WO2007056919A1 - Composition detergente aqueuse - Google Patents

Composition detergente aqueuse Download PDF

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Publication number
WO2007056919A1
WO2007056919A1 PCT/CN2006/002621 CN2006002621W WO2007056919A1 WO 2007056919 A1 WO2007056919 A1 WO 2007056919A1 CN 2006002621 W CN2006002621 W CN 2006002621W WO 2007056919 A1 WO2007056919 A1 WO 2007056919A1
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WO
WIPO (PCT)
Prior art keywords
concentration
liquid composition
cleaning liquid
ammonium
fluoride
Prior art date
Application number
PCT/CN2006/002621
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English (en)
French (fr)
Inventor
Thomas Teo
Ivan Jianying Yin
Original Assignee
Anji Microelectronics (Shanghai) Co., Ltd
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Publication date
Application filed by Anji Microelectronics (Shanghai) Co., Ltd filed Critical Anji Microelectronics (Shanghai) Co., Ltd
Publication of WO2007056919A1 publication Critical patent/WO2007056919A1/zh

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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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic 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
    • 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
    • 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
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • 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
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention relates to a cleaning fluid composition, and more particularly to a cleaning fluid composition for use in the manufacture of chips for integrated circuits.
  • the material to be removed is a photoresist and a polymer residue.
  • the material to be removed is the residue remaining after etching or polishing, or other contaminants, the purpose of the cleaning solution composition. It is necessary to remove unwanted materials on the semiconductor substrate to prevent corrosion, dissolution or passivation of the substrate.
  • Typical 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 liquids need to be cleaned at high temperatures, generally between 65 ° C and 85 °; and existing fluoride-based cleaning solutions still have various disadvantages, such as the following patents: US 6,593,282, US 6,828,289,
  • Various cleaning fluid compositions are disclosed in US Pat. No. 6, 972, 862, US Pat. No. 6, 592, 433, and US Pat. No. 6,773, 873.
  • 6,828,289 includes: an acidic buffer, an organic polar solvent, a fluorine-containing substance and water, and has a pH of 3 to 7. Between the acidic buffer or the polybasic acid and the corresponding ammonium salt, the composition ratio is between 10:1 and 1:10.
  • a cleaning composition containing a fluorine-containing substance which comprises a fluorine-containing substance, a weak acid and a weak base such as an ammonium salt-constituting buffer, an organic polar solvent, and a pH of 7 to 11, and the cleaning effect is not very effective, and there are various problem.
  • This type of cleaning solution usually has a high copper etching rate and cannot be used for copper damascene structure cleaning.
  • An object of the present invention is to solve the above problems and to provide a cleaning liquid composition.
  • the cleaning liquid composition of the present invention comprises the following components: a solvent, a buffer, a fluoride, a corrosion inhibitor and water, characterized in that the buffer comprises: weak acid, ammonium And amines.
  • the weak acid may be acetic acid and/or citric acid, ft selected acetic acid;
  • the ammonium may be ammonium acetate, ammonium citrate and/or ammonia water, preferably ammonium acetate.
  • the buffering agent of the present invention is preferably acetic acid, ammonium acetate and triethanolamine.
  • the buffer of the present invention contains three or more components, and the use of three or more components as a buffer can significantly lower the used temperature, from the high temperature in the prior art to room temperature and 35. Between °C, it does not enlarge the size of the channel, eliminates uneven etching, metal or metal oxide without loss, eliminates electroplating corrosion of the geometric device, and can also be used for copper damascene process cleaning.
  • the buffer of the present invention may also function as a corrosion inhibitor or a corrosion inhibiting property, such as certain specific amines: monoethanolamine (MEA), diethanolamine (DEA) or triethanolamine (TEA), and organic acids.
  • the buffer of the present invention may also function as a surfactant, such as certain specific amines: monoethanolamine (MEA), diethanolamine (DEA) or triethanolamine (TEA), and the like.
  • the content of each group of the cleaning liquid of the present invention can be referred to the prior art.
  • the concentration of the solvent is 47 to 88%
  • the concentration of the fluoride is 0.05 to 3%.
  • the concentration of the corrosion inhibitor is 0.01 to 1.5%, the concentration of water is 9.9 to 40%, the concentration of the weak acid is 0.5 to 4%, the concentration of the ammonium is 0.5 to 5%, and the concentration of the amine is 0.1 to 5%.
  • the above % refers to the weight percentage of the entire cleaning liquid composition.
  • the solvent has a concentration of 73% and a fluoride concentration of 0.4 °/.
  • the concentration of the corrosion inhibitor is 0.75%
  • the concentration of water is 21%
  • the concentration of the weak acid is ?%
  • the concentration of the ammonium is 2.6%
  • the concentration of the amine is 0.25%.
  • the solvent may be various organic solvents, preferably dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC).., N-methylpyrrolidone (NMP) And/or ethylene glycol, preferably N-methylpyrrolidone.
  • DMSO dimethyl sulfoxide
  • DMAC dimethylacetamide
  • NMP N-methylpyrrolidone
  • ethylene glycol preferably N-methylpyrrolidone
  • the fluoride is preferably hydrogen fluoride, ammonium hydrogen fluoride, ammonium fluoride, tetramethylammonium fluoride (TMAF) and/or organic fluorine.
  • the corrosion inhibitor is preferably benzotriazole (BTA), benzotriazole derivative, gallic acid, catechol and/or benzene.
  • the pH of the cleaning liquid composition of the present invention is preferably from 3.0 to 5.8.
  • the cleaning fluid compositions of the present invention may also include surfactants and/or complexing agents.
  • the surfactant may be various surfactants in the prior art, and the complexing agent may also be various complexing agents.
  • the positive progress of the present invention is as follows: 1) The cleaning liquid composition of the present invention can be used.
  • the use temperature can be used between room temperature and 35 ° C; 2)
  • the cleaning of the present invention is due to the three components as a buffering agent. Fluoride in the liquid does not enlarge the size of the channel, and can eliminate the etching etch rate to cause uneven etching; 3) the defect rate on the surface of the wafer is reduced after using the cleaning solution of the invention; 4) it is especially helpful To prevent electrolytic corrosion of small geometric components; 5) it is available Damascene process cleaning in copper because the etch rate of low dielectric materials is negligible.
  • Figure 1 is an SEM image of the silicon wafer before cleaning
  • Figure 2 is an SEM image of the wafer after 4 minutes of cleaning
  • Figure 3 is an SEM image of the silicon wafer after 6 minutes of cleaning
  • Figure 4 is an SEM image of the wafer after 8 minutes of cleaning
  • Figure 5 is a SEM image of the surface of the relevant channel in the wafer before cleaning
  • Figure 6 is a SEM image of the surface of the relevant channel in the silicon wafer after cleaning
  • Figure 7 is a cross-sectional SEM image of the relevant channel in the silicon wafer before cleaning
  • Figure 8 is a cross-sectional SEM image of the relevant channel in the silicon wafer after cleaning
  • Figure 9 is a graph showing the etching rate of a CORAL film when the cleaning composition of the present invention is washed at 40 ° C;
  • Figure 10 is a graph showing the etching rate of a BPSG film when the cleaning composition of the present invention is washed at 40 ° C;
  • Fig. 11 is a graph showing the etching rate of a silicon dioxide film when the cleaning composition of the present invention is washed at 40 °C.
  • Components of the cleaning liquid composition 1 73% by weight of N-methylpyrrolidone, 2% by weight of acetic acid, 2.6% by weight of ammonium acetate, 0.25 % by weight of triethanolamine, 21% by weight of water, 0.4% by weight of ammonium fluoride, benzotriazole ( BTA) 0.75 wt%, pH 5.2.
  • Example 2 Components of the cleaning liquid composition 1 : 73% by weight of N-methylpyrrolidone, 2% by weight of acetic acid, 2.6% by weight of ammonium acetate, 0.25 % by weight of triethanolamine, 21% by weight of water, 0.4% by weight of ammonium fluoride, benzotriazole ( BTA) 0.75 wt%, pH 5.2.
  • BTA benzotriazole
  • the components of the cleaning liquid composition 2 dimethyl sulfoxide 70% by weight, acetic acid 2% by weight, ammonium acetate 2.6% by weight, diethanolamine 0.25wt%/. Water 21.4 wt%, ammonium fluoride 3 wt%, benzotriazole (BTA) 0.75 t%, pH 5.2.
  • the azole was 1.5 wt% and the pH was 3.2.
  • the components of the cleaning liquid composition 4 dimethylacetamide 87.4 wt%, acetic acid 0.5 wt%, ammonium acetate 0.6 t%, monoethanolamine 0.2 wt%, water 9.9 wt%, tetramethylammonium fluoride 0.4 wt%, Benzotriazole 1.0 wt%, pH 5.2.
  • the components of the cleaning liquid composition 5 dimethyl sulfone 76.04 wt%, citric acid 1.3 wt%, ammonium hydroxide 0.5 wt%, triethanolamine 0.25 wt. /. Water 20.81% by weight, tetramethylammonium fluoride lwt%, gallic acid 0.01wt%, ethylenediaminetetraacetic acid 0.09%, pH 3.2.
  • the components of the cleaning liquid composition 6 are: ethylene glycol 47.05 wt%, acetic acid 3.85 wt%, ammonium acetate 5 wt%, diethanolamine 0.1 wt%, water 39.8 wt%, hydrogen fluoride 0.4 wt%, catechol 1.3 wt%, Polyacrylic acid 2.5 ° /. , pH is 5.2.
  • N-methylpyrrolidone 68.25 wt%, acetic acid 2 wt%, ammonium acetate 2.6 wt%, triethanolamine 5 wt%, water 21 wt%, ammonium fluoride 0.4 wt%, benzotriazole
  • the azole (BTA) was 0.75 wt% and the pH was 5.8.
  • the silicon wafer with the metal wire etched is divided into several pieces, and then four pieces are taken out, and three pieces are respectively washed with the above-mentioned cleaning liquid composition 1 at room temperature, the cleaning temperature is 35 ° C, and the cleaning time is 4 minutes respectively. , 6 minutes, 8 minutes.
  • Observation by electron microscopy showed that after using the cleaning liquid composition of the present invention, the metal surface had no obvious defects, as shown in Figs. 2 to 4, the residue was completely removed, and the cleaning was performed for 4 minutes as compared with that before Fig. 1 (Fig. 2) The loss of metal after 6 minutes (Fig. 3) and 8 minutes (Fig. 4) is negligible.
  • a silicon wafer etched with a plug was divided into a plurality of sheets, and two of the silicon wafers were randomly taken out and washed with the above-mentioned cleaning liquid composition 1 at 35 Torr for a cleaning time of 8 minutes.
  • the etching rate of the CORAL film is negligible (as shown in Fig. 9), and the etching rate of the TEOS film (Fig. 10) and the etching rate of the BPSG film (Fig. 11) are 1: At 1.04, there is no uneven oxidation etch in the channel.

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Description

清洗液组合物 技术领域
本发明涉及一种清洗液组合物，尤其涉及用于集成电路的芯片制造中的 清洗液组合物。 技术背景
在半导体或微电路半导体的制造过程中，从半导体元器件衬底表面上除 去材料是很有必要的。 在有 情况下待除去的材料是光阻和聚合物残留物， 在某些情况下待除去的材料是蚀刻或抛光后剩下的残留物，或者是其它的污 染物， 清洗液组合物的目的是除去半导体衬底上不需要的材料， 以免衬底发 生腐蚀、 溶解或钝化。
现有技术中典型的清洗液有以下几种： 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 65°C到 85Ό之间； 而现存的氟化物类清洗液仍然存在着各种各样的 缺点，例如下列专利： US 6,593,282, US 6,828,289, US 5,972,862, US 6,592,433 和 US 6,773,873公开了各种清洗液组合物，如 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聚碱酸与所对应的铵盐组成， 组成比 例为 10: 1至 1 : 10之间。 Π US 5,972,862公开了含氟物质的清洗组合物， 其包括含氟物质、弱酸和弱碱如铵盐组成缓冲液、有机极性溶剂， pH为 7〜 11， 清洗效果不是很有效， 存在多样的问题。 这一类清洗液通常具有较高的 铜蚀刻速率， 不能用于铜大马士革结构清洗； 同时， 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； 尤其是具有不同的 TEOS (原硅酸四 乙酯）和 BPSG. (硼磷硅酸盐玻璃）蚀刻速率； 另外， 操作温度通常仍需要 在室温以上。
因此， 有必要开发出新型的清洗液组合物来解决现有技术中存在的问 题。
发明概要
本发明的目的是为了解决上述问题， 提供一种清洗液组合物。
本发明的上述目的通过下列技术方案来实现:本发明的清洗液组合物包 括如下组分： 溶剂、 缓冲剂、 氟化物、 腐蚀抑制剂和水， 其特征在于该缓冲 剂包括： 弱酸、 铵类和胺类。
在本发明中，所述的弱酸可为醋酸和 /或柠檬酸， ft选醋酸；所述的铵类 可为醋酸铵、 柠檬酸铵和 /或氨水， 优选醋酸铵 所述的胺类可为一乙醇胺、 二乙醇胺和 /或三乙醇胺， 优选三乙醇胺。
本发明的缓冲剂优选醋酸、 醋酸铵和三乙醇胺。
本发明的缓冲剂含有三种或三种以上的组分，含有三种或三种以上的组 分作为缓冲剂可以显著地降低使用过的温度，从现有技术中的高温降低至室 温与 35°C之间， 同时不会扩大通道的尺寸， 消除了不平坦的蚀刻，金属或金 属氧化物不会有损失， 消除几何器件的电镀腐蚀， 其还可以用于铜的大马士 革制程清洗。
本发明的缓冲剂还可以起到腐蚀抑制剂的作用或者是腐蚀抑制的特性， 例如某些特殊的胺类：一乙醇胺 (MEA)、二乙醇胺 (DEA)或三乙醇胺 (TEA), 以及有机酸等； 本发明的缓冲剂还可以起到表面活性剂的特性， 例如某些特 殊的胺类： 一乙醇胺（MEA)、 二乙醇胺 (DEA)或三乙醇胺（TEA)等等。 本发明的清洗液的各组^ >含量均可参照现有技术，在本发明的一较佳实 施例中， 所述的溶剂的浓度为 47〜88%， 氟化物的浓度为 0.05〜3%， 腐蚀 抑制剂的浓度为 0.01〜1.5%，水的浓度为 9.9〜40%，弱酸的浓度为 0.5〜4%、 铵类的浓度为 0.5〜5%、 胺类的浓度为 0.1〜5%， 以上％均指占整个清洗液 组合物的重量百分比。
在本发明的进一步较佳实施例中，所述的溶剂的浓度为 73%， 氟化物的 浓度为 0.4°/。，腐蚀抑制剂的浓度为 0.75%， 水的浓度为 21%， 弱酸的浓度为 ?%、 铵类的浓度为 2.6%、 胺类的浓度为 0.25%。
在本发明中， 所述的溶剂可为各种有机溶剂， 较佳地为二甲基亚砜 (DMSO) 、 二甲基乙酰胺（DMAC)..'、 N-甲基吡咯垸酮 （NMP)和 /或乙 二醇， 优选 N-甲基吡咯烷酮。
所述的氟化物较佳地为氟化氢、 氟化氢铵、 氟化铵、 四甲基氟化铵 (TMAF)和 /或有机氟。
所述的腐蚀抑制剂较佳地为苯并三氮唑 （BTA)、 苯并三氮唑衍生物、 没食子酸、 邻苯二酚和 /或苯类。
本发明的清洗液组合物的 pH较佳地为 3.0〜5.8。
本发明的清洗液组合物还可以包括表面活性剂和 /或络合剂。所述的表面 活性剂可以为现有技术中的各种表面活性剂，所述的络合剂也可以为各种络 合剂。
本发明的积极进步效果在于： 1 )使用本发明的清洗液组合物可以降低. 使用温度， 可以在室温至 35°C之间使用； 2) 因有三种成分作为缓冲剂， 所 以本发明的清洗液中的氟化物不会扩大通道的尺寸，而且可以消除不同的氧 化蚀刻速率引起蚀刻不平坦； 3 )使用本发明的清洗液后， 晶片表面上的缺 陷率得到降低； 4)其尤其有助于防止小几何元器件的电解腐蚀； 5 )其可用 于铜的大马士革制程清洗， 因为低介电材料的蚀刻速率可以忽略不计。
附图说明
图 1为清洗前硅片的 SEM图；
图 2为硅片清洗 4分钟后的 SEM图；
图 3为硅片清洗 6分钟后的 SEM图；
图 4为硅片清洗 8分钟后的 SEM图；
图 5为清洗前硅片中有关通道的表面 SEM图；
图 6为清洗后硅片中有关通道的表面 SEM图；
图 7为清洗前硅片中有关通道的剖面 SEM图；
图 8为清洗后硅片中有关通道的剖面 SEM图；
图 9为使用本发明的清洗液组合物在 40°C清洗时， CORAL膜的蚀刻速率行 为图；
图 10为使用本发明的清洗液组合物在 40°C清洗时， BPSG膜的蚀刻速率行 为图；
图 11使用本发明的清洗液组合物在 40°C清洗时， 二氧化硅膜的蚀刻速率行 为图。
发明内容
实施例 1
清洗液组合物 1 的组分： N-甲基吡咯烷酮 73wt%， 醋酸 2wt%， 醋酸 铵 2.6wt%，三乙醇胺 0.25wt%,水 21wt%，氟化铵 0.4wt%，苯并三氮唑（BTA) 0.75wt%, pH为 5.2。 实施例 2
清洗液组合物 2 的组分： 二甲基亚砜 70wt%， 醋酸 2wt%， 醋酸铵 2.6wt%,二乙醇胺 0.25wt°/。，水 21.4wt%，氟化铵 3wt%，苯并三氮唑（BTA) 0.75 t%, pH为 5.2。
实施例 3 .
清洗液组合物 3的组分: N-甲基吡咯烷酮 73wt%， 柠檬酸 1.3wt%， 氢 氧化铵 0.5wt%， 三乙醇胺 0.25wt%， 水 23.4wt%, 氟化氢铵 0.05wt%， 苯并 三氮唑 1.5wt%， pH为 3.2。 实施例 4
清洗液组合物 4的组分： 二甲基乙酰胺 87.4wt%， 醋酸 0.5wt%， 醋酸 铵 0.6 t%， 一乙醇胺 0.2wt%， 水 9.9wt%， 四甲基氟化铵 0.4wt%， 苯并三 氮唑 1.0wt%， pH为 5.2。
实施例 5
清洗液组合物 5的组分： 二甲基 砜 76.04wt%， 柠檬酸 1.3wt%， 氢氧 化铵 0.5wt%， 三乙醇胺 0.25wt。/。， 水 20.81wt%， 四甲基氟化铵 lwt%， 没食 子酸 0.01wt%， 乙二胺四乙酸 0.09%， pH为 3.2。
实施例 6
清洗液组合物 6 的组分： 乙二醇 47.05wt%， 醋酸 3.85wt%， 醋酸铵 5wt%, 二乙醇胺 0.1wt%， 水 39.8wt%， 氟化氢 0.4wt%， 邻苯二酚 1.3wt%， 聚丙烯酸 2.5°/。， pH为 5.2。
实施例 7
清洗液组合物 7的组分： N-甲基吡咯垸酮 68.25wt%, 醋酸 2wt%, 醋 酸铵 2.6wt%，三乙醇胺 5wt%，水 21wt%，氟化铵 0.4wt%，苯并三氮唑（BTA) 0.75wt%, pH为 5.8。 效果实施例 1
将一刻蚀有金属线的硅片分割成若干块，随即拿出 4片，其中 3片在室 温下分别用上述清洗液组合物 1进行清洗，清洗温度为 35°C，清洗时间分别 为 4分钟、 6分钟、 8分钟。 , 电子显微镜观察结果表明：使用本发明的清洗液组合物后，金属表面无 明显缺陷， 如图 2〜4所示， 残留物全被去掉， 与图 1清洗前相比， 清洗 4 分钟 （图 2) 、 6分钟 （图 3 ) 、 8分钟 （图 4)后的金属的损失可以忽略不 计。
效果实施例 2
将一刻蚀有插栓的硅片分割成若干片， 随机拿出其中 2片硅片在 35Ό 分别用上述清洗液组合物 1进行清洗， 清洗时间为 8分钟。
电子显微镜观察结果表明： 与清洗前（如图 5) 的晶片表面相比， 使用 本发明的清洗液组合物后 （如图 6) 的金属表面无明显缺陷； 而且从硅片的 剖面显微镜图可以看出， 与清洗前（如图 7)相比， 清洗后 （如图 8) 的硅 片内的通道尺寸沒有改变， 而且清洗后的通道内的残留物全被去掉。
效果实施例 3
分别测试清洗液组合物 1在 40°C时对 CORAL (美国诺发系统公司提供 的低电介质物质）膜， TEOS (原硅酸四乙酯）膜和 BPSG (硼磷硅酸盐玻璃） 膜的刻蚀速率。
结果表明： 使用本发明的清洗液组合物， CORAL膜的蚀刻速率可以忽 略不计 （如图 9) ， TEOS膜的蚀刻速率 （如图 10)与 BPSG膜的蚀刻速率 (如图 11 ) 为 1 : 1.04时， 通道内没有不平坦氧化蚀刻存在。

Claims

权利要求
1、 一种清洗液组合物， 其包括如下组分： 溶剂、 缓冲剂、 氟化物、 腐 蚀抑制剂和水， 其特征在于该缓冲剂包括： 弱酸、 铵类和胺类。
2、 稂据权利要求 1所述的清洗液组合物， 其特征在于： 所述的弱酸为 醋酸和 /或柠檬酸； 所述的铵类为醋酸铵、 柠檬酸铵和 /或氨水； 所述的胺类 为一乙醇胺、 二乙醇胺和 /或三乙醇胺。'
3、 根据权利要求 1或 2所述的清冼液组合物， 其特征在于： 所述的溶 剂的浓度为 47〜88%， 氟化物的浓度为 0.05〜3%， 腐蚀抑制剂的浓度为 0.01〜1.5%, 水的浓度为 9.9〜40%， 弱酸的浓度为 0.5〜4%、 铵类的浓度为 0.5〜5%、 胺类的浓度为 0.1〜5%。
4、 根据权利要求 3所述的清洗液组合物， 其特征在于： 所述的溶剂的 浓度为 73%， 氟化物的浓度为 0.4%，腐蚀抑制剂的浓度为 0.75%， 水的浓度 为 21%, 弱酸的浓度为 2%、 铵类的浓度为 2.6%、 胺类的浓度为 0.25%。
5、 根据权利要求 1或 2所述的清洗液组合物， 其特征在于： 所述的溶 剂为二甲基亚砜、 二甲基乙酰胺、. N-甲基吡咯垸酮和 /或乙二醇。
6、 根据权利要求 1或 2所述的清洗液组合物， 其特征在于： 所述的氟 化物为氟化氢、 氟化氢铵、 氟化铵、 四甲基氟化铵和 /或有机氟。
7、 根据权利要求 1或 2所述的清洗液组合物， 其特征在于： 所述的腐 蚀抑制剂为苯并三氮唑、苯并三氮唑衍生物、没食子酸、邻苯二酚和 /或苯类。
8、 根据权利要求 1或 2所述的清洗液组合物， 其特征在于： 该清洗液 组合物的 pH为 3.0〜5.8。
9、 根据权利要求 1或 2所述的清洗液组合物， 其特征在于： 该清洗液 组合物还包括表面活性剂和 /或络合剂。
PCT/CN2006/002621 2005-11-15 2006-10-08 Composition detergente aqueuse WO2007056919A1 (fr)

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CN101597548A (zh) * 2008-06-06 2009-12-09 安集微电子科技(上海)有限公司 一种等离子刻蚀残留物清洗液
CN101955852A (zh) * 2009-07-13 2011-01-26 安集微电子（上海）有限公司 一种等离子刻蚀残留物清洗液
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