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WO2007068176A1 - A system of corrosion inhibitor for cleaning semiconductor wafets - Google Patents

A system of corrosion inhibitor for cleaning semiconductor wafets Download PDF

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Publication number
WO2007068176A1
WO2007068176A1 PCT/CN2006/002622 CN2006002622W WO2007068176A1 WO 2007068176 A1 WO2007068176 A1 WO 2007068176A1 CN 2006002622 W CN2006002622 W CN 2006002622W WO 2007068176 A1 WO2007068176 A1 WO 2007068176A1
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WO
WIPO (PCT)
Prior art keywords
corrosion inhibitor
acid
inhibitor system
carboxyl group
small molecule
Prior art date
Application number
PCT/CN2006/002622
Other languages
French (fr)
Chinese (zh)
Inventor
Bing Liu
Libbert Hongxiu Peng
Shumin Wang
Original Assignee
Anji Microelectronics (Shanghai) Co., Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anji Microelectronics (Shanghai) Co., Ltd filed Critical Anji Microelectronics (Shanghai) Co., Ltd
Publication of WO2007068176A1 publication Critical patent/WO2007068176A1/en

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Classifications

    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • 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
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, 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
    • 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
    • C11D7/263—Ethers
    • 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
    • C11D7/267—Heterocyclic 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
    • 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
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3263—Amides or imides
    • 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 corrosion inhibitor system for semiconductor wafer cleaning in a semiconductor fabrication process.
  • 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).
  • the ion bombardment hardens the photoresist layer polymer during the doping step, thus making the photoresist layer less soluble and more difficult to remove.
  • this layer of photoresist film has been removed by a two-step process (dry ashing and wet etching).
  • the first step utilizes dry ashing to remove most of the photoresist layer;
  • the second step utilizes the corrosion inhibitor composition wet etch/clean process to remove and clean away the remaining photoresist layer.
  • the corrosion inhibitor composition can only remove the polymer photoresist layer (PR) and the inorganic residue, and cannot attack the damaged metal layer such as the aluminum layer, which usually takes a long time;
  • PR polymer photoresist layer
  • the inorganic residue In order to facilitate the removal of the photoresist layer, it is often required to carry out at a high temperature.
  • 6030932 (Leon, Olin) and US 6,635,186 (Small, EKC) and other patents disclose some corrosion inhibitor compositions for wet etching removal of photoresist layers, including corrosion inhibitor compositions including catechol or 8-hydroxyl groups. Toxic substances such as quinoline. Although these corrosion inhibitor compositions containing catechol or its derivatives, 8-hydroxyquinoline or other corrosion inhibitors have good corrosion inhibition effects, the corrosion inhibitor compositions are generally high in concentration and highly toxic, and need to be When used at high temperatures, it is not friendly to the environment, causing great harm to human health. Therefore, it is urgent to develop a new type of corrosion inhibition system. Summary of invention
  • the corrosion inhibitor system for semiconductor wafer cleaning of the present invention comprises a carboxyl group-containing polymer which can inhibit corrosion of a metal such as A1 or the like, or a non-metal Si, or a non-metal oxide SiO 2 , etc.;
  • the carboxyl group-containing polymer in the agent system can function as a corrosion inhibitor, a surfactant, a chelating agent, etc.;
  • the corrosion inhibitor system for semiconductor wafer cleaning of the present invention is not only environmentally friendly, safe and non-toxic, and has It is good for health; and it has a good inhibitory effect in both fluorine-containing and fluorine-free systems; the use of the corrosion inhibitor system of the present invention can reduce the etching rate of aluminum and hardly attack 0 2 and Si.
  • the corrosion inhibitor system for semiconductor wafer cleaning of the present invention can be used between room temperature and 85 ° C and can be used in recycling systems, sputtering tools, and single wafer processing.
  • the carboxyl group-containing polymer is a carboxyl group-containing homopolymer and/or a carboxyl group-containing copolymer and/or a carboxyl group-containing homopolymer salt and/or a carboxyl group-containing copolymer salt.
  • the carboxyl group-containing homopolymer is polymaleic anhydride (HPMA), polyacrylic acid (PAA) and/or polymethacrylic acid, preferably polymaleic anhydride and/or Polyacrylic acid;
  • the carboxyl group-containing copolymer is a copolymer between carboxyl group-containing monomers (eg, acrylic acid and maleic acid copolymer, methacrylic acid and horse) An acid copolymer), or a copolymer between a vinyl monomer and a carboxyl group-containing monomer (eg, a copolymer of styrene and acrylic acid, a copolymer of styrene and maleic acid, a copolymer of acrylonitrile and maleic acid, Copolymer of ethylene and acrylic acid, copolymer of acrylonitrile and acrylic acid, copolymer of styrene and methacrylic acid, copo
  • the molecular weight of the carboxyl group-containing polymer does not affect the object of the present invention. If the corrosion inhibitor system of the present invention has a certain concentration of polymer, the corrosion inhibitor system also It should have a certain concentration of carboxyl groups.
  • the concentration of the carboxyl group on the polymer is preferably 25 ⁇ ! ⁇ 50,000ppm.
  • the corrosion inhibitor system may further comprise a small molecule acid and/or a small molecule base.
  • the small molecule acid may be various small molecule acids, preferably organic acids, more preferably small molecule acids containing mono or polycarboxy groups; the organic acid is preferably 2-phosphonium 2-phosphonate-1,2,4-tricarboxylate Acid (PBTCA;), oxalic acid (OA), citric acid and/or gallic acid, more preferably butane-1,2,4-tricarboxylic acid (PBTCA) and/or oxalic acid.
  • PBTCA 2-phosphonium 2-phosphonate-1,2,4-tricarboxylate Acid
  • OA oxalic acid
  • citric acid and/or gallic acid more preferably butane-1,2,4-tricarboxylic acid (PBTCA) and/or oxalic acid.
  • the small molecule base may be a variety of small molecule bases, preferably a small molecule base containing a mono or polyhydroxy group, more preferably aqueous ammonia and/or tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • the concentration of the carboxyl group-containing polymer may be various concentrations, preferably 0.00001 to 10%, more preferably 0.01 to 3%; and the concentration of the small molecule acid and/or small molecule base is preferably 0 to 10%, more preferably 0 to 5%; the concentration of the water and/or solvent may be various concentrations in the prior art, preferably 80 to 99.99999%, more preferably 92 to 99.99%, and the above concentrations are all The mass concentration of the corrosion inhibitor system.
  • the solvent means an organic solvent, and may be various organic solvents or a mixture thereof, such as: N-methylpyrrolidone (NMP), Y-butyrolactone (GBL), N, N- Dimethylacetamide (DMAC), diethylene glycol monobutyl ether (DGMBE) and/or ethanolamine (EA), more preferably NMP, DGMBE and/or EAo
  • NMP N-methylpyrrolidone
  • GBL Y-butyrolactone
  • DMAC N- Dimethylacetamide
  • DGMBE diethylene glycol monobutyl ether
  • EA ethanolamine
  • the corrosion inhibitor system for semiconductor wafer cleaning of the present invention may also include other corrosion inhibitors, surfactants, and/or chelating agents.
  • the positive progress of the present invention is that the corrosion inhibitor system for semiconductor wafer cleaning of the present invention has the characteristics of being environmentally friendly, safe, non-toxic and health-friendly, and can be used between room temperature and 85 ° C, and Both fluorine and fluorine-free systems have good inhibitory effects on metals or non-metals. Summary of the invention
  • Polymer I Deionized water; NA is not added to the ⁇ .
  • DI Deionized water
  • NA is not added to this ingredient.
  • Rate represents the etch rate; the etch rate is negative, indicating that the etch rate is almost zero.
  • the corrosion inhibitor system has a relatively good corrosion inhibition effect.
  • the corrosion rate of the corrosion inhibitor system containing no carboxyl group-containing polymer on the blank A1 wafer is greater than 2.0 A/min; the carboxyl group-containing of the present invention
  • the polymer corrosion inhibitor system is used to clean the blank Al wafer.
  • the A1 etching rate is less than 2.0 A/min, which can significantly reduce the etching rate of A1, even reaching 0 A/min, completely inhibiting the A1 corrosion. Therefore, the corrosion inhibitor system of the carboxyl group-containing polymer of the present invention can significantly inhibit A1 corrosion, thereby facilitating effective removal of organic residues and/or inorganic residues of the photoresist layer of the A1 wafer.
  • Example 4 corrosion inhibitor system was used to clean the etched blank Si0 2 wafer, test method and conditions: 25 ° C, shaker 60 rpm, time 30 minutes, using NANOSPEC film thickness gauge (purchased in NANO Metrics) measured the etch rate of the surface film thickness change before and after etching of the Si0 2 wafer.
  • NANOSPEC film thickness gauge purchased in NANO Metrics
  • the etch rate of Si0 2 was 0.78A / min, the etching rate which is less than 2A / min, described corrosion inhibitor system of the present invention may also inhibit the corrosion Si0 2.
  • Comparative Example 4 The system of Comparative Example 4 and the corrosion inhibitor system of Examples 15 to 22 were used to clean the etched blank A1 wafer. Test methods and conditions: 25 ° C, shaker 60 rpm, time 30 minutes. The etching rate was calculated by testing the surface resistance change before and after etching by a quadrupole prober. The results are shown in Table 4.
  • fluoride is commonly used to assist in the removal of residues on the wafer, but fluoride also tends to increase the rate of metal etch.
  • the corrosion inhibitor system of the present invention is used for cleaning the blank A1 wafer, and the etching rate of A1 is also small, and the etching rate of A1 can also be reduced to 2.0 A/min or less. Even a corrosion inhibitor system containing only a carboxyl group-containing polymer and no small molecular acid and small molecule base (as in Example 21) can reduce the A1 etch rate to 1.88 A/min, and the corrosion of A1 is completely suppressed.
  • the corrosion inhibitor system of the carboxyl group-containing polymer for semiconductor wafer cleaning of the present invention has 07/068176
  • ⁇ ⁇ ” healthy characteristics, can be used between room temperature and 85 ° C, and in the fluorine-containing and non-systems for metal or non-metal bribery.

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  • Life Sciences & Earth Sciences (AREA)
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  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

A system of corrosion inhibitor for cleaning semiconductor wafers includes water and/or solvents, which is characterized by also comprising a polymer with carboxyl. In the polymer at least one kind of monomer is carboxyl. The system of corrosion inhibitor can be used from room temperature to 85 °C, and has an effect on preventing the metal or nonmetal from corrosion in the system of fluor-containing or no flour-containing.

Description

用于半导体晶片清洗的缓蚀剂体系 技术领域  Corrosion inhibitor system for semiconductor wafer cleaning
本发明涉及一种半导体制造过程中用于半导体晶片清洗的缓蚀剂体系。  The present invention relates to a corrosion inhibitor system for semiconductor wafer cleaning in a semiconductor fabrication process.
议不 Negotiating
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（ion bombardment)会硬化光阻层聚合物， 因 此使得光阻层变得不易溶从而更难于除去。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 去光阻层的大部分;第二步利用缓蚀剂组合物湿蚀刻 /清洗工艺除去且清洗掉 剩余的光阻层。在第二步的清洗工艺过程中， 缓蚀剂组合物只能除去聚合物 光阻层（PR)和无机残留物， 而不能攻击损害金属层如铝层， 通常该步骤需 要很长时间； 且为了有助于光阻层的除去， 常需要在高温下进行。  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). The ion bombardment hardens the photoresist layer polymer during the doping step, 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 by a two-step process (dry ashing and wet etching). The first step utilizes dry ashing to remove most of the photoresist layer; the second step utilizes the corrosion inhibitor composition wet etch/clean process to remove and clean away the remaining photoresist layer. In the cleaning process of the second step, the corrosion inhibitor composition can only remove the polymer photoresist layer (PR) and the inorganic residue, and cannot attack the damaged metal layer such as the aluminum layer, which usually takes a long time; In order to facilitate the removal of the photoresist layer, it is often required to carry out at a high temperature.
如现有技术中 US 5334332 (Lee, EKC), US 5417877 (Ward, Ashland) US As in the prior art US 5334332 (Lee, EKC), US 5417877 (Ward, Ashland) US
6030932 (Leon, Olin)和 US 6635186 (Small, EKC)等专利都公开了一些用于湿 蚀刻除去光阻层的缓蚀剂组合物，这些缓蚀剂组合物包括邻苯二酚或 8-羟基 喹啉等毒性物质。 尽管这些含有邻苯二酚或其衍生物、 8-羟基喹啉或其它缓 蚀剂的缓蚀剂组合物缓蚀效果良好， 但该缓蚀剂组合物通常浓度高且毒性 强， 而且需要在高温下使用， 对环境不友善、 产生很大的危害， 对人体健康 不利。 因此迫切需要开发出新型的缓蚀液体系。 发明概要 6030932 (Leon, Olin) and US 6,635,186 (Small, EKC) and other patents disclose some corrosion inhibitor compositions for wet etching removal of photoresist layers, including corrosion inhibitor compositions including catechol or 8-hydroxyl groups. Toxic substances such as quinoline. Although these corrosion inhibitor compositions containing catechol or its derivatives, 8-hydroxyquinoline or other corrosion inhibitors have good corrosion inhibition effects, the corrosion inhibitor compositions are generally high in concentration and highly toxic, and need to be When used at high temperatures, it is not friendly to the environment, causing great harm to human health. Therefore, it is urgent to develop a new type of corrosion inhibition system. Summary of invention
本发明的目的在于提供一种用于半导体晶片清洗的缓蚀剂体系，该缓蚀 剂体系包括水和 /或溶剂，其特征在于还包括一种含羧基的聚合物，其中，合 成该聚合物的至少一种单体含有竣基。  It is an object of the present invention to provide a corrosion inhibitor system for semiconductor wafer cleaning, the corrosion inhibitor system comprising water and/or a solvent, characterized by further comprising a carboxyl group-containing polymer, wherein the polymer is synthesized At least one monomer contains a thiol group.
本发明的用于半导体晶片清洗的缓蚀剂体系包括含羧基的聚合物，其可 以对金属如 A1等、 或非金属 Si、 或非金属氧化物 Si02等的腐蚀产生抑制作 用； 该缓蚀剂体系中的含羧基的聚合物可以起到腐蚀抑制剂、表面活性剂和 螯合剂等的作用；本发明的用于半导体晶片清洗的缓蚀剂体系不但具有对环 境友善、 安全无毒、 有利于健康的特点； 而且在含氟和不含氟的体系中均有 很好的抑制效果； 使用本发明的缓蚀剂体系可以降低铝的蚀刻速率， 而且几 乎不攻击 02和 Si。 本发明的用于半导体晶片清洗的缓蚀剂体系可在室温 至 85°C之间使用， 可用于再循环系统、 喷镀工具和单晶片处理。 The corrosion inhibitor system for semiconductor wafer cleaning of the present invention comprises a carboxyl group-containing polymer which can inhibit corrosion of a metal such as A1 or the like, or a non-metal Si, or a non-metal oxide SiO 2 , etc.; The carboxyl group-containing polymer in the agent system can function as a corrosion inhibitor, a surfactant, a chelating agent, etc.; the corrosion inhibitor system for semiconductor wafer cleaning of the present invention is not only environmentally friendly, safe and non-toxic, and has It is good for health; and it has a good inhibitory effect in both fluorine-containing and fluorine-free systems; the use of the corrosion inhibitor system of the present invention can reduce the etching rate of aluminum and hardly attack 0 2 and Si. The corrosion inhibitor system for semiconductor wafer cleaning of the present invention can be used between room temperature and 85 ° C and can be used in recycling systems, sputtering tools, and single wafer processing.
在本发明中，所述的含羧基的聚合物是含羧基的均聚物和 /或含羧基的共 聚物和 /或含羧基的均聚物盐和 /或含羧基的共聚物盐。  In the present invention, the carboxyl group-containing polymer is a carboxyl group-containing homopolymer and/or a carboxyl group-containing copolymer and/or a carboxyl group-containing homopolymer salt and/or a carboxyl group-containing copolymer salt.
在本发明的一较佳实施例中， 所述的含羧基的均聚物是聚马来酸酐 (HPMA)、 聚丙烯酸（PAA)和 /或聚甲基丙烯酸， 优选聚马来酸酐和 /或聚 丙烯酸； 在本发明的另一较佳实施例中， 所述的含羧基的共聚物是含羧基的 单体之间的共聚物（如： 丙烯酸与马来酸共聚物， 甲基丙烯酸与马来酸共聚 物）， 或乙烯基单体与含羧基的单体之间的共聚物 （如： 苯乙烯与丙烯酸共 聚物、 苯乙烯与马来酸共聚物、 丙烯腈与马来酸共聚物、 乙烯与丙烯酸共聚 物、 丙烯腈与丙烯酸共聚物、苯乙烯与甲基丙烯酸共聚物、 乙烯与甲基丙烯 酸共聚物和 /或丙烯腈与甲基丙烯酸共聚物等等）， 优选丙烯酸与马来酸共聚 物； 在本发明的再一较佳实施例中， 所述的盐是铵盐、钾盐和 /或钠盐， 优选 铵盐， 如聚丙烯酸铵 （SD)。  In a preferred embodiment of the invention, the carboxyl group-containing homopolymer is polymaleic anhydride (HPMA), polyacrylic acid (PAA) and/or polymethacrylic acid, preferably polymaleic anhydride and/or Polyacrylic acid; In another preferred embodiment of the invention, the carboxyl group-containing copolymer is a copolymer between carboxyl group-containing monomers (eg, acrylic acid and maleic acid copolymer, methacrylic acid and horse) An acid copolymer), or a copolymer between a vinyl monomer and a carboxyl group-containing monomer (eg, a copolymer of styrene and acrylic acid, a copolymer of styrene and maleic acid, a copolymer of acrylonitrile and maleic acid, Copolymer of ethylene and acrylic acid, copolymer of acrylonitrile and acrylic acid, copolymer of styrene and methacrylic acid, copolymer of ethylene and methacrylic acid and/or copolymer of acrylonitrile and methacrylic acid, etc., preferably acrylic acid and maleic acid Copolymer; In a further preferred embodiment of the invention, the salt is an ammonium salt, a potassium salt and/or a sodium salt, preferably an ammonium salt such as ammonium polyacrylate (SD).
在本发明中，只要是现有技术中已有的含羧基的聚合物均可用于本发明 的缓蚀剂体系中， 含羧基的聚合物分子量大小并不影响实现本发明的目的。 若本发明的缓蚀剂体系中具有一定质量浓度的聚合物，该缓蚀剂体系中也相 应地具有一定浓度的羧基。这是因为对于一定质量浓度的聚合物而言， 若聚 合物的分子量大， 缓蚀剂体系中聚合物的摩尔数就相应地少； 若聚合物的分 子量小， 缓蚀剂体系中聚合物的摩尔,数也就相应地多， 也就是说， 组成一定 的聚合物， 其一定质量浓度的聚合物上也就相应地含有一定浓度的羧基。不 管该聚合物的分子量大小，只要该聚合物上的羧基在缓蚀剂体系中达到一定 的浓度即可，即含羧基聚合物的缓蚀剂体系用于清洗半导体晶片均可以抑制 金属如 Al、 非金属如 Si和废金属氧化物如 Si02等的腐蚀。 在本发明的缓蚀 剂体系中， 聚合物上的羧基的浓度较佳地为 25ρρπ！〜 50,000ppm。 In the present invention, as long as the carboxyl group-containing polymer existing in the prior art can be used in the corrosion inhibitor system of the present invention, the molecular weight of the carboxyl group-containing polymer does not affect the object of the present invention. If the corrosion inhibitor system of the present invention has a certain concentration of polymer, the corrosion inhibitor system also It should have a certain concentration of carboxyl groups. This is because for a certain concentration of polymer, if the molecular weight of the polymer is large, the number of moles of the polymer in the corrosion inhibitor system is correspondingly small; if the molecular weight of the polymer is small, the polymer in the corrosion inhibitor system Moore, the number is correspondingly more, that is to say, the composition of a certain polymer, the polymer of a certain mass concentration correspondingly contains a certain concentration of carboxyl groups. Regardless of the molecular weight of the polymer, as long as the carboxyl group on the polymer reaches a certain concentration in the corrosion inhibitor system, that is, the corrosion inhibitor system containing the carboxyl group can suppress the metal such as Al, for cleaning the semiconductor wafer. Corrosion of non-metals such as Si and scrap metal oxides such as SiO 2 . In the corrosion inhibitor system of the present invention, the concentration of the carboxyl group on the polymer is preferably 25 ρρπ! ~ 50,000ppm.
在本发明的进一步较佳实施例中，该缓蚀剂体系还可以包含小分子酸和 /或小分子碱。  In a further preferred embodiment of the invention, the corrosion inhibitor system may further comprise a small molecule acid and/or a small molecule base.
该小分子酸可以是各种小分子酸， 优选有机酸， 更优选含有单或多羧基 的小分子酸； 该有机酸较佳地是 2-膦酸丁垸 -1,2,4-三羧酸（PBTCA；)、 草酸 (OA),柠檬酸和 /或没食子酸，更佳地是 2-膦酸丁烷 -1,2,4-三羧酸（PBTCA) 和 /或草酸。  The small molecule acid may be various small molecule acids, preferably organic acids, more preferably small molecule acids containing mono or polycarboxy groups; the organic acid is preferably 2-phosphonium 2-phosphonate-1,2,4-tricarboxylate Acid (PBTCA;), oxalic acid (OA), citric acid and/or gallic acid, more preferably butane-1,2,4-tricarboxylic acid (PBTCA) and/or oxalic acid.
该小分子碱可以是各种小分子碱， 优选含有单或多羟基的小分子碱， 更 优选氨水和 /或四甲基氢氧化铵 （TMAH)。  The small molecule base may be a variety of small molecule bases, preferably a small molecule base containing a mono or polyhydroxy group, more preferably aqueous ammonia and/or tetramethylammonium hydroxide (TMAH).
在本发明的缓蚀剂体系中， 该含羧基的聚合物的浓度可以是各种浓度， 优选 0.00001〜10%， 更优选 0.01〜3%； 该小分子酸和 /或小分子碱的浓度优 选 0〜10%， 更优选 0〜5%； 该水和 /或溶剂的浓度可以是现有技术中的各种 浓度，优选 80〜99.99999%， 更优选 92〜99.99%， 以上浓度均指占整个缓蚀 剂体系的质量浓度。  In the corrosion inhibitor system of the present invention, the concentration of the carboxyl group-containing polymer may be various concentrations, preferably 0.00001 to 10%, more preferably 0.01 to 3%; and the concentration of the small molecule acid and/or small molecule base is preferably 0 to 10%, more preferably 0 to 5%; the concentration of the water and/or solvent may be various concentrations in the prior art, preferably 80 to 99.99999%, more preferably 92 to 99.99%, and the above concentrations are all The mass concentration of the corrosion inhibitor system.
在本发明中，所述的溶剂是指有机溶剂，可为各种有机溶剂或其混合物， 如： N-甲基吡咯垸酮 (NMP)、 Y -丁内酯（GBL)、N,N-二甲基乙酰胺（DMAC)、 一缩二乙二醇单丁醚（DGMBE)和 /或乙醇胺（EA)，更佳地是 NMP、DGMBE 和 /或 EAo  In the present invention, the solvent means an organic solvent, and may be various organic solvents or a mixture thereof, such as: N-methylpyrrolidone (NMP), Y-butyrolactone (GBL), N, N- Dimethylacetamide (DMAC), diethylene glycol monobutyl ether (DGMBE) and/or ethanolamine (EA), more preferably NMP, DGMBE and/or EAo
本发明的用于半导体晶片清洗的缓蚀剂体系还可以包括其它腐蚀抑制 剂、 表面活性剂和 /或螯合剂。 本发明的积极进步效果在于：本发明的用于半导体晶片清洗的缓蚀剂体 系具有对环境友善、安全无毒、有利于健康的特点，可在室温至 85°C之间使 用， 而且在含氟和不含氟的体系中对金属或非金属均有很好的抑制效果。 发明内容 The corrosion inhibitor system for semiconductor wafer cleaning of the present invention may also include other corrosion inhibitors, surfactants, and/or chelating agents. The positive progress of the present invention is that the corrosion inhibitor system for semiconductor wafer cleaning of the present invention has the characteristics of being environmentally friendly, safe, non-toxic and health-friendly, and can be used between room temperature and 85 ° C, and Both fluorine and fluorine-free systems have good inhibitory effects on metals or non-metals. Summary of the invention
对比实施例 1，〜4，及实施 I 1〜22  Comparative Example 1, ~4, and implementation I 1~22
表 1 本发明的缓蚀剂体系及对比体系 （不含氟体系) 实施 DI GBL NMP EA DGMBE 小分子酸和 /或碱 含羧基的聚合物 例 % % % % % 成份 浓度,％ 成份 浓度, % Table 1 Corrosion inhibitor system and comparison system of the present invention (no fluorine system) Implementation DI GBL NMP EA DGMBE Small molecule acid and / or alkali Carboxyl group-containing polymer Example % % % % % Component concentration, % Component concentration, %
V 16.1 9.8 11.8 16.1 46.2 NA NA V 16.1 9.8 11.8 16.1 46.2 NA NA
17.9 NA 13.1 17.9 51.1 NA NA  17.9 NA 13.1 17.9 51.1 NA NA
3' 18.0 NA 13.1 17.8 51.0 PBTCA 0.1 NA  3' 18.0 NA 13.1 17.8 51.0 PBTCA 0.1 NA
1 29.8 NA 70 NA NA . PBTCA 0.1 HPMA 0.1 1 29.8 NA 70 NA NA . PBTCA 0.1 HPMA 0.1
2 16.8 NA 12.3 16.8 48.1 PBTCA 3 HPMA 32 16.8 NA 12.3 16.8 48.1 PBTCA 3 HPMA 3
3 17.8 NA 13.1 17.8 51.0 PBTCA 0.1 HPMA 0.23 17.8 NA 13.1 17.8 51.0 PBTCA 0.1 HPMA 0.2
4 17.5 NA 12.8 17.5 50.2 PBTCA 1 HPMA 14 17.5 NA 12.8 17.5 50.2 PBTCA 1 HPMA 1
5 9.75 NA NA NA 85 OA 0.25 HPMA 55 9.75 NA NA NA 85 OA 0.25 HPMA 5
6 15.1 9.2 11.1 15.1 43.5 PBTCA 3 HPMA 36 15.1 9.2 11.1 15.1 43.5 PBTCA 3 HPMA 3
7 15.8 9:5 11.6 15.8 45.3 PBTCA 1 HPMA 17 15.8 9:5 11.6 15.8 45.3 PBTCA 1 HPMA 1
8 15.9 9.6 11.6 15.9 45.6 PBTCA 0.7 HPMA 0.78 15.9 9.6 11.6 15.9 45.6 PBTCA 0.7 HPMA 0.7
9 15.6 10.4 11.6 15.6 44.8 PBTCA 1 SD 1 9 15.6 10.4 11.6 15.6 44.8 PBTCA 1 SD 1
丙烯酸  Acrylic
与马来  With Malay
10 20 10 NA 10 49.99999 氨水 10 0.00001 酸共聚  10 20 10 NA 10 49.99999 Ammonia 10 0.00001 Acid copolymerization
物  Object
11 10 10 40 7 30 NA SD 3 ' 11 10 10 40 7 30 NA SD 3 '
12 15 NA 9.9 15 50 TMAH 0.1 SD 1012 15 NA 9.9 15 50 TMAH 0.1 SD 10
13 98 NA NA NA NA NA NA SD 213 98 NA NA NA NA NA NA SD 2
14 NA NA 95 NA 4 NA NA 苯乙烯 1 14 NA NA 95 NA 4 NA NA Styrene 1
与马来  With Malay
酸酐共  Alkoxide
聚物 I: 去离子水； NA是没有加入该成^。 Polymer I: Deionized water; NA is not added to the ^.
表 2本发明的缓蚀剂体系及对比体系 （含氟体系)  Table 2 Corrosion inhibitor system and comparison system of the present invention (fluorine system)
Figure imgf000006_0001
Figure imgf000006_0001
DI: 去离子水； NA是没有加入该成份。  DI: Deionized water; NA is not added to this ingredient.
将上述表 1和表 2中的各成份按照比例混合均匀，制得本发明的缓蚀剂 体系及对比的体系。  The components of the above Tables 1 and 2 were uniformly mixed in proportion to obtain a corrosion inhibitor system of the present invention and a comparative system.
效果实施例 1 ·: '  Effect Example 1 ·: '
将对比实施例 Γ〜3，的体系及实施例 1〜9的缓蚀剂体系在不含氟的体 系中用于清洗蚀刻空白 A1晶片。测试方法和条件： 25°C， 摇床为 60转每分 钟， 时间为 30分钟。 蚀刻速率是通过四极探针仪测试其蚀刻前后表面电阻 变化后计算而得， 结果如表 3 '所示。  The system of Comparative Example Γ3, and the corrosion inhibitor system of Examples 1 to 9 were used for cleaning the etched blank A1 wafer in a fluorine-free system. Test methods and conditions: 25 ° C, shaker 60 rpm, time 30 minutes. The etching rate was calculated by testing the surface resistance change before and after etching by a quadrupole prober, and the results are shown in Table 3'.
表 3 缓蚀剂体系在不含氟的体系中对空白 A1晶片的蚀刻速率  Table 3 Etching rate of blank A1 wafer in corrosion inhibitor system in fluorine-free system
Figure imgf000006_0002
Figure imgf000006_0002
注： Rate表示蚀刻速率； 蚀刻速率为负值， 表示蚀刻速率几乎为零。 在半导体清洗工艺中，若金属蚀刻速率小于或等于 2.0 A/min，则说明缓 蚀剂体系具有相当好的腐蚀抑制作用。从表 3可以看出， 不含含羧基聚合物 的缓蚀剂体系对空白 A1晶片的蚀刻速率大于 2.0 A/min; 本发明的含羧基的 聚合物的缓蚀剂体系用于清洗空白 Al晶片， A1蚀刻速率都小于 2.0 A/min， 可以明显降低 A1的蚀刻速率， 甚至达到 0 A/min， 完全抑制了 A1腐蚀作用。 从而说明本发明的含羧基的聚合物的缓蚀剂体系可以显著地抑制 A1腐蚀， 从而有利于 A1晶片的光阻层有机残留物和 /或无机残留物有效去除。 Note: Rate represents the etch rate; the etch rate is negative, indicating that the etch rate is almost zero. In the semiconductor cleaning process, if the metal etching rate is less than or equal to 2.0 A/min, the corrosion inhibitor system has a relatively good corrosion inhibition effect. As can be seen from Table 3, the corrosion rate of the corrosion inhibitor system containing no carboxyl group-containing polymer on the blank A1 wafer is greater than 2.0 A/min; the carboxyl group-containing of the present invention The polymer corrosion inhibitor system is used to clean the blank Al wafer. The A1 etching rate is less than 2.0 A/min, which can significantly reduce the etching rate of A1, even reaching 0 A/min, completely inhibiting the A1 corrosion. Therefore, the corrosion inhibitor system of the carboxyl group-containing polymer of the present invention can significantly inhibit A1 corrosion, thereby facilitating effective removal of organic residues and/or inorganic residues of the photoresist layer of the A1 wafer.
效果实施例 2  Effect Example 2
将上述实施例 4缓蚀剂体系用于清洗蚀刻空白 Si02晶片， 测试方法和 条件： 25°C， 摇床为 60转每分钟， 时间为 30分钟， 用 NANOSPEC薄膜测 厚仪（购于 NANO metrics公司）测试 Si02晶片蚀刻前后表面膜厚变化计算 得蚀刻速率。 The above Example 4 corrosion inhibitor system was used to clean the etched blank Si0 2 wafer, test method and conditions: 25 ° C, shaker 60 rpm, time 30 minutes, using NANOSPEC film thickness gauge (purchased in NANO Metrics) measured the etch rate of the surface film thickness change before and after etching of the Si0 2 wafer.
结果表明： 在本发明中， Si02的蚀刻速率为 0.78A/min， 其蚀刻速率小 于 2A/min， 说明本发明的缓蚀剂体系也可以抑制 Si02腐蚀。 The results showed that: In the present invention, the etch rate of Si0 2 was 0.78A / min, the etching rate which is less than 2A / min, described corrosion inhibitor system of the present invention may also inhibit the corrosion Si0 2.
效果实施例 3  Effect Example 3
将对比实施例 4，的体系及实施例 15〜22的缓蚀剂体系用于清洗蚀刻空 白 A1晶片。 测试方法和条件： 25°C， 摇床为 60转每分钟， 时间为 30分钟。 蚀刻速率是通过四极探针仪测试其蚀刻前后表面电阻变化后计算而得，结果 如表 4所示。  The system of Comparative Example 4 and the corrosion inhibitor system of Examples 15 to 22 were used to clean the etched blank A1 wafer. Test methods and conditions: 25 ° C, shaker 60 rpm, time 30 minutes. The etching rate was calculated by testing the surface resistance change before and after etching by a quadrupole prober. The results are shown in Table 4.
表 4 本发明的缓蚀剂体系用于含氟体系对空白 A1晶片的蚀刻速率
Figure imgf000007_0002
Table 4 Corrosion rate of the corrosion inhibitor system of the present invention for the blank A1 wafer of the fluorine-containing system
Figure imgf000007_0002
Figure imgf000007_0001
Figure imgf000007_0001
在半导体清洗工艺中， 常用氟化物来辅助除去晶片上的残留物， 但氟化 物往往同时也增加金属的蚀 j速率。如表 4数据表明， 在含有氟化物的体系 中， 本发明的缓蚀剂体系用于清洗空白 A1晶片， A1蚀刻速率也很小， 也可 以将 A1的蚀刻速率降至 2.0 A/min以下，即使只含有含羧基聚合物而不含小 分子酸和小分子碱的缓蚀剂体系 （如实施例 21 ) 也可以将 A1蚀刻速率降至 1.88A/min, A1的腐蚀得到了完全的抑制。  In semiconductor cleaning processes, fluoride is commonly used to assist in the removal of residues on the wafer, but fluoride also tends to increase the rate of metal etch. As shown in the data in Table 4, in the fluoride-containing system, the corrosion inhibitor system of the present invention is used for cleaning the blank A1 wafer, and the etching rate of A1 is also small, and the etching rate of A1 can also be reduced to 2.0 A/min or less. Even a corrosion inhibitor system containing only a carboxyl group-containing polymer and no small molecular acid and small molecule base (as in Example 21) can reduce the A1 etch rate to 1.88 A/min, and the corrosion of A1 is completely suppressed.
结论：本发明的用于半导体晶片清洗的含羧基聚合物的缓蚀剂体系具有 07/068176 Conclusion: The corrosion inhibitor system of the carboxyl group-containing polymer for semiconductor wafer cleaning of the present invention has 07/068176
PCT/CN2006/002622 对环境友善、安全无毒、有利于健康 ~r^^ ^  PCT/CN2006/002622 Environmentally friendly, safe and non-toxic, good for health ~r^^ ^
Ή 」卞健康的特点， 可在室温至 85°C之间使用， 而 且在含氟和不含 体系中对金属或非金属均 贿瞻制 。 Ή ” ” healthy characteristics, can be used between room temperature and 85 ° C, and in the fluorine-containing and non-systems for metal or non-metal bribery.

Claims

权利要求 Rights request
1、 一种用于半导体晶片清洗的缓蚀剂体系， 该缓蚀剂体系包括水和 /或 溶剂， 其特征在于还包括一种含羧基的聚合物， 其中， 合成该聚合物的至少 一种单体含有羧基。 · What is claimed is: 1. A corrosion inhibitor system for semiconductor wafer cleaning, the corrosion inhibitor system comprising water and/or a solvent, characterized by further comprising a carboxyl group-containing polymer, wherein at least one of the polymers is synthesized The monomer contains a carboxyl group. ·
2、 根据权利要求 1所述的缓蚀剂体系， 其特征在于： 该含羧基的聚合 物是含羧基的均聚物和 /或含羧基的共聚物和 /或其盐。  The corrosion inhibitor system according to claim 1, wherein the carboxyl group-containing polymer is a carboxyl group-containing homopolymer and/or a carboxyl group-containing copolymer and/or a salt thereof.
3、 根据权利要求 2所述的缓蚀剂体系， 其特征在于： 所述的含羧基的 均聚物是聚马来酸酐、聚丙烯酸和 /或聚甲基丙烯酸；所述的含羧基的共聚物 是丙烯酸与马来酸共聚物、苯乙烯与丙烯酸共聚物、苯乙烯与马来酸共聚物 和 /或丙烯腈与马来酸共聚物； 所述的盐是铵盐、 钾盐和 /或钠盐。  3. The corrosion inhibitor system according to claim 2, wherein: said carboxyl group-containing homopolymer is polymaleic anhydride, polyacrylic acid and/or polymethacrylic acid; said carboxyl group-containing copolymerization The copolymer is a copolymer of acrylic acid and maleic acid, a copolymer of styrene and acrylic acid, a copolymer of styrene and maleic acid and/or a copolymer of acrylonitrile and maleic acid; the salt is an ammonium salt, a potassium salt and/or Sodium salt.
4、 根据权利要求 1、 2或 3所述的缓蚀剂体系， 其特征在于： 该缓蚀剂 体系还包含小分子酸和 /或小分子碱。  4. A corrosion inhibitor system according to claim 1, 2 or 3, characterized in that the corrosion inhibitor system further comprises a small molecule acid and / or a small molecule base.
5、 根据权利要求 4所述的缓蚀剂体系， 其特征在于： 该小分子酸含有 单或多羧基； 该小分子碱含有单或多羟基。  The corrosion inhibitor system according to claim 4, wherein the small molecule acid contains a mono- or polycarboxy group; and the small molecule base contains a mono- or polyhydroxy group.
6、 根据权利要求 4所述的缓蚀剂体系， 其特征在于： 该小分子酸是 2- 膦酸丁烷 -1,2,4-三羧酸、 草酸、 柠檬酸、 没食子酸和 /或其混合物。  6. The corrosion inhibitor system according to claim 4, wherein the small molecule acid is butane-1,2,4-tricarboxylic acid, oxalic acid, citric acid, gallic acid and/or Its mixture.
7、 根据权利要求 4所述的缓蚀剂体系， 其特征在于： 该小分子碱是氨 水和 /或四甲基氢氧化铵。  7. The corrosion inhibitor system according to claim 4, wherein the small molecule base is ammonia and/or tetramethylammonium hydroxide.
8、 根据权利要求 4所述的缓蚀剂体系， 其特征在于： 该含羧基的聚合 物的浓度为 0.00001〜10%，该小分子酸和 /或小分子碱的浓度为 0〜10%，该 水和 /或溶剂的浓度为 80〜99.99999%。  The corrosion inhibitor system according to claim 4, wherein the concentration of the carboxyl group-containing polymer is 0.00001 to 10%, and the concentration of the small molecule acid and/or small molecule base is 0 to 10%. The concentration of the water and/or solvent is from 80 to 99.99999%.
9、 根据权利要求 8所述的缓蚀剂体系， 其特征在于： 该含羧基的聚合 物的浓度为 0.01〜3%。  The corrosion inhibitor system according to claim 8, wherein the carboxyl group-containing polymer has a concentration of 0.01 to 3%.
10、 根据权利要求 8所述的缓蚀剂体系， 其特征在于： 该小分子酸和 / 或小分子碱的浓度为 0〜5%。 10. The corrosion inhibitor system according to claim 8, wherein the concentration of the small molecule acid and/or small molecule base is from 0 to 5%.
11、根据权利要求 4所述的缓蚀剂体系，其特征在于该溶剂为 N-甲基吡 咯垸酮、 Y -丁内酯、 Ν,Ν-二甲基乙酰胺、一缩二乙二醇单丁醚和 /或乙醇胺。 The corrosion inhibitor system according to claim 4, wherein the solvent is N-methylpyrrolidone, Y-butyrolactone, hydrazine, hydrazine-dimethylacetamide, diethylene glycol. Monobutyl ether and / or ethanolamine.
PCT/CN2006/002622 2005-12-16 2006-10-08 A system of corrosion inhibitor for cleaning semiconductor wafets WO2007068176A1 (en)

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