WO2012009968A1 - 一种光刻胶的清洗液 - Google Patents

一种光刻胶的清洗液 Download PDF

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Publication number
WO2012009968A1
WO2012009968A1 PCT/CN2011/001217 CN2011001217W WO2012009968A1 WO 2012009968 A1 WO2012009968 A1 WO 2012009968A1 CN 2011001217 W CN2011001217 W CN 2011001217W WO 2012009968 A1 WO2012009968 A1 WO 2012009968A1
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WIPO (PCT)
Prior art keywords
cleaning solution
cleaning
photoresist
solution according
mass
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PCT/CN2011/001217
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English (en)
French (fr)
Inventor
刘兵
彭洪修
孙广胜
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安集微电子（上海）有限公司
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Publication of WO2012009968A1 publication Critical patent/WO2012009968A1/zh

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    • 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
    • C11D7/06—Hydroxides
    • 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
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • 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
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5013—Organic solvents containing nitrogen
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline compositions for etching copper or alloys thereof
    • 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
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • 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
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • 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
    • 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
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds

Definitions

  • the present invention relates to a cleaning fluid in a semiconductor process, and in particular to a thicker photoresist cleaning fluid.
  • a mask of a photoresist is formed on a surface of a metal such as silicon dioxide, Cu (copper), or a low-k material, and the pattern is transferred after exposure, and after the desired circuit pattern is obtained, The remaining photoresist needs to be stripped off before the next process.
  • a photoresist is required to form a mask, which needs to be removed after the microsphere is successfully implanted, but since the photoresist is thick, it is completely removed. More difficult.
  • a more common method for improving the removal is to extend the soaking time, increase the soaking temperature, and use a more aggressive solution, but this often results in corrosion of the wafer substrate and corrosion of the microspheres, resulting in a significant reduction in wafer yield.
  • the photoresist cleaning liquid is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in the cleaning liquid or rinsing the semiconductor wafer with the cleaning liquid.
  • the strong bases commonly used are mainly inorganic metal hydroxides (such as potassium hydroxide and the like) and organic hydroxides such as tetramethylammonium hydroxide.
  • JP1998239865 consists of an alkaline cleaning solution consisting of tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO), 1,3'-dimethyl-2-imidazolium (DMI) and water.
  • TMAH tetramethylammonium hydroxide
  • DMSO dimethyl sulfoxide
  • DMI 1,3'-dimethyl-2-imidazolium
  • WO2006/056298A1 utilizes an alkaline cleaning solution consisting of tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO), ethylene glycol (EG) and water for cleaning 50 ⁇ 100 ⁇ thick Photoresist, which is essentially non-corrosive to metallic copper; US6040117 utilizes alkaline cleaning consisting of hydrazine, dimethyl sulfoxide (DMSO), 1,3'-dimethyl-2-imidazolium (DMI) and water. The liquid is introduced into the cleaning solution to remove a thick film photoresist of 20 ⁇ m or more on the metal and dielectric substrate at 50 to 100 °C.
  • TMAH tetramethylammonium hydroxide
  • DMSO dimethyl sulfoxide
  • EG ethylene glycol
  • DMI 1,3'-dimethyl-2-imidazolium
  • US 5529887 consists of an alkaline cleaning solution consisting of potassium hydroxide (hydrazine), mercapto diol monodecyl ether, water-soluble fluoride and water, and the wafer is immersed in the cleaning solution to remove the metal at 40 to 90 ° C. And a thick film photoresist on a dielectric substrate. It has a high corrosion to the semiconductor wafer substrate.
  • the technical problem to be solved by the invention is to provide a thick film photoresist cleaning for the existing thick film photoresist cleaning liquid, which has insufficient cleaning ability or strong corrosion to the semiconductor wafer pattern and the substrate.
  • a photoresist cleaner that is highly capable and less corrosive to semiconductor wafer patterns and substrates.
  • a cleaning solution for a thick film photoresist comprising (a) potassium hydroxide, (b) a pyrrolidone solvent, (c) pentaerythritol, d) Alcoholamines, (e) Resorcinol.
  • the mass percentage of the potassium hydroxide in the cleaning solution is preferably 0.1 to 10%; the mass percentage of the pyrrolidone solvent in the cleaning solution is preferably 10 to 90%; the pentaerythritol is The mass percentage of the cleaning liquid is preferably 0.1 to 15% ; the mass percentage of the alcohol amine in the cleaning liquid is preferably 0.1 to 55%; and the mass percentage of the resorcin in the cleaning liquid is preferably 0.1 to 15%. 10%; the other cosolvent in the cleaning liquid mass percentage is preferably 0 ⁇ 85% ;
  • the pyrrolidone solvent described in the present invention is N-methylpyrrolidone, N-ethylpyrrolidone,
  • N-hydroxyethylpyrrolidone and N-cyclohexylpyrrolidone are N-hydroxyethylpyrrolidone and N-cyclohexylpyrrolidone.
  • the alcohol amine described in the present invention is one of monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2-(diethylamino)ethanol, ethyldiethanolamine and diglycolamine. Or several.
  • the presence of an alcoholamine is beneficial to increase the solubility of potassium hydroxide and pentaerythritol in the system and to protect the metal microspheres.
  • the present invention may further comprise a cosolvent which may be selected from one or more of sulfoxide, sulfone, imidazolidinone, imidazolidinone, alcohol, ether, amide.
  • the sulfoxide is preferably dimethyl sulfoxide; the sulfone is preferably sulfolane; and the imidazolium is preferably 1,3-dimethyl-2-imidazolium
  • the imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone (DMI);
  • the amide is preferably dimethylformamide or dimethylacetamide;
  • the alcohol is preferably propylene glycol or diethylene glycol; and the ether is preferably propylene glycol monomethyl ether or dipropylene glycol monomethyl ether.
  • the low-etching photoresist cleaning liquid of the present invention can clean the photoresist of a thickness of ⁇ or more at room temperature to 90 ,, and can have metal microspheres and metal microspheres due to the resorcinol and the alcoholamine contained therein.
  • a protective film is formed on the surface of the underlying metal (UBM) to reduce corrosion of the substrate.
  • UBM underlying metal
  • a complex solvent system of a pyrrolidone solvent and pentaerythritol is advantageous for improving the removal efficiency of the photoresist.
  • the specific method is as follows: The photoresist wafer-containing semiconductor wafer is immersed in the low-etching photoresist cleaning agent of the present invention, and after being immersed at room temperature to 90 ° C for a suitable period of time, it is taken out and washed, and then blown dry with high-purity nitrogen gas.
  • the cleaning liquid of the present invention can be obtained by simply mixing and mixing the above components.
  • the cleaning liquid of the invention can be Used in a wide temperature range, generally in the range of room temperature to 90 °C.
  • the reagents and starting materials used in the present invention are commercially available.
  • the photoresist cleaning liquid of the present invention can be applied to the cleaning of a thick (thickness greater than ⁇ ) photoresist.
  • the low etching photoresist cleaning liquid of the present invention can be used to clean the photoresist at room temperature to 90 °C.
  • the alcohol amine solvent used in the formulation improves the solubility of potassium hydroxide and pentaerythritol in the system and is beneficial to the protection of metal microspheres.
  • the resorcinol used in the formulation can effectively inhibit the corrosion of metals such as copper.
  • Table 1 shows Examples 1 to 27 of the present invention which are suitable for thicker photoresist cleaning liquids. According to the formulation in the table, the components are uniformly mixed, and the cleaning of each embodiment can be obtained. liquid.
  • NA is not added to this component.
  • the present invention adopts the following technical means: a semiconductor wafer containing a negative acrylate-based photoresist (having a thickness of about 120 ⁇ m and exposed and etched) (bump package)
  • the wafer was immersed in a cleaning agent, and oscillated at a vibration frequency of about 60 rpm for 15 to 120 minutes at 25 to 90 ° C using a constant temperature oscillator, and then washed with deionized water and then dried with high purity nitrogen gas.
  • Example 3 90 120 ⁇ ⁇ ⁇ Example 15 35 120 ⁇ ⁇ ⁇ Example 16 90 120 ⁇ ⁇ O Example 17 80 120 ⁇ ⁇ ⁇ Example 19 90 90 ⁇ ⁇ O Example 20 90 120 ⁇ ⁇ ⁇ Example 21 90 90 ⁇ ⁇ ⁇ Example 22 60 60 ⁇ ⁇ ⁇ Example 23 65 105 ⁇ ⁇ ⁇ Example 24 75 50 ⁇ ⁇ ⁇ Example 25 90 15 ⁇ ⁇ ⁇ Example 26 85 30 ⁇ ⁇ ⁇ Example 27 55 60 ⁇ ⁇ ⁇ Example 20 50 100 ⁇ ⁇ ⁇ Example 27 25 120 ⁇ ⁇ ⁇ ⁇ basically no corrosion; ⁇ completely removed;
  • the cleaning liquid of the present invention has a good cleaning effect on the thick film photoresist, has a wide temperature range of use, and has good corrosion inhibition effects on metal microspheres and metallic copper.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Description

一种光刻胶的清洗液 技术领域
本发明涉及半导体工艺中一种清洗液，具体的涉及一种较厚光刻胶清洗 液。 技术背景
在通常的半导体制造工艺中， 通过在二氧化硅、 Cu (铜）等金属以及低 k材料等表面上形成光刻胶的掩膜， 曝光后进行图形转移，在得到需要的电 路图形之后， 进行下一道工序之前， 需要剥去残留的光刻胶。 例如， 在晶圆 微球植入工艺（bumping technology) 中， 需要光刻胶形成掩膜， 该掩膜在微 球成功植入后同样需要去除， 但由于该光刻胶较厚， 完全去除常较为困难。 改善去除效果较为常用的方法是采用延长浸泡时间、提高浸泡温度和采用更 富有攻击性的溶液， 但这常会造成晶片基材的腐蚀和微球的腐蚀， 从而导致 晶片良率的显著降低。
目前， 光刻胶清洗液主要由极性有机溶剂、强碱和 /或水等组成，通过将 半导体晶片浸入清洗液中或者利用清洗液冲洗半导体晶片，去除半导体晶片 上的光刻胶。 其中其常用的强碱主要是无机金属氢氧化物 （如氢氧化钾等） 和有机氢氧化物如四甲基氢氧化胺等。
如 JP1998239865由四甲基氢氧化铵 （TMAH)、 二甲基亚砜（DMSO)、 1，3'-二甲基 -2-咪唑垸酮（DMI)和水等组成碱性清洗液， 将晶片浸入该清洗 液中，于 50〜100°C下除去金属和电介质基材上的 20μπι以上的厚膜光刻胶。 其对半导体晶片基材的腐蚀略高， 且不能完全去除半导体晶片上的光刻胶， 清洗能力不足； WO2006/056298A1利用由四甲基氢氧化铰 （TMAH)、 二甲 基亚砜（DMSO), 乙二醇（EG)和水组成碱性清洗液，用于清洗 50〜100μιη 厚的光刻胶， 同时对金属铜基本无腐蚀； US6040117利用由 ΤΜΑΗ、二甲基 亚砜 （DMSO)、 1，3'-二甲基 -2-咪唑垸酮 （DMI) 和水等组成碱性清洗液， 将晶片进入该清洗液中，于 50〜100°C下除去金属和电介质基材上的 20μηι以 上的厚膜光刻胶。 又例如 US5529887由氢氧化钾（ΚΟΗ)、垸基二醇单垸基 醚、 水溶性氟化物和水等组成碱性清洗液， 将晶片浸入该清洗液中， 在 40〜90°C下除去金属和电介质基材上的厚膜光刻胶。 其对半导体晶片基材的 腐蚀较高。
由此可见， 寻找更为有效抑制的金属腐蚀抑制剂， 溶解更多光刻胶的溶 剂体系该类光刻胶清洗液努力改进的优先方向。 发明概要
本发明要解决的技术问题就是针对现有的厚膜光刻胶清洗液存在的清 洗能力不足或者对半导体晶片图案和基材腐蚀性较强的缺陷，而提供一种对 厚膜光刻胶清洗能力强且对半导体晶片图案和基材腐蚀性较低的光刻胶清 洗剂。
本发明解决上述技术问题所采用的技术方案是：一种用于厚膜光刻胶的 清洗液， 该清洗液包含 （a)氢氧化钾， （b) 吡咯烷酮类溶剂， （c) 季戊四 醇， （d) 醇胺， （e) 间苯二酚。
其中， 所述的氢氧化钾在清洗液中质量百分比较佳为 0.1〜10%； 所述的 吡咯垸酮类溶剂在清洗液中质量百分比较佳为 10〜90%； 所述的季戊四醇在 清洗液中质量百分比较佳为 0.1〜15%; 所述的醇胺在清洗液中质量百分比较 佳为 0.1〜55%； 所述的间苯二酚在清洗液中质量百分比较佳为 0.1〜10%； 所 述的其它助溶剂在清洗液中质量百分比较佳为 0〜85%;
本发明中所述的吡咯垸酮类溶剂为 N-甲基吡咯垸酮、 N-乙基吡咯垸酮、
N-羟乙基吡咯垸酮和 N-环己基吡咯垸酮。
本发明中所述的醇胺为单乙醇胺、 二乙醇胺、 三乙醇胺、 正丙醇胺、 异 丙醇胺、 2- (二乙氨基） 乙醇、 乙基二乙醇胺和二甘醇胺中的一种或几种。 醇胺的存在有利于提高氢氧化钾和季戊四醇在体系中的溶解度，并有利于金 属微球的保护。 本发明还可以进一步含有助溶剂， 所述的助溶剂可选自亚砜、 砜、 咪唑 烷酮、 咪唑啉酮、 醇、 醚、 酰胺中的一种或多种。 其中， 所述的亚砜较佳的 为二甲基亚砜； 所述的砜较佳的为环丁砜； 所述的咪唑垸酮较佳的为 1,3-二 甲基 -2-咪唑垸酮；所述的咪唑啉酮较佳的为 1，3-二甲基 -2-咪唑啉酮（DMI); 所述的酰胺较佳的为二甲基甲酰胺、二甲基乙酰胺；所述的醇较佳的丙二醇、 二乙二醇； 所述的醚较佳的为丙二醇单甲醚、 二丙二醇单甲醚。
本发明中的低蚀刻性光刻胶清洗液， 可以在室温至 90Ό下清洗 ΙΟΟμηι 以上厚度的光刻胶， 而且由于其中含有的间苯二酚和醇胺， 可以对金属微球 和金属微球下面的金属（UBM)表面形成一层保护膜，从而降低基材的腐蚀。 吡咯烷酮类溶剂和季戊四醇的复合溶剂体系， 有利于提高光刻胶的去除效 率。具体方法如下： 将含有光刻胶的半导体晶片浸入本发明中的低蚀刻性的 光刻胶清洗剂，在室温至 90°C下浸泡合适的时间后，取出洗涤后用高纯氮气 吹干。
本发明的清洗液经上述成分简单混合均匀即可制得。本发明的清洗液可 在较大的温度范围内使用， 一般在室温到 90°C范围内。本发明所用试剂及原 料均市售可得。
本发明的积极进步效果在于：
( 1 ) 本发明的光刻胶清洗液， 可适用于较厚 （厚度大于 ΙΟΟμιη) 光刻 胶的清洗。
(2) 本发明中的低蚀刻性光刻胶清洗液， 可以在室温至 90°C下清洗光 刻胶。
(3 ) 配方中采用的醇胺溶剂， 提高了氢氧化钾和季戊四醇在体系中的 溶解度， 并有利于金属微球的保护。
(4) 配方中采用的吡咯垸酮类溶剂和季戊四醇的复合溶剂体系， 提高 了光刻胶的去除能力。
(5 )配方中采用的间苯二酚能对铜等金属起到有效的腐蚀抑制作用。 发明内容
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在 所述的实施例范围之中。
实施例 1~27 表 1给出了本发明的适用于较厚光刻胶清洗液的实施例 1~27，按表中配 方， 将各组分混合均匀， 即可制得各实施例的清洗液。
表 1 本发明实施例 1~27的组分和含量
醇胺 吡咯垸酮类溶剂
季戊 间苯 助溶 实 氢氧
四醇， 二酚，
施 化钾， 含 含量
含量 含量 名称 M 名称 含量 名称 例 含量 wt% wt% wt% wt% wt%
wt%
N-甲基吡
1 0.1 0.1 9.7 三乙醇胺 0.1 90 NA NA 咯垸酮 N-乙基吡
10 15 10 二乙醇胺 55 10 NA NA 咯烷酮
N-羟乙基
0.5 0.2 0.1 单乙醇胺 14.2 85 NA NA 吡咯垸酮
N-环己基
1 0.8 0.5 正丙醇胺 17.7 80 NA NA 吡咯烷酮
N-甲基吡
0.1 0.1 0.2 异丙醇胺 4.6 10 85 咯垸酮 亚砜
2- (二乙氨 N-甲基吡
2 3 8 10 75 环丁砜 2 基） 乙醇 咯垸酮
1，3-二甲 乙基二乙 N-甲基吡
1.5 5 0.5 20 70 基 -2-咪 3 醇胺 咯垸酮
唑烷酮
-二甲
N-甲基吡
4 8 6 二甘醇胺 25 17 基 -2-咪 40 咯烷酮
唑啉酮
N-乙基吡
6 10 4 单乙醇胺 30 20 30 咯垸酮 甲酰胺
N-乙基吡
1 12 2 单乙醇胺 35 25 25 咯垸酮 乙酰胺
N-羟乙基
8 1 1 单乙醇胺 50 30 丙二醇 10 吡咯烷酮
N-羟乙基 二乙二
1 14 1 单乙醇胺 45 35 4 吡咯烷酮 醇
N-羟乙基 丙二醇
5 9 1 单乙醇胺 40 40 5 吡咯垸酮 单甲醚
二丙二
N-甲基吡
3 7 3 单乙醇胺 15 45 醇单甲 27 咯烷酮
醚
N-甲基吡 二甲基
2 6 0.5 二甘醇胺 6.5 50 35 咯烷酮 亚砜
N-甲基吡
2 9.5 0.5 二甘醇胺 8 55 25 咯烷酮 亚砜
N-甲基吡
2 7 5 二甘醇胺 6 60 20 咯烷酮 亚砜
N-甲基吡
1 5 4 单乙醇胺 10 65 15 咯垸酮 亚砜
N-甲基吡
2 5 0.2 单乙醇胺 5 17.8 70 咯烷酮 亚砜
N-甲基吡
1 3 0.2 单乙醇胺 3 17.8 75 咯垸酮 亚砜
N-甲基吡
0.8 4 0.2 单乙醇胺 5 10 80 咯垸酮 亚砜
N-甲基吡
1.5 10 1 单乙醇胺 7.5 15 65 咯垸酮 亚砜
二甲基
2 5 0.5 单乙醇胺 12.5 N-甲基吡 20 60 亚砜 咯垸酮
N-甲基吡
二甲基
1 3 1 单乙醇胺 10 咯垸酮 30 55 亚砜 N-甲基吡
25 1.5 3.3 0.2 单乙醇胺 10 35 50 咯烷酮 亚砜
N-环己基
26 2 7.8 0.2 二甘醇胺 15 30 环丁砜 45 吡咯垸酮
N-甲基吡
单乙醇胺 15 30 30 咯垸酮 亚砜
27 3 5 0.2
N-环己基
三乙醇胺 0.5 10 环丁砜 6.3 吡咯垸酮
NA是没有加入该组分。
效果实施例
为了进一步考察该类清洗液的清洗情况， 本发明采用了如下技术手段： 即将含有负性丙烯酸酯类光刻胶 （厚度约为 120微米， 且经过曝光和刻蚀） 的半导体晶片 （凸点封装晶圆）浸入清洗剂中， 在 25〜90°C下利用恒温振荡 器以约 60转 /分的振动频率振荡 15〜120分钟， 然后经去离子水洗涤后用高 纯氮气吹干。 光刻胶的清洗效果和清洗液对晶片的腐蚀情况如表 2所示。 表 2实施例对晶圆清洗情况
清洗 光刻胶
晶片清洗结果
温度 清洗时间
实施例
(。C) (min) Cu基材 光刻胶 金属微球
腐蚀情况 清洗结果 腐蚀情况
实施例 3 90 120 ◎ Δ ◎ 实施例 15 35 120 ◎ 〇 ◎ 实施例 16 90 120 ◎ ◎ O 实施例 17 80 120 ◎ ◎ ◎ 实施例 19 90 90 ◎ ◎ O 实施例 20 90 120 ◎ ◎ ◎ 实施例 21 90 90 ◎ ◎ ◎ 实施例 22 60 60 ◎ ◎ ◎ 实施例 23 65 105 ◎ ◎ ◎ 实施例 24 75 50 ◎ ◎ ◎ 实施例 25 90 15 ◎ 〇 ◎ 实施例 26 85 30 ◎ ◎ ◎ 实施例 27 55 60 ◎ ◎ ◎ 实施例 20 50 100 ◎ ◎ ◎ 实施例 27 25 120 ◎ 〇 ◎ ◎ 基本无腐蚀; ◎ 完全去除;
o 略有腐蚀； o 少量残余;
△ 中等腐蚀； Δ 较多残余;
X 严重腐蚀。 X 大量残余。
从表 2可以看出， 本发明的清洗液对厚膜光刻胶具有良好的清洗效果， 使用温度范围广， 同时对金属微球和金属铜等有较好的腐蚀抑制作用。

Claims

权利要求
1.一种光刻胶清洗液， 其包含：
( a)氢氧化钾，
( b ) 吡咯垸酮类溶剂，
( c )季戊四醇，
( d ) 醇胺，
( e ) 间苯二酚。
2.如权利要求 1所述的清洗液， 其特征在于： 所述的氢氧化钾的含量为 质量百分比 0.1〜10%。
3.如权利要求 1所述的清洗液， 其特征在于： 所述的吡咯垸酮类溶剂的 含量为质量百分比 10〜90%。
4.如权利要求 1所述的清洗液， 其特征在于： 所述的季戊四醇的含量为 质量百分比 0.1〜15%。
5.如权利要求 1所述的清洗液， 其特征在于： 所述的醇胺的含量为质量 百分比 0.1〜55%。
6.如权利要求 1所述的清洗液， 其特征在于： 所述的间苯二酚的含量为 质量百分比 0.1〜10%。
7.如权利要求 1所述的清洗液， 其特征在于： 所述的清洗液还包含其它 助溶剂。
8. 如权利要求 Ί所述的清洗液， 其特征在于： 所述的其它助溶剂的含 量为质量百分比不超过 85%。
9.如权利要求 1所述的清洗液， 其特征在于： 所述的吡咯垸酮类溶剂选 自 N-甲基吡咯烷酮、 N-乙基吡咯垸酮、 N-羟乙基吡咯垸酮和 N-环己基吡咯 烷酮中的一种或多种。
10. 如权利要求 1所述的清洗液， 其特征在于： 所述的醇胺选自单乙 醇胺、 二乙醇胺、 三乙醇胺、 正丙醇胺、 异丙醇胺、 2- (二乙氨基） 乙醇、 乙基二乙醇胺和二甘醇胺中的一种或几种。
11. 如权利要求 7所述的清冼液， 其特征在于： 所述的其它助溶剂选 自亚砜、 砜、 咪唑烷酮、 咪唑啉酮、 醇、 醚和酰胺中的一种或多种。
12. 如权利要求 11所述的清洗液， 其特征在于： 所述的亚砜为二甲基 亚砜； 所述的砜为环丁砜； 所述的咪唑烷酮为 1，3-二甲基 -2-咪唑垸酮； 所述 的咪唑啉酮为 1,3-二甲基 -2-咪唑啉酮；所述的酰胺为二甲基甲酰胺和 /或二甲 基乙酰胺； 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。
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