TW202146638A - Chemical cleaning solution and its using method - Google Patents

Chemical cleaning solution and its using method Download PDF

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TW202146638A
TW202146638A TW110113238A TW110113238A TW202146638A TW 202146638 A TW202146638 A TW 202146638A TW 110113238 A TW110113238 A TW 110113238A TW 110113238 A TW110113238 A TW 110113238A TW 202146638 A TW202146638 A TW 202146638A
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Taiwan
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cleaning solution
chemical cleaning
solution according
acid
oxidant
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TW110113238A
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Chinese (zh)
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劉兵
彭洪修
肖林成
張維棚
趙鵬
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大陸商安集微電子科技(上海)股份有限公司
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Publication of TW202146638A publication Critical patent/TW202146638A/en

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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
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—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
    • C11D7/02—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
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble 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
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • 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
    • 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
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/3272—Urea, guanidine or derivatives thereof
    • 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
    • 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • H01L21/30608—Anisotropic liquid etching
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The present invention provides a chemical cleaning solution and its using method, which contains oxidant, pyrazoles and its derivatives, oxidant stabilizer, diethylene glycol amine, fluoride and water. The cleaning solution of the invention has strong cleaning ability, can effectively remove plasma etching residue and hard mask film titanium nitride in copper Damascus process by one step, and has low corrosion rate for metal Cu and non-metal media (such as SiON, TEOS, low dielectric constant material BDII, etc.).

Description

化學清洗液及其使用方法Chemical cleaning fluid and method of using the same

本發明涉及化學清洗領域，具體涉及一種化學清洗液及其使用方法。The invention relates to the field of chemical cleaning, in particular to a chemical cleaning solution and a method for using the same.

隨著微電子器件尺寸下降和性能要求的進一步提高，半導體器件中的金屬佈線臨界尺寸變得越來越小。為了減少信號的延遲和降低能耗，金屬銅取代金屬鋁、Low-k介質材料取代傳統介質材料成為一種新的趨勢。在廣泛使用銅雙大馬士革工藝的情況下，尋找能夠有效去除刻蝕殘留物的同時又能保護金屬銅及Low-k介質材料BDII的清洗液就越來越重要。As the size of microelectronic devices decreases and performance requirements further increase, the critical dimensions of metal wiring in semiconductor devices are becoming smaller and smaller. In order to reduce signal delay and reduce energy consumption, it has become a new trend that metal copper replaces metal aluminum and Low-k dielectric materials replace traditional dielectric materials. With the extensive use of the copper double damascene process, it is more and more important to find a cleaning solution that can effectively remove the etching residues while protecting the metal copper and the low-k dielectric material BDII.

同時隨著半導體制程尺寸越來越小，採用金屬硬掩膜氮化鈦可以有效控制圖形轉移從而提供更好刻蝕輪廓控制。但是圖形轉移後，殘留的金屬硬掩模氮化鈦不利於後續工藝填充工藝銅，常需要進一步去除金屬硬掩模氮化鈦。故能一步法去除金屬硬掩模和光抗蝕劑蝕刻殘餘物的組合物，就成為銅大馬士革工藝的必然要求。本發明的主要目的是高選擇性地去除氮化鈦硬掩膜和刻蝕殘留物，並且對金屬Cu和非金屬介質（如SiON、TEOS、Low-k介質材料BDII等）均有較小的腐蝕速率，操作視窗較大，在半導體晶圓清洗等微電子領域具有良好的應用前景。At the same time, as the size of the semiconductor process is getting smaller and smaller, the use of metal hard mask titanium nitride can effectively control the pattern transfer and provide better etching profile control. However, after the pattern is transferred, the remaining metal hard mask titanium nitride is not conducive to the subsequent process of filling copper, and it is often necessary to further remove the metal hard mask titanium nitride. Therefore, a composition capable of removing the metal hardmask and photoresist etching residues in one step has become an inevitable requirement of the copper damascene process. The main purpose of the present invention is to remove the titanium nitride hard mask and etching residues with high selectivity, and has a relatively small resistance to metal Cu and non-metal dielectrics (such as SiON, TEOS, Low-k dielectric material BDII, etc.). The corrosion rate and the operating window are large, and it has a good application prospect in the field of microelectronics such as semiconductor wafer cleaning.

為解決上述問題，本發明提供一種化學清洗液，能夠有效去除氮化鈦硬掩膜和刻蝕殘留物，同時對金屬Cu和非金屬介質（如SiON、TEOS、Low-k介質材料BDII等）均有較好的抑制腐蝕作用。In order to solve the above problems, the present invention provides a chemical cleaning solution, which can effectively remove titanium nitride hard masks and etching residues, and at the same time remove metal Cu and non-metal dielectrics (such as SiON, TEOS, Low-k dielectric materials BDII, etc.) All have good corrosion inhibition effect.

具體的，本發明中的化學清洗液含有氧化劑、吡唑及其衍生物、氧化劑穩定劑、二甘醇胺、氟化物以及水。Specifically, the chemical cleaning solution in the present invention contains oxidizing agent, pyrazole and its derivatives, oxidizing agent stabilizer, diethylene glycol amine, fluoride and water.

本發明中，所述氧化劑的質量百分比濃度為0.1%-15%。In the present invention, the mass percentage concentration of the oxidant is 0.1%-15%.

本發明中，所述吡唑及其衍生物的質量百分比濃度為0.1%-10%。In the present invention, the mass percentage concentration of the pyrazole and its derivatives is 0.1%-10%.

本發明中，所述氧化物穩定劑的質量百分比濃度為0.01-50ppm，優選的，所述氧化物穩定劑的質量百分比濃度為0.1-20ppm。In the present invention, the mass percent concentration of the oxide stabilizer is 0.01-50 ppm, preferably, the mass percent concentration of the oxide stabilizer is 0.1-20 ppm.

本發明中，所述二甘醇胺的質量百分比濃度為0.1%-9%。In the present invention, the mass percentage concentration of the diethylene glycol amine is 0.1%-9%.

本發明中，所述氟化物的質量百分比濃度為0.01%-3%。In the present invention, the mass percentage concentration of the fluoride is 0.01%-3%.

本發明中，所述氧化劑選自所述氧化劑選自H2 O2 、N-甲基嗎啉氧化物、臭氧、高氯酸、碘酸、高碘酸、過硫酸、過氧化脲((CO(NH2 )2 )H2 O2 )、過氧乙酸、過硫酸銨、過氧乙酸銨和四氧嘧啶中的一種或多種；優選的，所述氧化物為H2 O2 。In the present invention, the oxidant is selected from the oxidant selected from H 2 O 2 , N-methylmorpholine oxide, ozone, perchloric acid, iodic acid, periodic acid, persulfuric acid, carbamide peroxide ((CO One or more of (NH 2 ) 2 )H 2 O 2 ), peracetic acid, ammonium persulfate, ammonium peracetic acid and alloxan; preferably, the oxide is H 2 O 2 .

本發明中，所述吡唑及其衍生物選自吡唑、1-甲基吡唑、2-氨基吡唑、3-羥基吡唑、4-羧基吡唑、5-丙基吡唑、1-羥甲基吡唑、2-羥乙基吡唑、3-羥甲基吡唑、4-羥乙基吡唑、3，5-二甲基吡唑、3-氨基-5-甲基吡唑、3-羥基-5-氨基吡唑中的一種或多種。In the present invention, the pyrazole and its derivatives are selected from pyrazole, 1-methylpyrazole, 2-aminopyrazole, 3-hydroxypyrazole, 4-carboxypyrazole, 5-propylpyrazole, 1- -Hydroxymethylpyrazole, 2-hydroxyethylpyrazole, 3-hydroxymethylpyrazole, 4-hydroxyethylpyrazole, 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole One or more of azole and 3-hydroxy-5-aminopyrazole.

本發明中，所述氧化劑穩定劑選自甘氨酸、亞氨基二乙酸、氨三乙酸、乙二胺四乙酸、反式-1,2環己二胺四乙酸(CDTA)中的一種或多種。In the present invention, the oxidant stabilizer is selected from one or more of glycine, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and trans-1,2 cyclohexanediaminetetraacetic acid (CDTA).

本發明中，所述氟化物選自氟化氫、氟化銨和二氟化銨中的一種或多種。In the present invention, the fluoride is selected from one or more of hydrogen fluoride, ammonium fluoride and ammonium difluoride.

本發明中，水為餘量。In the present invention, water is the remainder.

本發明中，所述化學清洗液的pH值為7.5-10.5；優選的，所述化學清洗液的pH值為8-10。In the present invention, the pH value of the chemical cleaning solution is 7.5-10.5; preferably, the pH value of the chemical cleaning solution is 8-10.

本發明的另一方面，提供一種化學清洗液的使用方法，包括將本發明的化學清洗液用於銅大馬士革45nm及其以下工藝的清洗。Another aspect of the present invention provides a method for using a chemical cleaning solution, comprising using the chemical cleaning solution of the present invention for cleaning copper damascene 45nm and below processes.

本發明清洗液中含有的氧化物，用於去除硬膜氮化鈦；氧化物穩定劑用於清洗液中的氧化物組分，同時能夠有效促進清洗液對等離子體刻蝕殘留物的清洗效果；吡唑及其衍生物用於抑制清洗液對金屬銅的腐蝕。通過上述組分在一定含量範圍內的組合，本發明的清洗液清洗能力強，可一步有效去除銅大馬士革工藝中等離子體刻蝕殘留物和硬膜氮化鈦，並且對金屬Cu和非金屬介質（如SiON、TEOS、Low-k介質材料BDII等）均有較小的腐蝕速率。The oxide contained in the cleaning solution of the invention is used for removing hard film titanium nitride; the oxide stabilizer is used for the oxide component in the cleaning solution, and can effectively promote the cleaning effect of the cleaning solution on the plasma etching residues ; Pyrazole and its derivatives are used to inhibit the corrosion of metal copper by cleaning solution. Through the combination of the above components within a certain content range, the cleaning solution of the present invention has strong cleaning ability, can effectively remove plasma etching residues and hard film titanium nitride in the copper damascene process in one step, and can effectively remove metal Cu and non-metallic dielectrics. (such as SiON, TEOS, Low-k dielectric material BDII, etc.) all have a small corrosion rate.

下面結合附圖及具體實施例，詳細闡述本發明的優勢。The advantages of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

實施例Example

按照表1中實施例1~18和對比例1~6的組分及其含量，將所示組分混合均勻，其中，水為餘量。According to the components and contents of Examples 1 to 18 and Comparative Examples 1 to 6 in Table 1, the components shown are mixed uniformly, wherein water is the balance.

表1  實施例1~18和對比例1~6的組分及其含量 實施例 氧化劑 氧化劑穩定劑 氟化物 二甘醇胺 吡唑及其衍生物 水 種類 含量 種類 含量 種類 含量 含量 種類 含量 含量 1 過氧乙酸 15 甘氨酸 0.000001 氟化氫 3 5 吡唑 10 66.999999 2 N-甲基嗎啉氧化物 0.5 亞氨基二乙酸 0.005 氟化銨 0.01 0.1 1-甲基吡唑 0.5 98.885 3 臭氧 0.1 氨三乙酸、 0.00001 二氟化銨 0.05 9 2-氨基吡唑 0.1 90.74999 4 H2 O2 1 EDTA 0.0001 氟化氫 0.1 0.5 3-羥基吡唑 1 97.3999 5 碘酸 3 CDTA 0.00005 氟化銨 0.5 1 4-羧基吡唑 3 92.49995 6 高碘酸 5 甘氨酸 0.0002 二氟化銨 1 3 5-丙基吡唑 5 85.9998 7 過硫酸 7 亞氨基二乙酸 0.0005 氟化銨 2 8 1-羥甲基吡唑 7 75.9995 8 過氧化脲 9 氨三乙酸 0.001 氟化銨 1.5 6 2-羥乙基吡唑 9 74.499 9 高氯酸 10 EDTA 0.002 氟化銨 2.5 4 3-羥甲基吡唑 6 77.498 10 過硫酸銨 12 CDTA 0.003 氟化銨 0.3 9 4-羥乙基吡唑、 4 74.697 11 過氧乙酸銨 14 甘氨酸 0.0002 氟化銨 0.2 7 3，5-二甲基吡唑 2 76.7998 12 四氧嘧啶 6 亞氨基二乙酸 0.0004 氟化氫 0.7 2 3-氨基-5-甲基吡唑 5.5 85.7996 13 H2 O2 6 氨三乙酸 0.000005 氟化銨 0.9 7 3-羥基-5-氨基吡唑 3.5 82.599995 14 H2 O2 6 EDTA 0.0001 二氟化銨 1.2 8 吡唑 6 78.7999 15 H2 O2 6 CDTA 0.0008 氟化氫 2.8 9 吡唑 7 75.1992 16 H2 O2 6 EDTA 0.0005 氟化銨 0.8 3 吡唑 8 82.1995 17 H2 O2 9 CDTA 0.0003 氟化銨 0.6 4 吡唑 7.5 78.8997 18 H2 O2 8 EDTA 0.0001 氟化銨 1 5 吡唑 6.5 79.4999 對比例1 H2 O2 0 EDTA 0.0005 氟化銨 0.8 3 吡唑 8 82.1995 對比例2 H2 O2 6 EDTA 0 氟化銨 0.8 3 吡唑 8 82.1995 對比例3 H2 O2 6 EDTA 0.0005 氟化銨 0 3 吡唑 8 82.1995 對比例4 H2 O2 6 EDTA 0.0005 氟化銨 0.8 3 吡唑 0 82.1995 對比例5 H2 O2 6 EDTA 0.0005 氟化銨 0.8 10 吡唑 8 75.1995 對比例6 H2 O2 6 EDTA 0.0005 氟化銨 0.8 20 吡唑 8 65.1995 Table 1 Components and their contents of Examples 1-18 and Comparative Examples 1-6 Example Oxidizer Oxidant stabilizer Fluoride Diglycolamine Pyrazole and its derivatives water type content type content type content content type content content 1 peracetic acid 15 Glycine 0.000001 hydrogen fluoride 3 5 Pyrazole 10 66.999999 2 N-Methylmorpholine oxide 0.5 iminodiacetic acid 0.005 Ammonium fluoride 0.01 0.1 1-Methylpyrazole 0.5 98.885 3 ozone 0.1 nitrilotriacetic acid, 0.00001 Ammonium difluoride 0.05 9 2-Aminopyrazole 0.1 90.74999 4 H 2 O 2 1 EDTA 0.0001 hydrogen fluoride 0.1 0.5 3-Hydroxypyrazole 1 97.3999 5 iodic acid 3 CDTA 0.00005 Ammonium fluoride 0.5 1 4-Carboxypyrazole 3 92.49995 6 Periodic acid 5 Glycine 0.0002 Ammonium difluoride 1 3 5-propylpyrazole 5 85.9998 7 persulfuric acid 7 iminodiacetic acid 0.0005 Ammonium fluoride 2 8 1-Hydroxymethylpyrazole 7 75.9995 8 carbamide peroxide 9 nitrilotriacetic acid 0.001 Ammonium fluoride 1.5 6 2-Hydroxyethylpyrazole 9 74.499 9 perchloric acid 10 EDTA 0.002 Ammonium fluoride 2.5 4 3-Hydroxymethylpyrazole 6 77.498 10 Ammonium persulfate 12 CDTA 0.003 Ammonium fluoride 0.3 9 4-Hydroxyethylpyrazole, 4 74.697 11 ammonium peracetate 14 Glycine 0.0002 Ammonium fluoride 0.2 7 3,5-Dimethylpyrazole 2 76.7998 12 alloxan 6 iminodiacetic acid 0.0004 hydrogen fluoride 0.7 2 3-Amino-5-methylpyrazole 5.5 85.7996 13 H 2 O 2 6 nitrilotriacetic acid 0.000005 Ammonium fluoride 0.9 7 3-Hydroxy-5-aminopyrazole 3.5 82.599995 14 H 2 O 2 6 EDTA 0.0001 Ammonium difluoride 1.2 8 Pyrazole 6 78.7999 15 H 2 O 2 6 CDTA 0.0008 hydrogen fluoride 2.8 9 Pyrazole 7 75.1992 16 H 2 O 2 6 EDTA 0.0005 Ammonium fluoride 0.8 3 Pyrazole 8 82.1995 17 H 2 O 2 9 CDTA 0.0003 Ammonium fluoride 0.6 4 Pyrazole 7.5 78.8997 18 H 2 O 2 8 EDTA 0.0001 Ammonium fluoride 1 5 Pyrazole 6.5 79.4999 Comparative Example 1 H 2 O 2 0 EDTA 0.0005 Ammonium fluoride 0.8 3 Pyrazole 8 82.1995 Comparative Example 2 H 2 O 2 6 EDTA 0 Ammonium fluoride 0.8 3 Pyrazole 8 82.1995 Comparative Example 3 H 2 O 2 6 EDTA 0.0005 Ammonium fluoride 0 3 Pyrazole 8 82.1995 Comparative Example 4 H 2 O 2 6 EDTA 0.0005 Ammonium fluoride 0.8 3 Pyrazole 0 82.1995 Comparative Example 5 H 2 O 2 6 EDTA 0.0005 Ammonium fluoride 0.8 10 Pyrazole 8 75.1995 Comparative Example 6 H 2 O 2 6 EDTA 0.0005 Ammonium fluoride 0.8 20 Pyrazole 8 65.1995

可以理解的是，表1中所述含量均為質量百分比濃度。It can be understood that the contents described in Table 1 are all mass percentage concentrations.

隨後使用實施例4、實施例8、實施例13、實施例16以及對比例1~6的清洗液在35℃進行對氮化鈦、金屬銅以及非金屬材料的刻蝕速率的測試，並使用上述清洗液對晶圓進行清洗。實施例4、8、13、16及對比例1~6清洗液的刻蝕速率、氧化劑的穩定性及清洗效果資料記於表2。Subsequently, using the cleaning solutions of Example 4, Example 8, Example 13, Example 16 and Comparative Examples 1 to 6, the etching rates of titanium nitride, metallic copper and non-metallic materials were tested at 35° C. The above cleaning solution cleans the wafer. The etching rate of the cleaning solutions of Examples 4, 8, 13, 16 and Comparative Examples 1 to 6, the stability of the oxidizing agent and the cleaning effect data are recorded in Table 2.

其中，測試在北方華創單片機上進行。Among them, the test is carried out on the North Huachuang MCU.

表2  部分實施例與對比例的35℃蝕刻速率和清洗效果 清洗液 35℃氮化鈦蝕刻速率，Å/min 35℃金屬Cu蝕刻速率，Å/min 35℃非金屬蝕刻速率，Å/min 35℃/24小時氧化劑穩定性 晶圓清洗結果 SiON TEOS BDII 等離子體刻蝕殘留物的去除 硬膜氮化鈦的去除 實施例4 25.3 1.8 ＜1 ＜1 ＜1 ◎ ◎ ○ 實施例8 35.2 2.6 ＜1 ＜1 ＜1 ○ ◎ ◎ 實施例13 32.6 2.2 ＜1 ＜1 ＜1 ◎ ◎ ◎ 實施例16 38.1 1.5 ＜1 ＜1 ＜1 ◎ ◎ ◎ 對比例1 0 未測試 未測試 未測試 未測試 未測試 未測試 未測試 對比例2 33.4 1.3 ＜1 ＜1 ＜1 △ ○ ◎ 對比例3 19.7 2.1 ＜1 ＜1 ＜1 ◎ △ ○ 對比例4 27.8 18 ＜1 ＜1 ＜1 ◎ 未測試 未測試 對比例5 37.8 5.2 未測試 未測試 未測試 未測試 未測試 未測試 對比例6 36.3 8.4 未測試 未測試 未測試 未測試 未測試 未測試 35℃/24小時氧化劑穩定性 等離子體刻蝕殘留物及硬膜氮化鈦的去除 ◎ 基本無分解 ◎ 基本去除乾淨 ○ 輕微分解 ○ 少量殘留 △ 較多分解 △ 較多殘留 × 嚴重分解 × 大量殘留 Table 2 35℃ etching rate and cleaning effect of some examples and comparative examples Cleaning fluid Titanium nitride etch rate at 35℃, Å/min 35℃ metal Cu etching rate, Å/min 35℃ non-metal etch rate, Å/min Oxidant stability at 35°C/24 hours Wafer Cleaning Results SiON TEOS BDII Plasma Etch Residue Removal Removal of hard film titanium nitride Example 4 25.3 1.8 <1 <1 <1 ◎ ◎ ○ Example 8 35.2 2.6 <1 <1 <1 ○ ◎ ◎ Example 13 32.6 2.2 <1 <1 <1 ◎ ◎ ◎ Example 16 38.1 1.5 <1 <1 <1 ◎ ◎ ◎ Comparative Example 1 0 Not tested Not tested Not tested Not tested Not tested Not tested Not tested Comparative Example 2 33.4 1.3 <1 <1 <1 △ ○ ◎ Comparative Example 3 19.7 2.1 <1 <1 <1 ◎ △ ○ Comparative Example 4 27.8 18 <1 <1 <1 ◎ Not tested Not tested Comparative Example 5 37.8 5.2 Not tested Not tested Not tested Not tested Not tested Not tested Comparative Example 6 36.3 8.4 Not tested Not tested Not tested Not tested Not tested Not tested Oxidant stability at 35°C/24 hours Removal of Plasma Etch Residues and Hard Coated Titanium Nitride ◎ Basically no decomposition ◎ Basically remove clean ○ Slight decomposition ○ A small amount of residue △ more decomposition △ More residues × Severely decomposed × A lot of residue

根據表2，對比例1與實施例16的清洗資料表明：如若清洗液中不含有氧化劑，則清洗液對硬膜氮化鈦進行刻蝕。對比例2與實施例16對照表明，如若不添加氧化劑穩定劑，化學清洗液中含有的氧化劑的無法穩定存在，進而影響化學清洗液的整體穩定性，從而影響化學清洗液的清洗效果；同時，對比例2中的清洗液無法清洗等離子體刻蝕殘留物，表明本發明中選用的氧化劑穩定劑還可以有效促進清洗液對等離子體刻蝕殘留物的清洗效果。對比例3與實施例16對照表明氟化物能夠有效促進清洗液對等離子體刻蝕殘留物和硬膜氮化鈦的去除。對比例4與實施例16對照表明吡唑及其衍生物可以有效抑制清洗液對銅的腐蝕速率，從而實現對銅大馬士革工藝器件進行有效清洗同時保證對金屬銅有較好的抑制腐蝕作用。對比例5和6與實施例16對照表明，如若二甘醇胺的含量過高，超過9%時，銅的腐蝕速率過高，如果對銅大馬士革工藝器件進行清洗，會使器件的電性能受到負面影響。According to Table 2, the cleaning data of Comparative Example 1 and Example 16 show that: if the cleaning solution does not contain an oxidant, the cleaning solution will etch the hard film titanium nitride. Comparative example 2 and Example 16 contrast show, if do not add oxidant stabilizer, the oxidant contained in the chemical cleaning solution cannot exist stably, and then affects the overall stability of the chemical cleaning solution, thereby affecting the cleaning effect of the chemical cleaning solution; At the same time, The cleaning solution in Comparative Example 2 could not clean the plasma etching residues, indicating that the oxidant stabilizer selected in the present invention can also effectively promote the cleaning effect of the cleaning solution on the plasma etching residues. The comparison between Comparative Example 3 and Example 16 shows that fluoride can effectively promote the removal of plasma etching residues and hard film titanium nitride by the cleaning solution. The comparison between Comparative Example 4 and Example 16 shows that pyrazole and its derivatives can effectively inhibit the corrosion rate of copper by the cleaning solution, thereby achieving effective cleaning of copper damascene process devices and ensuring good corrosion inhibition of metal copper. Comparative Examples 5 and 6 compared with Example 16 show that if the content of diethylene glycol amine is too high, when it exceeds 9%, the corrosion rate of copper is too high, and if the copper damascene process device is cleaned, the electrical properties of the device will be affected. Negative impact.

綜上，本發明的積極進步效果在於：本發明的清洗液清洗能力強，可一步有效去除銅大馬士革工藝中等離子體刻蝕殘留物和硬膜氮化鈦，並且對金屬Cu和非金屬介質（如SiON、TEOS、Low-k介質材料BDII等）均有較小的腐蝕速率，操作視窗較大，在半導體晶圓清洗等微電子領域具有良好的應用前景。To sum up, the positive improvement effect of the present invention is that: the cleaning solution of the present invention has strong cleaning ability, can effectively remove plasma etching residues and hard film titanium nitride in the copper damascene process in one step, and can effectively remove metal Cu and non-metallic dielectrics ( Such as SiON, TEOS, Low-k dielectric materials BDII, etc.) all have a small corrosion rate, a large operating window, and have a good application prospect in the field of microelectronics such as semiconductor wafer cleaning.

以上對本發明的具體實施例進行了詳細描述，但其只是作為範例，本發明並不限制於以上描述的具體實施例。對於本領域技術人員而言，任何對本發明進行的等同修改和替代也都在本發明的範疇之中。因此，在不脫離本發明的精神和範圍下所作的均等變換和修改，都應涵蓋在本發明的範圍內。The specific embodiments of the present invention have been described above in detail, but they are only used as examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be included within the scope of the present invention.

無none

Claims (15)

一種化學清洗液，其特徵在於，含有氧化劑、吡唑及其衍生物、氧化劑穩定劑、二甘醇胺、氟化物以及水。A chemical cleaning solution is characterized in that it contains oxidant, pyrazole and its derivatives, oxidant stabilizer, diethylene glycol amine, fluoride and water. 如請求項1所述的化學清洗液，其中，所述氧化劑的質量百分比濃度為0.1%-15%。The chemical cleaning solution according to claim 1, wherein the mass percentage concentration of the oxidant is 0.1%-15%. 如請求項1所述的化學清洗液，其中，所述吡唑及其衍生物的質量百分比濃度為0.1%-10%。The chemical cleaning solution according to claim 1, wherein the mass percentage concentration of the pyrazole and its derivatives is 0.1%-10%. 如請求項1所述的化學清洗液，其中，所述氧化物穩定劑的質量百分比濃度為0.01-50ppm。The chemical cleaning solution according to claim 1, wherein the mass percentage concentration of the oxide stabilizer is 0.01-50 ppm. 如請求項4所述的化學清洗液，其中，所述氧化物穩定劑的質量百分比濃度為0.1-20ppm。The chemical cleaning solution according to claim 4, wherein the mass percentage concentration of the oxide stabilizer is 0.1-20 ppm. 如請求項1所述的化學清洗液，其中，所述二甘醇胺的質量百分比濃度為0.1%-9%。The chemical cleaning solution according to claim 1, wherein the mass percentage concentration of the diethylene glycol amine is 0.1%-9%. 如請求項1所述的化學清洗液，其中，所述氟化物的質量百分比濃度為0.01%-3%。The chemical cleaning solution according to claim 1, wherein the mass percentage concentration of the fluoride is 0.01%-3%. 如請求項1所述的化學清洗液，其中，所述氧化劑選自H2 O2 、N-甲基嗎啉氧化物、臭氧、高氯酸、碘酸、高碘酸、過硫酸、過氧化脲((CO(NH2 )2 )H2 O2 )、過氧乙酸、過硫酸銨、過氧乙酸銨和四氧嘧啶中的一種或多種。The chemical cleaning solution according to claim 1, wherein the oxidant is selected from H 2 O 2 , N-methylmorpholine oxide, ozone, perchloric acid, iodic acid, periodic acid, persulfuric acid, and peroxide urea ((CO (NH 2) 2 ) H 2 O 2), peracetic acid, ammonium persulfate, ammonium acetate and peroxygen alloxan one or more. 如請求項8所述的化學清洗液，其中，所述氧化劑為H2 O2 。The chemical cleaning solution according to claim 8, wherein the oxidant is H 2 O 2 . 如請求項1所述的化學清洗液，其中，所述吡唑及其衍生物選自吡唑、1-甲基吡唑、2-氨基吡唑、3-羥基吡唑、4-羧基吡唑、5-丙基吡唑、1-羥甲基吡唑、2-羥乙基吡唑、3-羥甲基吡唑、4-羥乙基吡唑、3，5-二甲基吡唑、3-氨基-5-甲基吡唑、3-羥基-5-氨基吡唑中的一種或多種。The chemical cleaning solution according to claim 1, wherein the pyrazole and its derivatives are selected from pyrazole, 1-methylpyrazole, 2-aminopyrazole, 3-hydroxypyrazole, and 4-carboxypyrazole , 5-propylpyrazole, 1-hydroxymethylpyrazole, 2-hydroxyethylpyrazole, 3-hydroxymethylpyrazole, 4-hydroxyethylpyrazole, 3,5-dimethylpyrazole, One or more of 3-amino-5-methylpyrazole and 3-hydroxy-5-aminopyrazole. 如請求項1所述的化學清洗液，其中，所述氧化劑穩定劑選自甘氨酸、亞氨基二乙酸、氨三乙酸、乙二胺四乙酸、反式-1,2環己二胺四乙酸(CDTA)中的一種或多種。The chemical cleaning solution according to claim 1, wherein the oxidant stabilizer is selected from glycine, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, trans-1,2 cyclohexanediaminetetraacetic acid ( one or more of CDTA). 如請求項1所述的化學清洗液，其中，所述氟化物選自氟化氫、氟化銨和二氟化銨中的一種或多種。The chemical cleaning solution according to claim 1, wherein the fluoride is selected from one or more of hydrogen fluoride, ammonium fluoride and ammonium difluoride. 如請求項1所述的化學清洗液，其中，所述化學清洗液的pH值為7.5-10.5。The chemical cleaning solution according to claim 1, wherein the pH value of the chemical cleaning solution is 7.5-10.5. 如請求項13所述的化學清洗液，其中，所述化學清洗液的pH值為8-10。The chemical cleaning solution according to claim 13, wherein the pH value of the chemical cleaning solution is 8-10. 一種化學清洗液的使用方法，其特徵在於，將請求項1-14中任一所述的清洗液用於銅大馬士革45nm及其以下工藝的清洗。A method of using a chemical cleaning solution, characterized in that the cleaning solution described in any one of claims 1-14 is used for the cleaning of copper damascene 45nm and below processes.
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