether and amide. One or more of them.
  • the sulfoxide is preferably -C 4 sulfoxide and/or C 7 -C 1Q aryl sulfoxide, more preferably dimethyl sulfoxide; and the sulfone is preferably C C4 Sulfone and/or C 7 -C 1Q aryl sulfone, more preferably sulfolane; said imidazolium ketone is preferably 1,3-dimethyl-2-imidazolium; said pyrrolidone is preferably N-methylpyrrolidone and/or hydroxyethylpyrrolidone; the imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone (DMI); Preferred are -C 4 mercapto alcohol and/or C 7 -C 1Q aryl alcohol, more preferably propylene glycol and/or diethylene glycol; and the ether is preferably C 3 -C 2 .
  • the fluoride of the present invention is a fluoride commonly used in fluorine-containing cleaning liquids of the art. Preferred are one or more of hydrogen fluoride, fluorosilicic acid, ammonium fluorosilicate, fluoroboric acid, ammonium fluoroborate and a salt of hydrogen fluoride and a base, preferably aqueous ammonia, quaternary ammonium hydroxide or Alcoholamine.
  • the salt formed by the hydrogen fluoride and the base is more preferably ammonium hydrogen fluoride (NH 4 HF 2 ), ammonium tetramethylammonium fluoride (N(C 3 ⁇ 4) 4 F) and trishydroxyethyl ammonium fluoride (N (CH) One or more of 2 OH) 3 HF).
  • the cleaning solution of the present invention can be pH adjusted using a pH adjusting agent conventional in the art.
  • a pH adjusting agent conventional in the art.
  • this invention preferred are organic acids, bases or salts thereof which are commonly used for pH adjustment in the art.
  • the organic acid is preferably one or more of acetic acid, lactic acid, oxalic acid, citric acid and iminodiacetic acid
  • the base is preferably ammonia water, organic hydroxide, alcohol amine and One or more of the organic amines
  • the salt is preferably one of ammonium acetate, ammonium citrate, hydroxylamine sulfate, tetramethylammonium acetate, and tetramethylammonium citrate.
  • the organic hydroxide is preferably tetramethylammonium hydroxide and/or trimethylethylammonium hydroxide; and the alcoholamine is preferably hydroxylamine, ethanolamine, isopropanolamine, N One or more of N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine; the organic amine is preferably ethylamine, diethylamine, triethylamine, pentamethyldiethylene One or more of a triamine and a polyethene polyamine.
  • the content of the pH adjusting agent is preferably ⁇ 30% by mass.
  • the cleaning solution of the present invention may also contain other conventional additives in the art, such as corrosion inhibitors of metallic copper (e.g., benzotriazole).
  • corrosion inhibitors of metallic copper e.g., benzotriazole
  • the content of the additive is preferably ⁇ 10% by mass.
  • the star polymer having a pigment-affinity group in the present invention can effectively inhibit the corrosion of a metal (especially aluminum), and therefore it can also be used in the preparation of other plasma etching residue cleaning liquids.
  • the starting materials and reagents used in the present invention are commercially available.
  • the cleaning liquid of the present invention can be obtained by simply and uniformly mixing the above components.
  • the cleaning liquid of the present invention is used in the following manner: after removing the etching residue on the wafer by the plasma etching residue cleaning liquid of the present invention, it is directly rinsed with deionized water and then dried.
  • the cleaning liquid of the invention can effectively remove the photoresist residue, and at the same time, the corrosion rate of the metal (especially aluminum) and the non-metal is small, and the general fluorine cleaning liquid can not effectively control the corrosion rate of the metal and the non-metal at the same time. problem.
  • the cleaning solution can be directly rinsed with water after cleaning the photoresist residue, and the metal corrosion rate is small when rinsing in water, which increases the operation window of wafer rinsing.
  • Table 1 shows Examples 1 to 28, and the components of each of the examples were simply mixed to obtain a plasma etching residue cleaning solution. Among them, Mn is a number average molecular weight. Table 1 Plasma etching residue cleaning solution Example 1 ⁇ 28
  • Mn 800 10 styrene and propene N, N-dimethyl enoate dimethyl ester
  • Table 2 shows the cleaning liquids 29 to 44 and the comparative cleaning liquids 1 to 2. According to the formula in the table, the components are simply mixed to prepare each cleaning liquid. Among them, Mn is a number average molecular weight. Table 2 comparison of the cleaning solution 29 ⁇ 44 and the comparison cleaning solution 1 ⁇ 2
  • NMP N-methylpyrrolidone
  • DMAC dimethylacetamide
  • AcNH 4 ammonium acetate
  • Ac acetic acid
  • BTA benzotriazole
  • the cleaning solution can effectively remove photoresist residues, and the corrosion rate of the contacted metal and non-metal is less than 2 A/min.
  • the corrosion rate of Comparative Example 1 was larger (3.09 A/min) without adding any polymer, and 0.1% of linear polyacrylic acid was added to Comparative Example 2, which was favorable for the corrosion rate of aluminum metal.
  • the reduction was (1.88 A/min), and the cleaning solution 29 was added to the same 0.1% star polyacrylic acid, and the metal aluminum had a lower corrosion rate (1.52 A/min).
  • the solvent was replaced by dimethylacetamide instead of N-methylpyrrolidone, and the corrosion rate of the metal aluminum was still low (1.45 A/min). It shows that the corrosion inhibition efficiency of the star polymer is not selective to the solvent, and the corrosion resistance to the metal aluminum is maintained.
  • Table 4 lists the changes in the corrosion rate of the metal aluminum during the rinsing process of the conventional hydroxylamine cleaning solution, the fluorine-containing cleaning solution, and the cleaning solution 44.
  • the percentage is the mass percentage.
  • Table 5 selected some cleaning solution formulations to clean three wafers (metal wire, metal; channel, Via; metal pad, Pad). It was found through experiments that these formulations can effectively remove the photoresist. Residues without significant corrosion to metals and non-metals.
  • the cleaning liquid of the invention can effectively remove the photoresist residue, and can effectively inhibit the corrosion of the metal (especially aluminum), and the corrosion rate to the non-metal is small, effectively improving the general fluorine type.
  • the cleaning solution cannot simultaneously control the corrosion rate of metal and non-metal;
  • the cleaning solution of the present invention has a small metal corrosion rate when rinsing in water after cleaning the photoresist residue, and increases the operation window of the wafer rinsing.

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Abstract

A rinse solution for removal of plasm etching residues includes solvent，water and fluoride. The rinse solution also includes a kind of stelliform polymer with pigment affinity group. The rinse solution can be used to remove plasm etching residues. And the corrosion rate of the rinse solution to some metals especially such as Al and to some non-metals is low. The rinse solution has larger operation window.

Description

一种等离子刻蚀残留物清洗液  Plasma etching residue cleaning solution
技术领域 Technical field
本发明涉及一种半导体制造工艺中的清洗液， 具体的涉及一种等离子刻 蚀残留物清洗液。 技术背景  The present invention relates to a cleaning liquid in a semiconductor manufacturing process, and in particular to a plasma etching residue cleaning liquid. technical background
在半导体元器件制造过程中， 光阻层的涂敷、 曝光和成像对元器件的图 案制造来说是必要的工艺步骤。在图案化的最后（即在光阻层的涂敷、成像、 离子植入和蚀刻之后）进行下一工艺步骤之前， 光阻层材料的残留物需彻底 除去。在掺杂步骤中离子轰击会硬化光阻层聚合物， 因此使得光阻层变得不 易溶解从而更难于除去。 至今在半导体制造工业中一般使用两步法（干法灰 化和湿蚀刻）除去这层光阻层膜。第一步利用干法灰化除去光阻层（PR)的 大部分； 第二步利用等离子刻蚀残留物清洗液进行清洗工艺， 以除去剩余的 光阻层， 其步骤一般为先甩等离子刻蚀残留物清洗液清洗， 然后用溶剂或去 离子水漂洗， 最后再用去离子水漂洗。 在这个过程中只能除去残留的光阻层 聚合物和无机物， 而不能攻击损害金属层如铝层。  In the fabrication of semiconductor components, the application, exposure and imaging of the photoresist layer is a necessary process step for the pattern fabrication of the components. The residue of the photoresist layer material needs to be completely removed before the next process step (i.e., after coating, imaging, ion implantation, and etching of the photoresist layer). Ion bombardment in the doping step hardens the photoresist layer polymer, thus making the photoresist layer less soluble and more difficult to remove. Up to now, in the semiconductor manufacturing industry, this layer of photoresist film has been removed using a two-step process (dry ashing and wet etching). The first step uses dry ashing to remove most of the photoresist layer (PR); the second step uses a plasma etch residue cleaning solution to perform the cleaning process to remove the remaining photoresist layer, the steps of which are generally preceded by plasma etching. The etch residue cleaning solution is rinsed, then rinsed with solvent or deionized water, and finally rinsed with deionized water. In this process, only the residual photoresist layer polymer and inorganic matter can be removed, and the damage to the metal layer such as the aluminum layer cannot be attacked.
现有技术中典型的等离子刻蚀残留物清洗液有以下几种： 胺类清洗液， 半水性胺基（非羟胺类）清洗液以及氟化物类清洗液。 其中前两类清洗液需 要在高温下清洗， 一般在 60°C到 80°C之间， 这类清洗液目前主要是有 EKC和 ACT两家公司开发， 并占有较大的市场。 其典型的专利有 US6319885、 US5672577、 US6030932 US6825156和 US5419779等。 经过不断改进， 其 溶液本身对金属铝的腐蚀速率己经大幅降低，但该类清洗液由于其在水中漂 洗时金属铝的腐蚀速率较高， 在清洗完等离子蚀刻残留物后， 常采用溶剂漂 洗。 所用的溶剂主要有异丙醇和 N-甲基吡咯烷酮。 前者由于闪点比较低、 易 挥发， 在一些半导体制造公司已经逐步被淘汰； 而后者虽然闪点比较高、 不 易挥发， 很多半导体制造公司一直在使用； 但是随着环保意识增强和成本压 力加大，越来越多的公司希望能用去离子水直接漂洗，而不造成金属的腐蚀。 而现存的氟化物类清洗液虽然能在较低的温度 （室温到 50°C ) 下进行清洗， 然后用去离子水漂洗， 但仍然存在着各种各样的缺点， 例如不能同时控制金 属和非金属基材的腐蚀， 清洗后容易造成通道特征尺寸的改变， 从而改变半 导体结构； 另一方面由于其漂洗时较大的金属蚀刻速率， 清洗操作窗口比较 小等。 US 6, 828,289公开的清洗液组合物包括： 酸性缓冲液、 有机极性溶剂、 含氟物质和水，且 pH值在 3〜7之间，其中的酸性缓冲液由有机羧酸或多元酸 与所对应的铵盐组成， 组成比例为 10: 1至 1 : 10之间。 如 US 5， 698, 503公 开了含氟清洗液， 但大量使用乙二醇， 其清洗液的粘度与表面张力都很大， 从而影响清洗效果。 如 US 5,972,862公开了含氟物质的清洗组合物， 其包括 含氟物质、 无机或有机酸、 季铵盐和有机极性溶剂， pH为 7〜11， 由于其清 洗效果不是很稳定， 存在多样的问题。 Typical plasma etching residue cleaning solutions in the prior art are as follows: amine cleaning solution, semi-aqueous amine based (non-hydroxylamine) cleaning solution and fluoride cleaning solution. The first two types of cleaning fluids need to be cleaned at high temperatures, generally between 60 ° C and 80 ° C. These cleaning fluids are currently developed mainly by EKC and ACT, and occupy a large market. Typical patents are US6319885, US5672577, US6030932 US6825156 and US5419779. After continuous improvement, the corrosion rate of the solution itself to the metal aluminum has been greatly reduced, but the cleaning liquid is bleached in the water due to its The metal aluminum has a high corrosion rate during washing, and is often rinsed with a solvent after cleaning the plasma etching residue. The solvents used were mainly isopropanol and N-methylpyrrolidone. The former is gradually eliminated in some semiconductor manufacturing companies due to its low flash point and volatility. The latter has been used in many semiconductor manufacturing companies because of its high flash point and low volatilization. However, as environmental awareness increases and cost pressures increase More and more companies hope to rinse directly with deionized water without causing corrosion of the metal. While existing fluoride-based cleaning solutions can be cleaned at lower temperatures (room temperature to 50 ° C) and then rinsed with deionized water, there are still various disadvantages such as the inability to simultaneously control metals and The corrosion of the non-metallic substrate is likely to cause a change in the feature size of the channel after cleaning, thereby changing the semiconductor structure; on the other hand, the cleaning operation window is relatively small due to the large metal etching rate during rinsing. The cleaning solution composition disclosed in US 6,828,289 comprises: an acidic buffer, an organic polar solvent, a fluorine-containing substance and water, and having a pH between 3 and 7, wherein the acidic buffer is composed of an organic carboxylic acid or a polybasic acid. The corresponding ammonium salt composition has a composition ratio of between 10:1 and 1:10. Fluorine-containing cleaning fluids are disclosed, for example, in US Pat. A cleaning composition for a fluorine-containing substance, which comprises a fluorine-containing substance, an inorganic or organic acid, a quaternary ammonium salt and an organic polar solvent, having a pH of from 7 to 11, is disclosed in US Pat. No. 5,972,862, the disclosure of which is problem.
因此尽管已经揭示了一些清洗液组合物，但还是需要而且近来更加需要 制备一类更合适的清洗组合物或体系， 适应新的清洗要求， 比如环境更为友 善、 低缺陷水平、 低刻蚀率以及较大操作窗口。 发明概要  Thus, although some cleaning fluid compositions have been disclosed, there is a need and a greater need to prepare a more suitable cleaning composition or system to accommodate new cleaning requirements, such as a more environmentally friendly, low defect level, low etch rate. And a larger operating window. Summary of invention
本发明所要解决的技术问题是为了克服传统的等离子刻蚀残留物清洗 液清洗所需温度较高， 清洗完后需要用溶剂漂洗， 用去离子水漂洗时金属蚀 刻速率较高， 清洗操作窗口较小， 清洗液的粘度和表面张力较大的缺陷而提 供了一种可以有效去除等离子刻蚀后的光阻残留物， 同时可以高效的抑制金 属 （尤其是铝）和非金属的腐蚀， 有较大的清洗和漂洗的操作窗口的等离子 刻蚀残留物清洗液。 本发明的等离子刻蚀残留物清洗液包含溶剂、水和氟化物，其还含有含 颜料亲和基团的星形聚合物。 The technical problem to be solved by the present invention is to overcome the conventional plasma etching residue cleaning The temperature required for liquid cleaning is high. It needs to be rinsed with solvent after cleaning. The metal etching rate is higher when rinsed with deionized water, the cleaning operation window is smaller, and the viscosity and surface tension of the cleaning solution are large. It can effectively remove the photoresist residue after plasma etching, and can effectively inhibit the corrosion of metal (especially aluminum) and non-metal, and has a large plasma cleaning residue cleaning liquid for cleaning and rinsing operation window. The plasma etch residue cleaning solution of the present invention comprises a solvent, water, and fluoride, which further contains a star polymer containing a pigment affinity group.
其中， 所述的含颜料亲和基团的星形聚合物的质量分数较佳的为 Wherein, the mass fraction of the star polymer containing the pigment-affinity group is preferably
0.001%〜3%， 更佳的为 0.001%〜1%； 所述的溶剂的质量分数较佳的为 20%〜85%； 所述的水的质量分数较佳的为 10%~70%； 所述的氟化物的质量 分数较佳的为 0.1%〜30%。 0.001%〜3%, more preferably 0.001%~1%; the mass fraction of the solvent is preferably 20%~85%; the mass fraction of water is preferably 10%~70%; The mass fraction of the fluoride is preferably from 0.1% to 30%.
• 本发明中， 所述的颜料亲和基团是指含有氧、 氮和硫中的一种或多种元 素的基团， 较佳的为羟基、 氨基或羧基； 所述的星形聚合物是指以分子中一 个对称中心为中心， 以放射形式联接三条或三条以上分子链的聚合物。所述 的含颜料亲和基团的星形聚合物中所含的颜料亲和基团的种类可为一种或 多种。  In the present invention, the pigment affinity group refers to a group containing one or more elements of oxygen, nitrogen and sulfur, preferably a hydroxyl group, an amino group or a carboxyl group; It refers to a polymer that connects three or more molecular chains in a radial form centering on a symmetrical center in a molecule. The type of the pigment affinity group contained in the star polymer containing the pigment-affinity group may be one or more kinds.
所述的含颜料亲和基团的星形聚合物可为均聚物或共聚物。形成该聚合 物的聚合单体较佳的包括下列中的一种或多种：含颜料亲和基团的丙烯酸类 单体、含颜料亲和基团的丙烯酸酯类单体和含颜料亲和基团的丙烯酰胺类单 体。 所述的颜料亲和基团较佳的为羟基、 氨基或羧基。 其中， 所述的丙烯酸 类单体较佳的为丙烯酸或甲基丙烯酸；所述的丙烯酸酯类单体较佳的为丙烯 酸甲酯、 甲基丙烯酸甲酯、 丙烯酸乙酯、 甲基丙烯酸乙酯、 丙烯酸丙酯、 甲 基丙烯酸丙酯、 丙烯酸丁酯、 甲基丙烯酸丁酯、 丙烯酸羟乙酯或甲基丙烯酸 羟乙酯； 所述的丙烯酰胺类单体较佳的为丙烯酰胺或甲基丙烯酰胺。  The star polymer containing the pigment-affinity group may be a homopolymer or a copolymer. The polymerizable monomer forming the polymer preferably includes one or more of the following: an acrylic monomer containing a pigment affinity group, an acrylate monomer containing a pigment affinity group, and a pigment-containing affinity. A group of acrylamide monomers. The pigment affinity group is preferably a hydroxyl group, an amino group or a carboxyl group. Wherein, the acrylic monomer is preferably acrylic acid or methacrylic acid; and the acrylate monomer is preferably methyl acrylate, methyl methacrylate, ethyl acrylate or ethyl methacrylate. , propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate; the acrylamide monomer is preferably acrylamide or methyl Acrylamide.
较佳的，形成上述含颜料亲和基团的星形聚合物中的单体还可以含有其 他不含颜料亲和基团的聚合单体， 如其他乙烯基类单体， 优选乙烯、 丙烯或 苯乙烯。 本发明中， 所述的乙烯基单体是指含乙烯基单元的聚合单体。 Preferably, the monomer in the star polymer forming the pigment-containing affinity group may further contain He does not contain polymeric monomers of the pigment affinity group, such as other vinyl monomers, preferably ethylene, propylene or styrene. In the present invention, the vinyl monomer means a polymerizable monomer containing a vinyl unit.
本发明中， 优选的含颜料亲和基团的星形聚合物为聚丙烯酸星形均聚 物， 苯乙烯与丙烯酸羟乙酯的二元星形共聚物， 丙烯酸甲酯与丙烯酸羟乙酯 的二元星形共聚物，丙烯酸与丙烯酸羟乙酯的二元星形共聚物，以及丙烯酸、 丙烯酸丁酯和丙烯酰胺的三元星形共聚物中的一种或多种。  In the present invention, preferred star polymers containing pigment-affinity groups are polyacrylic acid star homopolymers, binary star copolymers of styrene and hydroxyethyl acrylate, methyl acrylate and hydroxyethyl acrylate. A binary star copolymer, a binary star copolymer of acrylic acid and hydroxyethyl acrylate, and one or more of a ternary star copolymer of acrylic acid, butyl acrylate and acrylamide.
本发明中，所述的含颜料亲和基团的星形聚合物的数均分子量较佳的为 In the present invention, the number average molecular weight of the star polymer containing the pigment-affinity group is preferably
800-50000, 更佳的为 800-10000。 本发明中， 所述的溶剂为本领域等离子刻蚀残留物清洗液中常规的溶 剂， 较佳的选自亚砜、 砜、 咪唑垸酮、 吡咯垸酮、 咪唑啉酮、 醇、 醚和酰胺 中的一种或多种。其中， 所述的亚砜较佳的为 -C4亚砜和 /或 C7-C1Q的芳基 亚砜， 更佳的为二甲基亚砜； 所述的砜较佳的为 C C4砜和 /或 C7-C1Q的芳基 砜， 更佳的为环丁砜； 所述的咪唑垸酮较佳的为 1， 3-二甲基 -2-咪唑垸酮； 所述的吡咯烷酮较佳的为 N-甲基吡咯垸酮和 /或羟乙基吡咯垸酮； 所述的咪 唑啉酮较佳的为 1， 3-二甲基 -2-咪唑啉酮 （DMI); 所述的醇较佳的为 -C4 垸基醇和 /或 C7-C1Q的芳基醇， 更佳的为丙二醇和 /或二乙二醇； 所述的醚较 佳的为 C3-C2。的醚， 更佳的为丙二醇单甲醚和 /或二丙二醇单甲醚； 所述的 酰胺较佳的为 CrC6垸基酰胺， 更佳的为二甲基甲酰胺和 /或二甲基乙酰胺。 本发明所述的氟化物为本领域含氟类清洗液中常用的氟化物。较佳的为 氟化氢、 氟硅酸、 氟硅酸铵、 氟硼酸、 氟硼酸铵和氟化氢与碱形成的盐中的 一种或多种， 该碱较佳的为氨水、 季胺氢氧化物或醇胺。 其中， 所述的氟化 氢与碱形成的盐更佳的为氟化氢铵 （NH4HF2) 、 四甲基氟化铵 （N(C¾)4F) 和三羟乙基氟化铵 （N(CH2OH)3HF) 中的一种或多种。 800-50000, more preferably 800-10000. In the present invention, the solvent is a conventional solvent in the plasma etching residue cleaning liquid, preferably selected from the group consisting of sulfoxide, sulfone, imidazolium, pyrrolidone, imidazolidinone, alcohol, ether and amide. One or more of them. Wherein, the sulfoxide is preferably -C 4 sulfoxide and/or C 7 -C 1Q aryl sulfoxide, more preferably dimethyl sulfoxide; and the sulfone is preferably C C4 Sulfone and/or C 7 -C 1Q aryl sulfone, more preferably sulfolane; said imidazolium ketone is preferably 1,3-dimethyl-2-imidazolium; said pyrrolidone is preferably N-methylpyrrolidone and/or hydroxyethylpyrrolidone; the imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone (DMI); Preferred are -C 4 mercapto alcohol and/or C 7 -C 1Q aryl alcohol, more preferably propylene glycol and/or diethylene glycol; and the ether is preferably C 3 -C 2 . More preferably, it is propylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether; the amide is preferably C r C 6 mercapto amide, more preferably dimethylformamide and/or dimethyl Acetamide. The fluoride of the present invention is a fluoride commonly used in fluorine-containing cleaning liquids of the art. Preferred are one or more of hydrogen fluoride, fluorosilicic acid, ammonium fluorosilicate, fluoroboric acid, ammonium fluoroborate and a salt of hydrogen fluoride and a base, preferably aqueous ammonia, quaternary ammonium hydroxide or Alcoholamine. Wherein the salt formed by the hydrogen fluoride and the base is more preferably ammonium hydrogen fluoride (NH 4 HF 2 ), ammonium tetramethylammonium fluoride (N(C 3⁄4) 4 F) and trishydroxyethyl ammonium fluoride (N (CH) One or more of 2 OH) 3 HF).
本发明的清洗液可采用本领域常规的 pH调节剂进行 pH调节。 本发明 中， 较佳的为本领域调节 pH常用的有机酸、 碱或它们的盐。 其中， 所述的 有机酸较佳的为乙酸、乳酸、草酸、柠檬酸和亚氨基二乙酸中的一种或多种； 所述的碱较佳的为氨水、 有机氢氧化物、 醇胺和有机胺中的一种或多种； 所 述的盐较佳的为乙酸铵、 柠檬酸铵、羟胺硫酸盐、 乙酸四甲基铵盐和柠檬酸 四甲基铵盐中的一种多种。 其中，所述的有机氢氧化物较佳的为四甲基氢氧化铵和 /或三甲基乙基氢 氧化铵； 所述的醇胺较佳的为羟胺、 乙醇胺、 异丙醇胺、 N， N-二甲基乙醇 胺、 N-甲基二乙醇胺和三乙醇胺中的一种或多种； 所述的有机胺较佳的为乙 胺、 二乙胺、 三乙胺、 五甲基二乙烯三胺和多乙烯多胺中的一种或多种。所 述的 pH调节剂的含量较佳的为质量分数≤30%。 The cleaning solution of the present invention can be pH adjusted using a pH adjusting agent conventional in the art. this invention Among them, preferred are organic acids, bases or salts thereof which are commonly used for pH adjustment in the art. Wherein, the organic acid is preferably one or more of acetic acid, lactic acid, oxalic acid, citric acid and iminodiacetic acid; and the base is preferably ammonia water, organic hydroxide, alcohol amine and One or more of the organic amines; the salt is preferably one of ammonium acetate, ammonium citrate, hydroxylamine sulfate, tetramethylammonium acetate, and tetramethylammonium citrate. Wherein, the organic hydroxide is preferably tetramethylammonium hydroxide and/or trimethylethylammonium hydroxide; and the alcoholamine is preferably hydroxylamine, ethanolamine, isopropanolamine, N One or more of N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine; the organic amine is preferably ethylamine, diethylamine, triethylamine, pentamethyldiethylene One or more of a triamine and a polyethene polyamine. The content of the pH adjusting agent is preferably ≤ 30% by mass.
本发明的清洗液还可含有其他本领域的常规添加剂，如金属铜的腐蚀抑 制剂 （如苯并三氮唑）。 添加剂的含量较佳的为质量分数≤10%。  The cleaning solution of the present invention may also contain other conventional additives in the art, such as corrosion inhibitors of metallic copper (e.g., benzotriazole). The content of the additive is preferably ≤10% by mass.
本发明中的含颜料亲和基团的星形聚合物可以高效的抑制金属（尤其是 铝） 的腐蚀， 因此它还可以应用在制备其他等离子刻蚀残留物清洗液中。  The star polymer having a pigment-affinity group in the present invention can effectively inhibit the corrosion of a metal (especially aluminum), and therefore it can also be used in the preparation of other plasma etching residue cleaning liquids.
本发明所用的原料和试剂均市售可得。  The starting materials and reagents used in the present invention are commercially available.
本发明的清洗液由上述成分简单均匀混合即可制得。  The cleaning liquid of the present invention can be obtained by simply and uniformly mixing the above components.
本发明的清洗液的使用方法如下:在用本发明的等离子刻蚀残留物清洗 液去除晶圆上刻蚀残留物以后， 直接用去离子水漂洗之后干燥即可。  The cleaning liquid of the present invention is used in the following manner: after removing the etching residue on the wafer by the plasma etching residue cleaning liquid of the present invention, it is directly rinsed with deionized water and then dried.
本发明的积极进步效果在于：  The positive effects of the present invention are:
1 )本发明的清洗液能有效清除光阻残留， 同时对金属 （尤其是铝）和 非金属的腐蚀速率较小，有效的改善了一般氟类清洗液不能同时控制金属和 非金属腐蚀速率的问题。  1) The cleaning liquid of the invention can effectively remove the photoresist residue, and at the same time, the corrosion rate of the metal (especially aluminum) and the non-metal is small, and the general fluorine cleaning liquid can not effectively control the corrosion rate of the metal and the non-metal at the same time. problem.
2) 该清洗液在清洗完光阻残留物后可以直接用水漂洗， 且在水中漂洗 时， 金属腐蚀速率小， 增加了晶圆漂洗的操作窗口。  2) The cleaning solution can be directly rinsed with water after cleaning the photoresist residue, and the metal corrosion rate is small when rinsing in water, which increases the operation window of wafer rinsing.
发明内容 Summary of the invention
下面用实施例来进一步说明本发明， 但本发明并不受其限制。 实施例 1~28 The invention is further illustrated by the following examples, but the invention is not limited thereto. Example 1~28
表 1为实施例 1~28， 将每一实施例中的各组分简单混匀即可得等离子刻 蚀残留物清洗液。 其中， Mn均为数均分子量。 表 1 等离子刻蚀残留物清洗液实施例 1~28  Table 1 shows Examples 1 to 28, and the components of each of the examples were simply mixed to obtain a plasma etching residue cleaning solution. Among them, Mn is a number average molecular weight. Table 1 Plasma etching residue cleaning solution Example 1~28
Figure imgf000007_0001
二丙
Figure imgf000007_0001
Dipropylene
三羟乙基氟  Trishydroxyethyl fluoride
星形聚丙烯  Star polypropylene
70 15 14.9999 0.0001 0 0 单甲 化铵 酸 Mn=3000  70 15 14.9999 0.0001 0 0 Monomethylammonium Mn=3000
醚 甲基丙烯酸  Ether methacrylic acid
羟乙 乙酯与甲基 Hydroxyethyl ester and methyl
基吡 Kiti
2 丙烯酸羟乙  2 Acrylic acid acrylate
60 氟化铰 37 1 0 0 咯烷 酯的星形共  60 fluorinated hinges 37 1 0 0
酮 聚物  Ketone polymer
Mn= 15000 丙烯酸甲酯、  Mn = 15000 methyl acrylate,
四甲基氟化 丙烯酸羟乙  Tetramethyl fluoride hydroxyethyl acrylate
丙二 C
40 15 44.5 酯和苯乙烯 0.5 0 0 醇 铵  40 15 44.5 Ester and styrene 0.5 0 0 Alcohol Ammonium
的三元星形  Trinity star
共聚物  Copolymer
Mn=30000  Mn=30000
丙烯酸丁酯、  Butyl acrylate,
二乙 丙烯酰胺和 Diethyl acrylamide and
62.9 氟化氢 0.1 30 2 氨水， 0 二醇 丙烯酸的三 5  62.9 Hydrogen fluoride 0.1 30 2 Ammonia water, 0 diol Three of acrylic acid 5
元星形共聚  Yuan star copolymerization
物 Mn= 10000  Mn= 10000
丙烯酸乙酯、  Ethyl acrylate,
羟乙 甲基丙烯酸 四甲 基吡 羟乙酯和苯 基氢 Hydroxyethyl methacrylate tetramethylpyridyl hydroxyethyl ester and phenyl hydrogen
40 氟硅酸 0.5 58 0.5 0 咯烷 乙烯的三元 氧化 酮 星形共聚物 铵， 1  40 fluorosilicic acid 0.5 58 0.5 0 ropane ethylene ternary oxidized ketone star copolymer ammonium, 1
Mn=30000  Mn=30000
甲基丙烯酸  Methacrylate
羟乙 Hydroxyethyl
与甲基丙烯  Methyl propylene
基吡 Kiti
65 氟硅酸铵 0.2 32.3 酸羟乙酯的 2.5 0 0 咯烷  65 ammonium fluorosilicate 0.2 32.3 hydroxyethyl ester 2.5 0 0 derotaxane
星形共聚物  Star copolymer
酮  Ketone
Mn=3000  Mn=3000
甲基丙烯酸  Methacrylate
三甲 二丙 丁酯、丙烯酸  Trimethyl dipropylene butyl ester, acrylic acid
二醇 羟乙酯和苯 Glycol hydroxyethyl ester and benzene
47 氟硼酸 1 50 1.5 基氢 0 单甲 乙烯的三元  47 fluoroboric acid 1 50 1.5 base hydrogen 0 ternary ethylene ternary
氧化 醚 星形共聚物  Oxide ether star copolymer
铵， 0.5 Mn= 10000  Ammonium, 0.5 Mn = 10000
二丙 丙烯酸丙酯 Propyl dipropacrylate
二醇 与丙烯酰胺 Glycol and acrylamide
50 氟硼酸铰 2 47.999 0.001 0 0 单甲 的星形共聚  50 fluoroboric acid hinge 2 47.999 0.001 0 0 single star star copolymer
醚 物 Mn=5000  Ether Mn=5000
丙烯酸羟乙  Hydroxyethyl acrylate
二甲 酯与丙烯酰 三乙 Dimethyl ester and acryloyl triethyl
三羟乙基氟  Trishydroxyethyl fluoride
基甲 40 5 24.99 胺的星形共 0.01 醇胺， 0 Base 40 5 24.99 amine star total 0.01 alcoholamine, 0
化铰  Hinge
酰胺 聚物， 30 Amide polymer, 30
Mn=50000 五甲 甲基丙烯酸 乙稀 二甲 甲酯与丙烯 三胺， Mn=50000 Ethylene dimethyl methacrylate and propylene triamine,
55 10 24.9 酸羟乙酯的 0.1 5 0  55 10 24.9 hydroxyethyl acetate 0.1 5 0
氟  Fluorine
酰胺 星形共聚物 亚氨 Amide star copolymer imine
Μη=7000  Μη=7000
乙酸，  Acetic acid,
5  5
乙醇 丙烯酸羟乙 胺， 0.2 酯、丙烯酰胺  Ethanol hydroxyethylamine acrylate, 0.2 ester, acrylamide
二甲 二乙 Dimethyl bromide
三羟乙基氟  Trishydroxyethyl fluoride
基甲 45 15 39 和丙烯酸的 Base 45 15 39 and acrylic
0.05 稀三 0 化铵 三元星形共  0.05 dilute three 0 ammonium ternary star
酰胺 胺， 0.2 Amide amine, 0.2
聚物 柠檬  Polymer lemon
Μη=3000 酸，  Μη=3000 acid,
0.55 丙烯酸乙酯、  0.55 ethyl acrylate,
甲基丙烯酸  Methacrylate
二甲 Dimethyl
三羟乙基氟 羟乙酯和苯  Trishydroxyethylfluorohydroxyethyl ester and benzene
基亚 55 10 29.995 0.005 羟胺， 0 Kea 55 10 29.995 0.005 Hydroxylamine, 0
化铰 乙烯的三元 5  Tie hinge ethylene ternary 5
砜  Sulfone
星形共聚物  Star copolymer
Μη=8000 丙烯酸甲酯、 乙酸 丙烯酸羟乙 铵， 15 二甲  Μη=8000 methyl acrylate, acetic acid hydroxyethylammonium acrylate, 15 dimethyl
酯和苯乙烯  Ester and styrene
基亚 43 氟化铵 2 29.9995 0.0005 0 Kea 43 Ammonium fluoride 2 29.9995 0.0005 0
的三元星形  Trinity star
砜  Sulfone
共聚物 乙酸，  Copolymer acetic acid,
Μη=3000 10 三乙 胺， 6 二甲 丙烯酸甲酯 苯并 二乙 基亚 60 氟化铵 2 18 与丙烯酰胺 0.1  Μη=3000 10 triethylamine, 6 dimethyl methacrylate benzodiethyl carbamide 60 ammonium fluoride 2 18 with acrylamide 0.1
胺， 3 唑， 砜 的星形共聚  Star copolymerization of amine, 3 azole, sulfone
物 Μη=5000 梓檬 10  Μη=5000 Lemon 10
酸， 0.9 丙烯酸乙酯 柠檬 二甲 与丙烯酰胺 酸， 0.3 苯并 基亚 50 氟化铵 3 37 的星形共聚 0.7  Acid, 0.9 Ethyl acrylate Lemon Dimethyl and acrylamide Acid, 0.3 Benzopyrene 50 Ammonium fluoride 3 37 Star copolymerization 0.7
砜 物 Μη=3000 唑， 5  Sulfone Μη=3000 azole, 5
4  4
丙烯酸丁酯 乳酸，  Butyl acrylate, lactic acid,
1 苯并 二甲 与丙烯酰胺  1 benzoxylene and acrylamide
基亚 45 三氮 氟化铰 1 45 的星形共聚 0.5 Star copolymerization of Kia 45 trinitrofluorinated hinge 1 45 0.5
唑， 砜 物 Μη=6000 乳酸  Oxazole, sulfone, Μη=6000, lactic acid
2.5 铵， 5 N, N- 丙烯酸羟乙 2.5 ammonium, 5 N, N- hydroxyethyl acrylate
二甲  Dimethyl
三羟乙基氟 二甲  Trishydroxyethyl fluoride
酯与丙烯酰  Ester and acryloyl
基亚 40 5 0.1  Kea 40 5 0.1
化铵 胺的星形共  Star of ammonium
砜 醇胺，  Sulfone alcohol amine,
聚物， 苯并  Polymer, benzo
10  10
Mn=5000  Mn=5000
24 28 三氮 唑， 羟乙 柠檬  24 28 triazole, hydroxyethyl lemon
丙烯酸甲酯 0.8 基吡 酸四  Methyl acrylate 0.8 pyridine
10 与丙烯酰胺  10 with acrylamide
氟化铰 1 0.1  Fluoride hinge 1 0.1
咯烷 甲基  Srrolidine methyl
的星形共聚  Star copolymerization
酮 铵盐，  Ketone ammonium salt,
物 Mn=3000  Mn=3000
5 甲基丙烯酸 N, N- 二甲 丙酯和甲基 二甲  5 methacrylic acid N, N- dimethyl propyl ester and methyl dimethyl methacrylate
25 基亚 45 氟化铰 5 39.3 丙烯酰胺的 0.7 0 砜 星形共聚物 醇胺，  25 Kia 45 fluorinated hinge 5 39.3 Acrylamide 0.7 0 sulfone Star copolymer Alcoholamine,
Mn=800 10 苯乙烯与丙 N, N- 二甲 烯酸羟乙酯 二甲  Mn=800 10 styrene and propene N, N-dimethyl enoate dimethyl ester
三羟乙基氟  Trishydroxyethyl fluoride
26 48 8 33 的二元星形 1 0  26 48 8 33 binary star 1 0
化铵  Ammonium
酰胺 共聚物 醇胺，  Amide copolymer
Mn=6000 10  Mn=6000 10
丙烯酸甲酯、  Methyl acrylate,
三甲 丙烯酸羟乙  Trimethyl acrylate
二乙 三羟乙基氟  Diethylene trihydroxyethyl fluoride
27 46 7 45 酯和乙烯的  27 46 7 45 Ester and ethylene
1.5 基氢 0 化铰 三元星形共  1.5 base hydrogen 0 hinges
氧化 聚物  Oxidized polymer
铰， 0.5 Mn=30000  Hinge, 0.5 Mn=30000
丙烯酸乙酯、  Ethyl acrylate,
甲基丙烯酸 四甲 环丁  Methacrylic acid
28 44 羟乙酯和丙 基氢  28 44 hydroxyethyl ester and propyl hydrogen
氟化铵 5 48.8 1.2 0 砜 . 烯的三元星 氧化  Ammonium fluoride 5 48.8 1.2 0 sulfone .
形共聚物 铰， 1  Shape copolymer hinge, 1
Mn=6000  Mn=6000
效果实施例 Effect embodiment
为了进一步体现本发明的效果，选择了清洗液 29〜44和对比清洗液 1〜2 进行了各项测试。  In order to further embody the effects of the present invention, various tests were carried out by selecting the cleaning liquids 29 to 44 and the comparative cleaning liquids 1 to 2.
表 2为清洗液 29〜44和对比清洗液 1〜2， 按表中配方， 将各组分简单混匀 即可制得各清洗液。 其中， Mn均为数均分子量。 表 2清洗液 29〜44和对比清洗液 1〜2的配方对比 Table 2 shows the cleaning liquids 29 to 44 and the comparative cleaning liquids 1 to 2. According to the formula in the table, the components are simply mixed to prepare each cleaning liquid. Among them, Mn is a number average molecular weight. Table 2 comparison of the cleaning solution 29~44 and the comparison cleaning solution 1~2
Figure imgf000011_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000012_0001
其中， NMP: N-甲基吡咯垸酮； DMAC: 二甲基乙酰胺； AcNH4 : 醋酸 铵； Ac: 醋酸； BTA: 苯并三氮唑。 1,本发明的部分清洗液在不同温度下的金属铝及非金属 TEOS腐蚀速率 测试 Among them, NMP: N-methylpyrrolidone; DMAC: dimethylacetamide; AcNH 4 : ammonium acetate; Ac: acetic acid; BTA: benzotriazole. 1, metal aluminum and non-metal TEOS corrosion rate test of some cleaning liquids of the invention at different temperatures
溶液的金属腐蚀速率测试方法：  Test method for metal corrosion rate of solution:
1)利用 Napson四点探针仪测试 4X4cm铝空白硅片的电阻初值（Rsl); 1) Using a Napson four-point prober to test the initial resistance value (Rsl) of a 4X4cm aluminum blank silicon wafer;
2)将该 4X4cm铝空白硅片浸泡在预先己经恒温到指定温度的溶液中 30分钟； 2) immersing the 4×4 cm aluminum blank silicon wafer in a solution which has been previously thermostated to a specified temperature for 30 minutes;
3)取出该 4X4cm铝空白硅片， 用去离子水清洗， 高纯氮气吹干， 再利 用 Napson四点探针仪测试 4X4cm铝空白硅片的电阻值（Rs2);  3) Remove the 4X4cm aluminum blank silicon wafer, wash it with deionized water, dry it with high purity nitrogen, and test the resistance value (Rs2) of 4X4cm aluminum blank silicon wafer by Napson four-point probe instrument;
4) 重复第二和第三步再测试一次， 电阻值记为 Rs3;  4) Repeat the second and third steps and test again, the resistance value is recorded as Rs3;
5) 把上述电阻值和浸泡时间输入到合适的程序可计算出其腐蚀速率。 溶液的非金属腐蚀速率测试方法：  5) Enter the resistance value and soak time into the appropriate program to calculate the corrosion rate. Test method for non-metallic corrosion rate of solution:
1)利用 Nanospec6100测厚仪测试 4X4cmPETEOS硅片的厚度 （T1); 1) Test the thickness of the 4X4cm PETEOS wafer (T1) using the Nanospec6100 thickness gauge;
2)将该 4X4cmPETEOS硅片浸泡在预先己经恒温到指定温度的溶液中 30分钟； 2) immersing the 4X4 cm PETEOS silicon wafer in a solution that has been previously thermostated to a specified temperature for 30 minutes;
3)取出该 4X4cmPETEOS硅片， 用去离子水清洗， 高纯氮气吹干， 再 利用 Nanospec6100测厚仪测试 4 X4cmPETEOS硅片的厚度 （T2);  3) Remove the 4X4cm PETEOS wafer, rinse it with deionized water, dry it with high purity nitrogen, and test the thickness of the 4 X4cm PETEOS wafer (T2) with a Nanospec6100 thickness gauge;
4) 重复第二和第三步再测试一次厚度记为 T3;  4) Repeat the second and third steps and test the thickness once again as T3;
5) 把上述厚度值和浸泡时间输入到合适的程序可计算出其腐蚀速率。 测试结果见表 3。  5) Enter the above thickness value and soak time into a suitable program to calculate the corrosion rate. The test results are shown in Table 3.
表 3部分清洗液在不同温度下的金属铝及非金属 TEOS腐蚀速率
Figure imgf000013_0001
清洗液 29 25 °C 1.52 未测试 清洗液 30 25 "C 1.45 未测试 Table 3 Metallic aluminum and non-metal TEOS corrosion rates of some cleaning solutions at different temperatures
Figure imgf000013_0001
Cleaning solution 29 25 °C 1.52 Untested cleaning solution 30 25 "C 1.45 Not tested
清洗液 36 25 0.18 0.63  Cleaning solution 36 25 0.18 0.63
清洗液 39 35。C 1.87 0.91  Cleaning solution 39 35. C 1.87 0.91
清洗液 41 35。C 0.75 1.01  Cleaning solution 41 35. C 0.75 1.01
清洗液 44 35 °C 0.20 1.53  Cleaning solution 44 35 °C 0.20 1.53
结论:  in conclusion:
在半导体清洗业界， 一般要求清洗液能有效去除光阻残留物， 而对接触 到的金属和非金属的腐蚀速率要求小于 2A/min。 从表 3中可以看出， 在不加 任何聚合物时， 对比例 1的腐蚀速率较大 （3.09A/min)， 对比例 2加入了 0.1% 的线性聚丙烯酸， 有利于金属铝腐蚀速率的降低 （1.88A/min)， 而清洗液 29 加入同样是 0.1%的星形聚丙烯酸， 其金属铝的腐蚀速率更低 （1.52A/min)。  In the semiconductor cleaning industry, it is generally required that the cleaning solution can effectively remove photoresist residues, and the corrosion rate of the contacted metal and non-metal is less than 2 A/min. As can be seen from Table 3, the corrosion rate of Comparative Example 1 was larger (3.09 A/min) without adding any polymer, and 0.1% of linear polyacrylic acid was added to Comparative Example 2, which was favorable for the corrosion rate of aluminum metal. The reduction was (1.88 A/min), and the cleaning solution 29 was added to the same 0.1% star polyacrylic acid, and the metal aluminum had a lower corrosion rate (1.52 A/min).
清洗液 30中， 溶剂用二甲基乙酰胺去代替 N-甲基吡咯垸酮， 金属铝的腐 蚀速率仍然较低 （1.45A/min) 。 说明该星形聚合物的腐蚀抑制效率对溶剂 没有选择性， 一直保持着对金属铝的良好的抗腐蚀性能。  In the cleaning solution 30, the solvent was replaced by dimethylacetamide instead of N-methylpyrrolidone, and the corrosion rate of the metal aluminum was still low (1.45 A/min). It shows that the corrosion inhibition efficiency of the star polymer is not selective to the solvent, and the corrosion resistance to the metal aluminum is maintained.
一般而言， 含氟清洗液的腐蚀速率会随温度的升高而增加。 为此， 进一 步测试了在 35°C下部分溶液的腐蚀速率。 从表 3中可以看出， 即使在 35°C下， 清冼液 39、 41和 44的金属铝和非金属 TEOS的腐蚀速率仍然小于 2A/min的业 界要求。 说明该类清洗液具有良好的金属和非金属的腐蚀抑制效率， 并具有 较大的温度操作窗口。  In general, the corrosion rate of a fluorine-containing cleaning solution increases with increasing temperature. For this reason, the corrosion rate of a part of the solution at 35 ° C was further tested. As can be seen from Table 3, even at 35 ° C, the corrosion rates of the metallic aluminum and non-metallic TEOS of the cleaning liquids 39, 41 and 44 are still less than the industry requirement of 2 A/min. This type of cleaning solution has good corrosion inhibition efficiency of metal and non-metal, and has a large temperature operation window.
2， 传统羟胺类的清洗液、 某含氟清洗液及清洗液 44在漂洗过程中金属 铝腐蚀速率变化情况比较  2, the comparison of the corrosion rate of metal aluminum during the rinsing process of traditional hydroxylamine cleaning solution, a fluorine-containing cleaning solution and cleaning solution 44
表 4列举了传统羟胺类的清洗液、 含氟清洗液及清洗液 44在漂洗过程中 金属铝腐蚀速率变化情况。  Table 4 lists the changes in the corrosion rate of the metal aluminum during the rinsing process of the conventional hydroxylamine cleaning solution, the fluorine-containing cleaning solution, and the cleaning solution 44.
表 4 传统羟胺类的清洗液、某含氟清洗液及清洗液 44在漂洗过程金属 铝腐蚀速率变化情况 Table 4 Traditional hydroxylamine cleaning solution, a fluorine-containing cleaning solution and cleaning solution 44 in the rinsing process metal Aluminum corrosion rate change
Figure imgf000015_0001
Figure imgf000015_0001
上表中， 百分比为质量百分比。  In the above table, the percentage is the mass percentage.
结论： 从表 4中可以看出， 清洗液 44在漂洗过程金属铝腐蚀速率比商业 化的传统羟胺类的清洗液和商业化的含氟清洗液均要低，故本发明的清洗液 不仅可以直接用水漂洗，而且其由于在漂洗过程中金属铝的腐蚀速率较小而 具有较大的漂洗操作窗口。 各清洗液配方中的各物质含量均为质量百分比。  Conclusion: It can be seen from Table 4 that the cleaning rate of the metal aluminum in the cleaning liquid 44 is lower than that of the commercial conventional hydroxylamine cleaning solution and the commercial fluorine-containing cleaning liquid, so the cleaning liquid of the present invention can not only It is rinsed directly with water, and it has a large rinsing operation window due to the small corrosion rate of metallic aluminum during the rinsing process. The content of each substance in each cleaning solution formulation is a mass percentage.
3, 清洗液 29、 33、 35、 36、 39和 41对晶圆清洗的结果  3, cleaning solution 29, 33, 35, 36, 39 and 41 wafer cleaning results
清洗结果见表 5。  The cleaning results are shown in Table 5.
表 5清洗液 29、 33、 35、 36、 39、 41对晶圆清洗的结果  Table 5 Cleaning solution 29, 33, 35, 36, 39, 41 wafer cleaning results
金属线 （Metal ) 通道 （Via) 金属垫 （Pad) 测试溶液  Metal channel (Via) metal pad (Pad) test solution
清洗条件 清洗结果 清洗条件 清洗结果 清洗条件 清洗结果 干净， 无腐 干净， 基本 干净， 无腐 清洗液 29 30°C/15min 30°C/10min 30"C/30min  Cleaning conditions Cleaning results Cleaning conditions Cleaning results Cleaning conditions Cleaning results Clean, non-corrosive Clean, basic Clean, non-corrosive Cleaning solution 29 30°C/15min 30°C/10min 30"C/30min
蚀 无腐烛 蚀 干净， 无腐 干净， 无腐 干净， 无腐 清洗液 33 35°C/10min 35°C/15min 35°C/30min  Corrosion Non-corrosive candle Eclipse Clean, non-corrosive Clean, non-corrosive Clean, non-corrosive Cleaning solution 33 35°C/10min 35°C/15min 35°C/30min
蚀 烛 蚀 干净， 无腐 干净， 无腐 干净， 无腐 清洗液 35 35°C/15min 35°C/15min 35°C/30min  Eclipse Candle erosion Clean, non-corrosive Clean, non-corrosive Clean, non-corrosive Cleaning solution 35 35°C/15min 35°C/15min 35°C/30min
蚀 烛 蚀 干净， 无腐 千净， 无腐 干净， 无腐 清洗液 36 35°C/20min 35°C/20min 35°C/30min  Eclipse Candle erosion Clean, non-corrosive, clean, non-corrosive Clean, non-corrosive cleaning solution 36 35°C/20min 35°C/20min 35°C/30min
蚀 蚀 蚀 干净， 无腐 干净， 无腐 干净， 无腐 清洗液 39 35°C/20min 35°C/20min 35°C/30min  Corrosion Erosion Clean, non-corrosive Clean, non-corrosive Clean, non-corrosive Cleaning solution 39 35°C/20min 35°C/20min 35°C/30min
蚀 蚀 蚀 干净， 无腐 干净， 无腐 干净， 无腐 清洗液 4】 35°C/20min 35°C/30min 35°C/30min Corrosion Clean, non-corrosive, non-corrosive, non-corrosive cleaning solution 4] 35°C/20min 35°C/30min 35°C/30min
蚀 蚀 蚀 结论： 表 5选择了一些清洗液配方对三种晶圆 （金属线， Metal; 通道， Via; 金属垫， Pad) 进行了清洗， 通过实验发现该类配方均能有效地去除光 阻残留物， 而未对金属和非金属产生明显的腐蚀。  Corrosion Conclusion: Table 5 selected some cleaning solution formulations to clean three wafers (metal wire, metal; channel, Via; metal pad, Pad). It was found through experiments that these formulations can effectively remove the photoresist. Residues without significant corrosion to metals and non-metals.
综上所述， 1 ) 本发明的清洗液能有效清除光阻残留， 同时可以高效的 抑制金属 （尤其是铝） 的腐蚀， 并且对非金属的腐蚀速率较小， 有效的改善 了一般氟类清洗液不能同时控制金属和非金属腐蚀速率的问题； 2) 本发明 的清洗液在清洗完光阻残留物后， 在水中漂洗时， 金属腐蚀速率小， 增加了 晶圆漂洗的操作窗口。  In summary, 1) the cleaning liquid of the invention can effectively remove the photoresist residue, and can effectively inhibit the corrosion of the metal (especially aluminum), and the corrosion rate to the non-metal is small, effectively improving the general fluorine type. The cleaning solution cannot simultaneously control the corrosion rate of metal and non-metal; 2) The cleaning solution of the present invention has a small metal corrosion rate when rinsing in water after cleaning the photoresist residue, and increases the operation window of the wafer rinsing.

Claims

权利要求 Rights request
1、 一种等离子刻蚀残留物清洗液， 包含溶剂、 水和氟化物， 其特征在 于： 其还含有含颜料亲和基团的星形聚合物。 A plasma etching residue cleaning solution comprising a solvent, water and fluoride, characterized in that it further comprises a star polymer containing a pigment affinity group.
2、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的含颜料亲和基团的星形聚合物的质量分数为 0.001%~3%。  The plasma etching residue cleaning solution according to claim 1, wherein the star polymer containing the pigment-affinity group has a mass fraction of 0.001% to 3%.
3、 如权利要求 2所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的含颜料亲和基团的星形聚合物的质量分数为 0.001%~1%。  The plasma etching residue cleaning solution according to claim 2, wherein the star polymer containing the pigment-affinity group has a mass fraction of 0.001% to 1%.
4、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的溶剂的质量分数为 20%〜85%。  The plasma etching residue cleaning solution according to claim 1, wherein the solvent has a mass fraction of 20% to 85%.
5、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的水的质量分数为 10%~70%。  The plasma etching residue cleaning solution according to claim 1, wherein the water has a mass fraction of 10% to 70%.
6、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的氟化物的质量分数为 0.1%〜30%。  The plasma etching residue cleaning solution according to claim 1, wherein the fluoride has a mass fraction of 0.1% to 30%.
7、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 形成 所述的含颜料亲和基团的星形聚合物的聚合单体包括下列中的一种或多种： 含颜料亲和基团的丙烯酸类单体、含颜料亲和基团的丙烯酸酯类单体和含颜 料亲和基团的丙烯酰胺类单体。  7. The plasma etch residue cleaning solution according to claim 1, wherein: the polymerizable monomer forming the star polymer containing the pigment-affinity group comprises one or more of the following: An acrylic monomer containing a pigment affinity group, an acrylate monomer containing a pigment affinity group, and an acrylamide monomer containing a pigment affinity group.
8、 如权利要求 1或 7所述的等离子刻蚀残留物清洗液， 其特征在于： 所述的颜料亲和基团为羟基、 氨基或羧基。  The plasma etching residue cleaning solution according to claim 1 or 7, wherein the pigment affinity group is a hydroxyl group, an amino group or a carboxyl group.
9、 如权利要求 7所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的丙烯酸类单体为丙烯酸或甲基丙烯酸；所述的丙烯酸酯类单体为丙烯酸甲 酯、 甲基丙烯酸甲酯、 丙烯酸乙酯、 甲基丙烯酸乙酯、 丙烯酸丙酯、 甲基丙 烯酸丙酯、 丙烯酸丁酯、 甲基丙烯酸丁酯、 丙烯酸羟乙酯或甲基丙烯酸羟乙 酯； 所述的丙烯酰胺类单体为丙烯酰胺或甲基丙烯酰胺。  9. The plasma etching residue cleaning solution according to claim 7, wherein: the acrylic monomer is acrylic acid or methacrylic acid; and the acrylate monomer is methyl acrylate or methyl group. Methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate; The amide monomer is acrylamide or methacrylamide.
10、 如权利要求 7所述的等离子刻蚀残留物清洗液， 其特征在于： 形成 所述的含颜料亲和基团的星形聚合物中的单体还包括其他乙烯棊类单体。10. The plasma etching residue cleaning solution according to claim 7, wherein: forming The monomer in the star polymer containing the pigment-affinity group also includes other vinyl quinone monomers.
11、 如权利要求 10所述的等离子刻蚀残留物清洗液， 其特征在于： 所 述的其他乙烯基类单体为乙烯、 丙烯或苯乙烯。 The plasma etching residue cleaning liquid according to claim 10, wherein the other vinyl monomer is ethylene, propylene or styrene.
12、 如权利要求 7所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的含颜料亲和基团的星形聚合物为聚丙烯酸星形均聚物，苯乙烯与丙烯酸羟 乙酯的二元星形共聚物， 丙烯酸甲酯与丙烯酸羟乙酯的二元星形共聚物， 丙 烯酸与丙烯酸羟乙酯的二元星形共聚物， 以及丙烯酸、丙烯酸丁酯和丙烯酰 胺的三元星形共聚物中的一种或多种。  12. The plasma etching residue cleaning solution according to claim 7, wherein: the star polymer containing the pigment-affinity group is a polyacrylic acid star homopolymer, styrene and hydroxyethyl acrylate. a binary star copolymer of ester, a binary star copolymer of methyl acrylate and hydroxyethyl acrylate, a binary star copolymer of acrylic acid and hydroxyethyl acrylate, and three of acrylic acid, butyl acrylate and acrylamide One or more of the metastar copolymers.
13、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的含颜料亲和基团的星形聚合物的数均分子量为 800-50000。  The plasma etching residue cleaning liquid according to claim 1, wherein the star polymer containing the pigment-affinity group has a number average molecular weight of 800 to 50,000.
14、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的溶剂为亚砜、 砜、 咪唑烷酮、 吡咯垸酮、 咪唑啉酮、 醇、 醚和酰胺中的一 种或多种。  14. The plasma etching residue cleaning solution according to claim 1, wherein: the solvent is sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolidinone, alcohol, ether and amide. One or more.
15、 如权利要求 14所述的等离子刻蚀残留物清洗液， 其特征在于： 所 述的亚砜为 -C4亚砜和 /或 C7-C1Q的芳基亚砜； 所述的砜为 d-C4砜和 /或 C7-C1Q的芳基砜； 所述的咪唑垸酮为 1， 3-二甲基 -2-咪唑垸酮； 所述的吡咯 烷酮为 N-甲基吡咯烷酮和 /或羟乙基吡咯垸酮；所述的咪唑啉酮为 1， 3-二甲 基 _2_咪唑啉酮；所述的醇为（^(^垸基醇和 /或 C7-C1Q的芳基醇；所述的醚为 C3-C2()的醚； 所述的酰胺为 -C6垸基酰胺。 The plasma etching residue cleaning solution according to claim 14, wherein: the sulfoxide is -C 4 sulfoxide and/or C 7 -C 1Q aryl sulfoxide; Is a dC 4 sulfone and/or a C 7 -C 1Q aryl sulfone; the imidazolium is 1, 3-dimethyl-2-imidazolium; the pyrrolidone is N-methylpyrrolidone and / Or hydroxyethylpyrrolidone; the imidazolidinone is 1, 3-dimethyl- 2- imidazolidinone; the alcohol is (^(^-mercaptool and/or C 7 -C 1Q aryl) The ether is an ether of C 3 -C 2 () ; the amide is -C 6 mercapto amide.
16、 如权利要求 15所述的等离子刻蚀残留物清洗液， 其特征在于： 所 述的亚砜为二甲基亚砜；所述的砜为环丁砜；所述的醇为丙二醇和 /或二乙二 醇；所述的醚为丙二醇单甲醚和 /或二丙二醇单甲醚；所述的酰胺为二甲基甲 酰胺和 /或二甲基乙酰胺。  The plasma etching residue cleaning solution according to claim 15, wherein: the sulfoxide is dimethyl sulfoxide; the sulfone is sulfolane; and the alcohol is propylene glycol and/or Ethylene glycol; the ether is propylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether; the amide is dimethylformamide and/or dimethylacetamide.
17、 如权利要求 1所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的氟化物为氟化氢、 氟硅酸、 氟硅酸铵、 氟硼酸、 氟硼酸铵和氟化氢与碱形 成的盐中的一种或多种。 17. The plasma etch residue cleaning solution according to claim 1, wherein: The fluoride is one or more of hydrogen fluoride, fluorosilicic acid, ammonium fluorosilicate, fluoroboric acid, ammonium fluoroborate, and a salt formed by hydrogen fluoride and a base.
18、 如权利要求 17所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的碱为氨水、 季胺氢氧化物或醇胺。  The plasma etching residue cleaning solution according to claim 17, wherein the base is ammonia water, quaternary ammonium hydroxide or alcohol amine.
19、 如权利要求 17所述的等离子刻蚀残留物清洗液， 其特征在于： 所述 的氟化氢与碱形成的盐为氟化氢铵、四甲基氟化铵和三羟乙基氟化铵中的一 种或多种。  The plasma etching residue cleaning solution according to claim 17, wherein the hydrogen fluoride and the base form a salt of ammonium hydrogen fluoride, tetramethylammonium fluoride and trishydroxyethyl ammonium fluoride. One or more.
PCT/CN2009/001001 2008-09-05 2009-09-04 Rinse solution for removal of plasm etching residues WO2010025624A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6176584B1 (en) * 2016-09-30 2017-08-09 パナソニックＩｐマネジメント株式会社 Resist stripper

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104345583B (en) * 2013-08-02 2020-07-03 安集微电子科技（上海）股份有限公司 Cleaning solution for removing photoresist residues
CN104570628B (en) * 2013-10-25 2021-12-17 安集微电子科技（上海）股份有限公司 Metal low-etching photoresist stripping liquid and application thereof
CN103555464B (en) * 2013-11-05 2015-01-07 朱永明 Cleaning fluid as well as configuration method and cleaning method thereof
CN105022237B (en) * 2014-04-23 2020-07-03 安集微电子科技（上海）股份有限公司 Metal low-etching photoresist stripping liquid
CN107678253A (en) * 2017-09-26 2018-02-09 合肥新汇成微电子有限公司 A kind of cleaning fluid for semiconductor crystal wafer plasma etch residues
CN112592777B (en) * 2020-12-03 2021-09-07 湖北兴福电子材料有限公司 Deep groove cleaning solution after 3D NAND structure piece dry etching

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005057281A2 (en) * 2003-12-02 2005-06-23 Advanced Technology Materials, Inc. Resist, barc and gap fill material stripping chemical and method
CN1982426A (en) * 2005-12-16 2007-06-20 安集微电子（上海）有限公司 Slow-releasing agent system for cleaning semiconductor chip
CN100410357C (en) * 2004-06-25 2008-08-13 捷时雅株式会社 Cleaning composition for semiconductor components and process for manufacturing semiconductor device
CN101412948A (en) * 2007-10-19 2009-04-22 安集微电子（上海）有限公司 Cleaning agent for plasma etching residue
CN101412949A (en) * 2007-10-19 2009-04-22 安集微电子（上海）有限公司 Cleaning liquid for plasma etching residue

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6006764A (en) * 1997-01-28 1999-12-28 Taiwan Semiconductor Manufacturing Company, Ltd. Method of stripping photoresist from Al bonding pads that prevents corrosion
MY143399A (en) * 2001-07-09 2011-05-13 Avantor Performance Mat Inc Microelectronic cleaning compositons containing ammonia-free fluoride salts for selective photoresist stripping and plasma ash residue cleaning
US20050136670A1 (en) * 2003-12-19 2005-06-23 Ameen Joseph G. Compositions and methods for controlled polishing of copper
US20050194562A1 (en) * 2004-02-23 2005-09-08 Lavoie Raymond L.Jr. Polishing compositions for controlling metal interconnect removal rate in semiconductor wafers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005057281A2 (en) * 2003-12-02 2005-06-23 Advanced Technology Materials, Inc. Resist, barc and gap fill material stripping chemical and method
CN100410357C (en) * 2004-06-25 2008-08-13 捷时雅株式会社 Cleaning composition for semiconductor components and process for manufacturing semiconductor device
CN1982426A (en) * 2005-12-16 2007-06-20 安集微电子（上海）有限公司 Slow-releasing agent system for cleaning semiconductor chip
CN101412948A (en) * 2007-10-19 2009-04-22 安集微电子（上海）有限公司 Cleaning agent for plasma etching residue
CN101412949A (en) * 2007-10-19 2009-04-22 安集微电子（上海）有限公司 Cleaning liquid for plasma etching residue

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6176584B1 (en) * 2016-09-30 2017-08-09 パナソニックＩｐマネジメント株式会社 Resist stripper
WO2018061065A1 (en) * 2016-09-30 2018-04-05 パナソニックＩｐマネジメント株式会社 Resist removal liquid

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