WO2023092278A1 - 一种清洗粘结层的组合物及其应用 - Google Patents

一种清洗粘结层的组合物及其应用 Download PDF

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Publication number
WO2023092278A1
WO2023092278A1 PCT/CN2021/132428 CN2021132428W WO2023092278A1 WO 2023092278 A1 WO2023092278 A1 WO 2023092278A1 CN 2021132428 W CN2021132428 W CN 2021132428W WO 2023092278 A1 WO2023092278 A1 WO 2023092278A1
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Prior art keywords
cleaning
composition
substrate
compound
residual glue
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PCT/CN2021/132428
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English (en)
French (fr)
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叶仁杰
林益升
蔡墨勋
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才将科技股份有限公司
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Priority to PCT/CN2021/132428 priority Critical patent/WO2023092278A1/zh
Publication of WO2023092278A1 publication Critical patent/WO2023092278A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a cleaning solution composition for cleaning the bonding layer; it adopts a chemical solvent formula that is harmless to the environment and the human body, and is used to remove the bonding layer composed of the adhesive used in the semiconductor manufacturing process, and will not corrode the semiconductor element cause damage.
  • the composition for cleaning the adhesive layer of the present invention can be applied to industries such as integrated circuits, wafer packaging, and printed circuit boards.
  • the bonding process is a step in the thinning of integrated circuit (IC) components in the semiconductor manufacturing process. It uses the front side of integrated circuit (IC) components (including metal lines, inorganic and organic materials)
  • IC integrated circuit
  • the ceramic substrate is temporarily bonded with an adhesive as a protective support for the integrated circuit (IC) component, and then the substrate on the back of the integrated circuit (IC) component is etched or ground until the substrate of the integrated circuit (IC) component is thinned
  • the integrated circuit (IC) element is separated from the protective substrate bonded by the temporary adhesive by means of laser dissociation, thermal dissociation, solvent dissociation or physical tearing. Since there will still be a large amount of residual glue on the surface of the separated component at this time, the residual adhesive on the surface of the component should be thoroughly cleaned with a cleaning solution, and the cleaning solution must not damage the integrated circuit and structure on the surface of the integrated circuit component.
  • TMAH tetramethylammonium hydroxide
  • KOH potassium hydroxide
  • MEA ethanolamine
  • the organic solvents used in the conventional binder cleaning liquid formula of the prior art are halogenated hydrocarbons, acetone (Acetone), toluene (Toluene), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP) , these traditional solvents have an excellent dissolution effect on binders or resin materials, but are prone to harm to human health or the environment.
  • acetone Acetone
  • Toluene toluene
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • trichlorethylene a halogenated hydrocarbon commonly used in cleaning agents, has an anesthetic effect on nerves.
  • the International Cancer Research Center (IARC) believes that trichlorethylene is a human carcinogen.
  • Acetone (Acetone) has a low flash point, and a large amount of it is likely to cause fire and industrial safety accidents.
  • Toluene has an excitatory effect on the central nervous system and the heart. Inhalation of toluene will produce pleasure, dizziness, fatigue, hand shaking, muscle weakness, affecting judgment, hallucinations, restlessness, amnesia symptoms, leading to vomiting, acidemia, kidney disease, etc. Failure, rhabdomyolysis, cardiac arrhythmia, bronchial inflammation or spasm, and pulmonary edema.
  • Dimethyl sulfoxide (DMSO) has good permeability, and when mixed with toxic substances, toxic substances can penetrate into the body of workers through the skin and respiratory tract.
  • NMP N-Methylpyrrolidone Due to the risk of health hazards, the European Chemical Agency (ECHA) has issued restrictions on N-Methylpyrrolidone (NMP) in 2018 (Regulation (EU) 2018/588). After May 9, 2020, unless manufacturers and downstream users take appropriate risk management measures and provide appropriate operating conditions to ensure that the exposure of workers is lower than the inhalation and exposure values, it is not allowed to manufacture or use containing A substance or mixture in a concentration equal to or greater than 0.3% (NMP).
  • the first object of the present invention is to provide a composition for cleaning an adhesive layer.
  • the composition for cleaning the adhesive layer includes N,N-dialkylamide compounds and cyclic compounds, and the cyclic compounds are cyclic ketone compounds, cyclic ester compounds or combinations thereof, and the composition Based on the total weight of the N,N-dialkylamide compound, the weight percentage is about 1-80wt.%, the weight percentage of the cyclic compound is about 20-99wt.%, and the composition The pH value is about 10 or less.
  • the N,N-dialkylamide compound used in the composition of the present invention has a weak alkalinity, and is especially suitable for decomposing or dissolving the adhesive layer, glue layer or residue formed by the resin used in the semiconductor bonding process (bonding process) Adhesive residue on semiconductor components or integrated circuits.
  • the N,N-dialkylamide compound comprises N,N-diethylformamide, N,N-diethylacetamide or N,N-dimethylacetamide.
  • the cyclic compound used in the composition of the present invention may remain on the adhesive layer, glue layer or residue on the semiconductor element or integrated circuit formed by the polyacrylic resin adhesive, epoxy resin adhesive, and phenolic resin adhesive.
  • the residual glue has excellent penetration, swelling, dilution, dissolution, and emulsification capabilities, and is suitable for use as a solvent component for cleaning the adhesive layer.
  • the cyclic compound comprises cyclopentanone, cyclohexanone, ⁇ -butyrolactone, ⁇ -valerolactone or a combination thereof.
  • the second object of the present invention is to provide a method for cleaning residual glue on the surface of a substrate or component, the steps of which include cleaning the substrate using the composition for cleaning the adhesive layer as described in the first object between room temperature and 90°C Or the residual glue on the surface of the component.
  • the material of the substrate or component includes copper, aluminum, tin, silicon, silicon oxide, gallium arsenide or a combination thereof.
  • the composition of the residual glue includes polyacrylic resin, epoxy resin, phenolic resin or its combination.
  • the above-mentioned method for cleaning the residual glue on the substrate or component surface has the advantage of not corroding the semiconductor element, and the residual glue will not produce sticking back after removal, so the composition for cleaning the adhesive layer provided by the present invention is easy Use, cleaning efficiency is fast and clean.
  • the third object of the present invention is to provide a method for preventing adhesive residue from sticking back to the surface of the substrate or component during the cleaning process, the steps of which include using the cleaning adhesive layer described in the first object between room temperature and 90°C
  • the composition cleans the residual glue on the surface of the substrate or component, thereby decomposing or dissolving the residual glue in the composition, and the material of the substrate or component includes copper, aluminum, tin, silicon, silicon oxide, gallium arsenide or its combination.
  • the composition of the residual glue includes polyacrylic resin, epoxy resin, phenolic resin or a combination thereof.
  • the composition for cleaning the adhesive layer of the present invention and the technical effects and means of its application include: the composition for cleaning the adhesive layer of the present invention adopts a composite solvent formula, does not contain strong alkaline compounds, and can quickly and effectively Decompose or dissolve the adhesive layer, adhesive layer or residual glue remaining on the semiconductor component or integrated circuit, and will not affect the semiconductor component and integrated circuit (copper, aluminum, tin, silicon, silicon oxide or arsenic) other than the adhesive layer Materials such as gallium chloride) cause corrosion.
  • the selected cyclic compound of the present invention has excellent penetration, swelling, dilution, dissolution to the adhesive layer formed by polyacrylic resin adhesive, epoxy resin adhesive, phenolic resin adhesive or its combination , emulsifying ability, especially suitable for cleaning the adhesive residue of the above adhesive layer or its composition.
  • the composition for cleaning the adhesive layer of the present invention uses a neutral slightly basic N,N-dialkylamide compound as one of the components, and controls its concentration to be less than or equal to 80wt.%, thereby avoiding Corrosion of semiconductor components or integrated circuits.
  • the present invention provides a composition for cleaning the adhesive layer, comprising N,N-dialkylamide compounds and cyclic compounds, the cyclic compounds are cyclic ketone compounds, cyclic Esters or combinations thereof, based on the total weight of the composition, the weight percentage of the N,N-dialkylamide compound is about 1-80 wt.%, and the weight percentage of the cyclic compound is about is 20-99wt.%, and the pH value of the composition is about 10 or less.
  • the N,N-dialkylamide compound comprises N,N-diethylformamide, N,N-diethylacetamide or N,N-dimethylacetamide.
  • the N,N-dialkylamide compound is N,N-diethylformamide (Diethylformamide).
  • the cyclic ketone compound comprises cyclopentanone or cyclohexanone.
  • the cyclic ester compound comprises ⁇ -butyrolactone or ⁇ -valerolactone.
  • the weight percentage of the N,N-dialkylamide compound is about 5-80 wt.%, and the weight percentage of the cyclic compound is about It is 20 to 95 wt.%.
  • the composition for cleaning the adhesive layer comprises 5-80wt.% of N,N-diethylformamide and 20-95wt.% of cyclohexanone or ⁇ -butyrolactone or its combination.
  • composition for cleaning the adhesive layer described in the first embodiment of the present invention includes: the advantage of not corroding the semiconductor element, the adhesive layer or adhesive layer or the residual glue remaining on the semiconductor element or integrated circuit After being removed by the composition of the present invention, sticking back will not occur, so the composition for cleaning the adhesive layer of the present invention is easy to use, the cleaning efficiency is fast and clean, and the operation flexibility is large.
  • the applicable temperature range is between room temperature and 90°C.
  • the present invention provides a method for cleaning residual glue on the surface of a substrate or component, the steps of which include using the combination of cleaning the adhesive layer as described in the first embodiment between room temperature and 90°C cleaning the residual glue on the surface of the substrate or component, and the material of the substrate or component includes copper, aluminum, tin, silicon, silicon oxide, gallium arsenide or a combination thereof.
  • the adhesive residue comprises polyacrylic resin, epoxy resin, phenolic resin or a combination thereof.
  • the method for cleaning the residual glue on the surface of the substrate or component is applied to the cleaning process of semiconductors or circuit boards, thereby preventing the above-mentioned substrate or component or integrated circuit from being damaged during the cleaning process. corrosion.
  • the experiment of the present invention proves that the higher the concentration of N,N-dialkylamide compound, the greater the degree of corrosion of copper.
  • N,N- The dialkylamide compound concentration needs to be controlled at about 80 wt.% or less.
  • the N,N-diethylformamide (DEF) used in the present invention is a neutral organic solvent with a slight alkalinity, which utilizes the nature of the weak alkalinity of the amide to decompose or dissolve the adhesive layer
  • the composition or structure of the resin makes it lose its viscosity and avoid the phenomenon of residual glue sticking back. It has been confirmed by experiments of the present invention that when N,N-diethylformamide (DEF) is dissolved in an organic solvent, especially a cyclic organic solvent, it can effectively maintain N,N-diethylformamide (DEF) with an amide functional group.
  • the weak alkalinity of DEF makes N,N-diethylformamide (DEF) or its composition with cyclic compounds not harmful to copper, aluminum, tin, silicon, silicon oxide or Materials such as gallium arsenide cause corrosion, and the organic solvent will not affect the ability of N,N-diethylformamide (DEF) to decompose or dissolve the resin composition or structure of the bonding layer, so the compound formulation of the present invention can Prevent the phenomenon of sticking back of residual glue, and will not corrode semiconductor components and integrated circuits.
  • the concentration of N,N-diethylformamide needs to be limited, and its concentration should be controlled at about 80wt.% or below, because when N,N - If the concentration of diethylformamide is greater than 80%wt., the copper material of the integrated circuit will be corroded, and as the concentration of N,N-diethylformamide increases, the degree of corrosion of copper will also increase. In order to prevent the composition of the present invention from corroding semiconductor elements and integrated circuits, the concentration of N,N-diethylformamide needs to be controlled at or below about 80 wt.%.
  • the present invention provides a method for preventing adhesive residue from sticking back to the surface of the substrate or component during the cleaning process, the steps of which include using the method as described in the first embodiment between room temperature and 90°C.
  • the composition for cleaning the bonding layer cleans the residual glue on the surface of the substrate or component, thereby decomposing or dissolving the residual glue in the composition, and the material of the substrate or component includes copper, aluminum, tin, silicon, silicon oxide , gallium arsenide or combinations thereof.
  • the adhesive residue comprises polyacrylic resin, epoxy resin, phenolic resin or a combination thereof.
  • the composition for cleaning the adhesive layer of the present invention and the technical effects and means of its application include: the composition for cleaning the adhesive layer of the present invention adopts a composite solvent formula, does not contain strong alkaline compounds, and can quickly and effectively Decompose or dissolve the bonding layer, and will not cause corrosion to semiconductor components and integrated circuits (copper, aluminum, tin, silicon, silicon oxide, gallium arsenide and other materials) other than the bonding layer.
  • the selected cyclic ketone compound or cyclic ester compound of the present invention is suitable for polyacrylic resin adhesives, epoxy resin adhesives, phenolic resin adhesives or combinations thereof With excellent penetrating, swelling, diluting, dissolving and emulsifying abilities, it is especially suitable for cleaning the residual glue of the above-mentioned adhesives or their components.
  • the composition for cleaning the adhesive layer of the present invention uses a neutral slightly basic N,N-dialkylamide compound as one of the components, and controls its concentration to be less than or equal to 80wt.%, thereby avoiding Corrosion of the copper material of the integrated circuit.
  • compositions for cleaning the bonding layer of the present invention will be described in detail below by means of specific preferred embodiments and comparative examples.
  • the compositions of each embodiment and comparative example were prepared using the ingredients and their ratios shown in Table 1.
  • GBL Gamma-Butyrolactone
  • DMSO Dimethyl sulfoxide
  • Toluene toluene (Methylbenzene).
  • BDG diethylene glycol monobutyl ether (2-(2-Butoxyethoxy)ethanol).
  • TMAH Tetramethylammonium hydroxide (Tetramethylammonium hydroxide), the pH value of 1wt.% aqueous solution is 12.9, which is a strong base with the same strength as caustic alkali.
  • MEA monoethanolamine (Monoethanolamine), the pH value of 10wt.% aqueous solution is 12.1.
  • BDG diethylene glycol monobutyl ether (2-(2-Butoxyethoxy)ethanol).
  • test pieces were immersed in the constant temperature cleaning solution containing the ingredients of each example and comparative example in sequence according to the temperature and time set in the operating conditions in Table 2, and left to soak for 2 minutes. After the time was over, they were quickly removed from the cleaning solution.
  • the composition of the present invention Compared with the adhesive layer cleaning composition used and the prior art mixed organic solvent and alkaline compound, the composition of the present invention has an excellent effect of cleaning the adhesive layer.
  • Silicon wafers gallium arsenide wafers, copper film wafers, aluminum film wafers, tin
  • Spherical wafers and silicon dioxide membrane wafers were cut into test pieces of about 20mm x 20mm in size, soaked in the 80°C constant temperature cleaning solution containing the ingredients of each example and comparative example in sequence, and left to soak for 30 minutes. At the end, quickly remove the test piece from the cleaning solution, immediately rinse the test piece with deionized water for 30 seconds, and then dry the test piece with clean and dry compressed air (CDA). Observe the thickness change of the test piece material by scanning electron microscope (SEM) or measure the film thickness change by using ellipsometer (Ellipsometer) to judge the damage condition of the material on the surface of the wafer. The corrosion resistance test results of the substrate are shown in Table 3 below.
  • composition of the bonding layer cleaning solution used in the method will not cause corrosion to the substrates used in semiconductor components, including copper, aluminum, tin, silicon, silicon oxide and gallium arsenide.
  • traditional cleaning solutions that mix organic solvents and alkaline compounds can cause substrate corrosion. Accordingly, the composition for cleaning the bonding layer of the present invention does have unexpected technical effects compared with the traditional cleaning solution mixed with an organic solvent and an alkaline compound.

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Abstract

本发明揭露一种清洗粘结层的组合物及其应用，适用于半导体或印刷电路板制程。以该组合物的总重量计，其包含约1重量％至约80重量％的N,N-二烷基酰胺化合物和约20重量％至约99重量％的环状酮或环状酯类化合物，且该组合物的酸碱值约等于或小于10。

Description

一种清洗粘结层的组合物及其应用 技术领域
本发明是关于一种清洗粘结层的清洗液组合物；采对环境和人体较无害的化学溶剂配方，用于去除半导体制程使用的粘着剂构成的粘结层，不会对半导体元件腐蚀造成受损。本发明的清洗粘结层的组合物可应用于集成电路、晶圆封装、印刷电路板等产业。
背景技术
接合制程(bonding process)是半导体制造过程中做为集成电路(IC)元件薄化的一个步骤，利用将集成电路(IC)元件的正面(包含金属线路、无机、有机材料)与另外一片玻璃或陶瓷基板以粘结剂暂时接合作为集成电路(IC)元件的保护支撑，然后对集成电路(IC)元件背面的底材进行蚀刻或研磨作业，直到集成电路(IC)元件的底材完成薄化后，再用激光解离、热熔解离、溶剂解离或物理撕裂等方式将集成电路(IC)元件与暂时粘结剂接合的保护基板分离。由于此时分离后的元件表面仍会留有大量残胶，所以要使用清洗液彻底洗净元件表面残留的粘结剂，并且清洗液必须不能伤害集成电路元件表面的集成线路和结构。
传统的粘结剂清洗剂一般是由有机溶剂与碱性化合物组合而成。选用极性与粘结剂相近的有机溶剂，可以对粘结剂产生渗透、膨润、分散的作用，达到清洗目的，再利用碱性化合物，破坏粘结剂的分子结构使失去粘性，避免粘结剂溶解后回沾到元件表面。常用的碱性化合物为四甲基氢氧化铵(TMAH)、氢氧化钾(KOH)或乙醇胺(MEA)。但是碱性化合物使用在半导体制程时，集成电路元件表面露出的集成线路会受到碱性化合物腐蚀，造成集成电路元件损坏。
现有习知技术常用的粘结剂清洗液配方所用的有机溶剂是卤化碳氢化 合物、丙酮(Acetone)、甲苯(Toluene)、二甲基亚砜(DMSO)和N-甲基吡咯烷酮(NMP)，这些传统溶剂对粘结剂或树酯材料具有优异溶解效果，但是对人体健康或环境容易产生危害。例如清洗剂常用的卤化碳氢化合物三氯乙烯，对神经有麻醉作用，国际癌症研究中心(IARC)认为三氯乙烯是人类致癌物。丙酮(Acetone)闪火点低，大量使用容易造成火警工安意外。甲苯(Toluene)对中枢神经及心脏有兴奋作用，吸入甲苯会产生快感，头晕、倦怠感、手抖、肌肉无力、影响判断力、幻觉、躁动不安、失忆症状，导致呕吐、酸血症、肾衰竭、横纹肌溶解症、心律不整、支气管发炎或痉挛、及肺水肿等。二甲基亚砜(DMSO)有良好渗透性，与毒性物质混和可将毒性物质经由皮肤、呼吸道渗透进作业人员的身体。尤其在高温、抽气环境不佳的工作场所或洗涤设备不完善的厂务区，二甲基亚砜(DMSO)的「毒性放大特性」会危害作业人员健康产生慢性伤害。N-甲基吡咯烷酮(NMP)因健康危害风险，欧盟化学署(ECHA)2018年已针对N-甲基吡咯烷酮(NMP)颁布限制(法规编号Regulation(EU)2018/588)。自2020年5月9日以后，除非制造商和下游使用者采取适当的风险管理措施并提供适当的操作条件，确保作业人员的暴露量低于吸入与接触量值规定，否则不得制造或使用含有浓度等于或大于0.3％(NMP)的物质或混合物。
综上所述，开发一种环保的粘结层清洗液组合物，其组成不能含有毒性或关注化学物质，避免对人员及环境形成危害，又具有高效能清洗效果，且对半导体元件及集成线路不会造成腐蚀，进而提升半导体清洗制程的良率，实为现今半导体清洗制程亟需发展和突破的技术领域。
发明内容
鉴于上述的发明背景，为了符合产业上的要求，本发明的第一目的在于提供一种清洗粘结层的组合物。具体的，该清洗粘结层的组合物包含N,N-二烷基酰胺化合物和环状化合物，该环状化合物是环状酮类化合物、环状酯类化合物或其组合，以该组合物的总重量计，该N,N-二烷基酰胺化合物 的所占的重量百分比约是1～80wt.％，该环状化合物所占的重量百分比约是20～99wt.％，和该组合物的酸碱值约小于或等于10。
本发明组合物所使用的N,N-二烷基酰胺化合物具有微弱碱性，特别适合用于分解或溶解半导体接合制程(bonding process)所使用的树脂形成的粘结层、胶层或残留在半导体元件或集成电路上的残胶。具体地，该N,N-二烷基酰胺化合物包含N,N-二乙基甲酰胺、N,N-二乙基乙酰胺或N,N-二甲基乙酰胺。
另一方面，本发明组合物使用的环状化合物对聚丙烯酸树脂粘结剂、环氧树脂粘结剂及酚醛树脂粘结剂形成的粘结层、胶层或残留在半导体元件或集成电路上的残胶具有优异的渗透、膨润、稀释、溶解、乳化能力，适合用来作为清洗粘结层的溶剂成分。具体地，该环状化合物包含环戊酮、环己酮、γ-丁内酯、δ-戊内酯或其组合。
本发明的第二目的在于提供一种清洗基材或元件表面残胶的方法，其步骤包含在室温到90℃之间使用如第一目的所述的清洗粘结层的组合物清洗该基材或元件表面的残胶，该基材或元件的材质包含铜、铝、锡、硅、氧化硅、砷化镓或其组合，该残胶的组成包含聚丙烯酸树脂、环氧树脂、酚醛树脂或其组合。
具体地，上述的清洗基材或元件表面残胶的方法具有不会腐蚀半导体元件的优点，并且该残胶在去除后不会产生回沾，因此本发明提供的清洗粘结层的组合物容易使用，清洗效率快速干净。
本发明的第三目的在于提供一种防止残胶在清洗制程中回沾到基材或元件表面的方法，其步骤包含在室温到90℃之间使用如第一目的所述的清洗粘结层的组合物清洗该基材或元件表面的残胶，借此分解或溶解该残胶于该组合物，该基材或元件的材质包含铜、铝、锡、硅、氧化硅、砷化镓或其组合。具体地，该残胶的组成包含聚丙烯酸树脂、环氧树脂、酚醛树脂或其组合。
根据上述发明内容，本发明的清洗粘结层的组合物和其应用的技术功 效和手段包含：本发明的清洗粘结层的组合物采复合溶剂配方，不含强碱性化合物，能够迅速有效分解或溶解粘结层、胶层或残留在半导体元件或集成电路上的残胶，并且不会对该粘结层以外的半导体元件和集成线路(铜、铝、锡，硅，氧化硅或砷化镓等材料)造成腐蚀。第二，本发明所选的环状化合物对聚丙烯酸树脂粘结剂、环氧树脂粘结剂、酚醛树脂粘结剂或其组合所组成的胶层具有优异的渗透、膨润、稀释、溶解、乳化能力，特别适合用来作为清洗上述粘结层或其组成的残胶。第三，本发明的清洗粘结层的组合物使用中性带有微弱碱性的N,N-二烷基酰胺化合物作为组成之一，并且控制其浓度小于或等于80wt.％，借此避免对半导体元件或集成线路造成腐蚀。
具体实施方式
有关本发明的前述及其他技术内容、特点与功效，在以下配合参考较佳实施例的详细说明中将可清楚的呈现。为了能彻底地了解本发明，将在下列的描述中提出详尽的步骤及其组成。显然地，本发明的施行并未限定于该领域的技艺者所熟习的特殊细节。另一方面，众所周知的组成或步骤并未描述于细节中，以避免造成本发明不必要的限制。本发明的较佳实施例会详细描述如下，然而除了这些详细描述之外，本发明还可以广泛地施行在其他的实施例中，且本发明的范围不受限定，其以之后的专利范围为准。
根据本发明的第一实施例，本发明提供一种清洗粘结层的组合物，包含N,N-二烷基酰胺化合物和环状化合物，该环状化合物是环状酮类化合物、环状酯类化合物或其组合，以该组合物的总重量计，该N,N-二烷基酰胺化合物的所占的重量百分比约是1～80wt.％，该环状化合物所占的重量百分比约是20～99wt.％，和该组合物的酸碱值约小于或等于10。
在一具体实施例，该N,N-二烷基酰胺化合物包含N,N-二乙基甲酰胺、N,N-二乙基乙酰胺或N,N-二甲基乙酰胺。较佳的，该N,N-二烷基酰胺化合 物是N,N-二乙基甲酰胺(Diethylformamide)。
在一具体实施例，该环状酮类化合物包含环戊酮或环己酮。
在一具体实施例，该环状酯类化合物包含γ-丁内酯或δ-戊内酯。
在一具体实施例，以该组合物的总重量计，该N,N-二烷基酰胺化合物的所占的重量百分比约是5～80wt.％，和该环状化合物所占的重量百分比约是20～95wt.％。
在一代表实施例，所述的清洗粘结层的组合物包含5～80wt.％的N,N-二乙基甲酰胺和20～95wt.％的环己酮或γ-丁内酯或其组合。
本发明第一实施例所述的清洗粘结层的组合物具有的技术特征包含：具有不会腐蚀半导体元件的优点、粘结层或胶层或残留在半导体元件或集成电路上的残胶在使用本发明组合物去除后不会产生回沾，所以本发明的清洗粘结层的组合物容易使用，清洗效率快速干净和操作弹性大，适用温度范围是室温到90℃之间。
根据本发明的第二实施例，本发明提供一种清洗基材或元件表面残胶的方法，其步骤包含在室温到90℃之间使用如第一实施例所述的清洗粘结层的组合物清洗该基材或元件表面的残胶，该基材或元件的材质包含铜、铝、锡、硅、氧化硅、砷化镓或其组合。
在一具体实施例，该残胶的组成包含聚丙烯酸树脂、环氧树脂、酚醛树脂或其组合。
在一具体实施例，所述的清洗基材或元件表面残胶的方法，是应用于半导体或电路板的清洗制程，借此防止在该清洗制程中造成上述的基材或元件或集成电路的腐蚀。
在一具体实施例，经过本发明实验证实N,N-二烷基酰胺化合物浓度愈高，腐蚀铜的程度也会变大，为避免本发明对半导体元件和集成线路造成腐蚀，N,N-二烷基酰胺化合物浓度需要控制在约80wt.％或以下。
在一代表实施例，本发明使用的N,N-二乙基甲酰胺(DEF)是一种中性带有微弱碱性的有机溶剂，利用酰胺具有微弱碱性的性质分解或溶解粘结层 的树脂组成或结构，使其失去粘性，避免发生残胶回沾的现象。经本发明实验证实N,N-二乙基甲酰胺(DEF)溶于有机溶剂时，特别是环状类有机溶剂，其可以有效维持具有酰胺官能基的N,N-二乙基甲酰胺(DEF)的微弱碱性，使N,N-二乙基甲酰胺(DEF)或其和环状类化合物的组合物不会对半导体元件或集成线路的铜、铝、锡、硅、氧化硅或砷化镓等材料造成腐蚀，并且该有机溶剂不会影响N,N-二乙基甲酰胺(DEF)对粘结层的树脂组成或结构产生分解或溶解的能力，所以本发明的复合配方可以防止残胶的回沾现象发生，也不会腐蚀半导体元件和集成线路。但是若要能够分解或溶解粘结层并且达到保护半导体元件的效果，N,N-二乙基甲酰胺的浓度需要受到限制，其浓度要控制在约80wt.％或以下，因为当N,N-二乙基甲酰胺浓度大于80％wt.以上，对集成线路的铜材料会造成腐蚀，且随着N,N-二乙基甲酰胺浓度愈高，腐蚀铜的程度也会变大。为了避免本发明的组合物对半导体元件和集成线路造成腐蚀，N,N-二乙基甲酰胺浓度需要控制在约80wt.％或以下。
根据本发明的第三实施例，本发明提供一种防止残胶在清洗制程中回沾到基材或元件表面的方法，其步骤包含在室温到90℃之间使用如第一实施例所述的清洗粘结层的组合物清洗该基材或元件表面的残胶，借此分解或溶解该残胶于该组合物，该基材或元件的材质包含铜、铝、锡、硅、氧化硅、砷化镓或其组合。
在一具体实施例，该残胶的组成包含聚丙烯酸树脂、环氧树脂、酚醛树脂或其组合。
根据上述实施例，本发明的清洗粘结层的组合物和其应用的技术功效和手段包含：本发明的清洗粘结层的组合物采复合溶剂配方，不含强碱性化合物，能够迅速有效分解或溶解粘结层，并且不会对粘结层以外的半导体元件和集成线路(铜、铝、锡，硅，氧化硅和砷化镓等材料)造成腐蚀。第二，本发明所选的环状酮类化合物或环状酯类化合物对聚丙烯酸树脂粘结剂、环氧树脂粘结剂、酚醛树脂粘结剂或其组合所组成的胶层或残胶具有 优异的渗透、膨润、稀释、溶解、乳化能力，特别适合用来作为清洗上述粘结剂或其组成的残胶。第三，本发明的清洗粘结层的组合物使用中性带有微弱碱性的N,N-二烷基酰胺化合物作为组成之一，并且控制其浓度小于或等于80wt.％，借此避免对集成线路的铜材料造成腐蚀。
以下借由具体的优选实施例及比较例详细说明本发明清洗粘结层的组合物的技术效果。利用表一所示的成份及其比例来配制各实施例和比较例的组合物。
表一
成份 DEF ANONE GBL DMSO Toluene BDG TMAH MEA
实施例1 1 30 69          
实施例2 5 30 65          
实施例3 5 60 35          
实施例4 10 30 60          
实施例5 10 60 30          
实施例6 10   90          
实施例7 20   80          
实施例8 40   60          
实施例9 60   40          
实施例10 80   20          
比较例1 100              
比较例2   100            
比较例3     100          
比较例4       100        
比较例5         100      
比较例6           100    
比较例7       92     2  
比较例8         80     20
比较例9           70   30
比较例10               100
表一数字的单位是重量百分比，英文缩写对应的化合物如下所述。
DEF：N,N-二乙基甲酰胺(N,N-diethylformamide)。
ANONE：环己酮(Cyclohexanone)。
GBL：γ-丁内酯(Gamma-Butyrolactone)。
DMSO：二甲基亚砜(Dimethyl sulfoxide)。
Toluene：甲苯(Methylbenzene)。
BDG：二乙二醇单丁醚(2-(2-Butoxyethoxy)ethanol)。
TMAH：四甲基氢氧化铵(Tetramethylammonium hydroxide)，1wt.％水溶液PH值为12.9，是与苛性碱同等强度的强碱。
MEA：单乙醇胺(Monoethanolamine)，10wt.％水溶液PH值是12.1。
BDG：二乙二醇单丁醚(2-(2-Butoxyethoxy)ethanol)。
粘结层洗净效果及基材耐蚀性检验
针对实施例与比较例的清洗液成份组合进行效能评价，通过如下技术手段，以「粘结剂洗净能力」与「基材耐蚀性」两个项目来实施。
清洗粘结层能力检测
将液态聚丙烯酸树脂粘结剂均匀涂布在硅晶圆基材表面，放进温度120℃烘箱加热烘烤5分钟，使晶圆表面的粘结剂干燥及硬化，取出烘箱后再把晶圆裁成约20mm x 20mm大小的试片，作为试验粘结层洗净效果的样本。上述试片依照表二操作条件所订定的温度和时间，依序分别浸泡于含有各实施例及比较例成份的恒温清洗液中，静置浸泡时间2分钟，时间结束就迅速从清洗液中取出试片，用去离子水连续冲洗试片30秒，再以干净干燥压缩空气(CDA)吹干试片。通过目视比较及光学显微镜观察试片表面是否有未洗净的粘结剂残留，结果如下表二所示。
表二
Figure PCTCN2021132428-appb-000001
Figure PCTCN2021132428-appb-000002
*评判标准：○表示显微镜观察粘结剂清洗干净，
没有残留。△表示目视粘结剂大部份清洗干净，仍有少数残留。X表示目视粘结剂大部份保持原状，没有清洗。
经由以上表二的测试结果可知，本发明在实施例中
所使用的粘结层清洗组合物和现有习知技术混合有机溶剂与碱性化合物比较，本发明的组合物具有优异的洗净粘结层效果。
基材耐蚀性检测
把硅晶片、砷化镓晶片，铜膜晶片、铝膜晶片，锡
球晶片，二氧化硅膜晶片，各别裁成约20mm x 20mm大小的试片，依序分别浸泡于含有各实施例及比较例成份的80℃恒温清洗液中，静置浸泡30分钟，时间结束要迅速从清洗液中取出试片，立即用去离子水连续冲洗试片30秒，再以干净干燥压缩空气(CDA)吹干试片。通过扫描式电子显微镜(SEM)观测试片材料厚度变化或使用椭圆偏光仪(Ellipsometer)测量膜厚变化，评判晶片表面的材料受损状况，基材耐蚀性检测结果如以下表三所示。
表三
Figure PCTCN2021132428-appb-000003
Figure PCTCN2021132428-appb-000004
评判标准：○表示表面无腐蚀。X表示表面发生腐
蚀或膜厚变薄。
由以上表三所示的检测结果可知，本发明在实施例
中所使用的粘结层清洗液的组合物，对半导体元件使用的基材，包含铜、铝、锡，硅，氧化硅和砷化镓等材料皆不会造成腐性现象。而传统混合有机溶剂与碱性化合物的清洗液则会造成基材腐蚀。据此，本发明的清洗粘结层的组合物相较于传统的混合有机溶剂与碱性化合物的清洗液确实具有现有习知技术无法预期的技术功效。
以上虽以特定实验例说明本发明，但并不因此限定
本发明的范围，只要不脱离本发明的要旨，熟悉本技艺者了解在不脱离本发明的意图及范围下可进行各种变形或变更。此外，摘要部分和标题仅是用来辅助专利文件搜寻之用，并非用来限制本发明的权利范围。

Claims (10)

  1. 一种清洗粘结层的组合物，其特征在于，包含N,N-二烷基酰胺化合物和环状化合物，该环状化合物是环状酮类化合物、环状酯类化合物或其组合，以该组合物的总重量计，该N,N-二烷基酰胺化合物的所占的重量百分比约是1～80wt.％，该环状化合物所占的重量百分比约是20～99wt.％，和该组合物的酸碱值约小于或等于10。
  2. 根据权利要求1所述的组合物，其特征在于，该N,N-二烷基酰胺化合物包含N,N-二乙基甲酰胺、N,N-二乙基乙酰胺或N,N-二甲基乙酰胺。
  3. 根据权利要求1所述的组合物，其特征在于，该环状酮类化合物包含环戊酮或环己酮。
  4. 根据权利要求1所述的组合物，其特征在于，该环状酯类化合物包含γ-丁内酯或δ-戊内酯。
  5. 根据权利要求1所述的组合物，其特征在于，该N,N-二烷基酰胺化合物的所占的重量百分比约是5～80wt.％，和该环状化合物所占的重量百分比约是20～95wt.％。
  6. 一种清洗基材或元件表面残胶的方法，其特征在于，其步骤包含在室温到90℃之间使用如权利要求1～5所述的清洗粘结层的组合物清洗该基材或元件表面的残胶，该基材或元件的材质包含铜、铝、锡、硅、氧化硅、砷化镓或其组合。
  7. 根据权利要求6所述的清洗基材或元件表面残胶的方法，其特征在于，该残胶的组成包含聚丙烯酸树脂、环氧树脂、酚醛树脂或其组合。
  8. 根据权利要求6所述的清洗基材或元件表面残胶的方法，其特征在于，是应用于半导体或电路板的清洗制程，借此防止在上述的清洗制程中造成基材、元件或集成电路的腐蚀。
  9. 一种防止残胶在清洗制程中回沾到基材或元件表面的方法，其特征在于，其步骤包含在室温到90℃之间使用如权利要求1～5所述的清洗粘结 层的组合物清洗该基材或元件表面的残胶，借此溶解该残胶于该组合物，该基材或元件的材质包含铜、铝、锡、硅、氧化硅、砷化镓或其组合。
  10. 根据权利要求9所述的防止残胶在清洗制程中回沾到基材或元件表面的方法，其特征在于，该残胶的组成包含聚丙烯酸树脂、环氧树脂、酚醛树脂或其组合。
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