CN113186036B - Application of post-chemical mechanical polishing cleaning solution - Google Patents
Application of post-chemical mechanical polishing cleaning solution Download PDFInfo
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- 238000004140 cleaning Methods 0.000 title claims abstract description 53
- 238000005498 polishing Methods 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000004699 copper complex Chemical class 0.000 claims abstract description 32
- 239000004065 semiconductor Substances 0.000 claims abstract description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 44
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 44
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- 239000010949 copper Substances 0.000 claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 27
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 22
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 22
- 229960005070 ascorbic acid Drugs 0.000 claims description 22
- 235000010323 ascorbic acid Nutrition 0.000 claims description 22
- 239000011668 ascorbic acid Substances 0.000 claims description 22
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 22
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001231 choline Drugs 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 22
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 13
- 239000003112 inhibitor Substances 0.000 abstract description 8
- -1 alcohol amine Chemical class 0.000 abstract description 7
- 230000005764 inhibitory process Effects 0.000 abstract description 7
- 239000003963 antioxidant agent Substances 0.000 abstract description 6
- 230000003078 antioxidant effect Effects 0.000 abstract description 6
- 239000002738 chelating agent Substances 0.000 abstract description 6
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 235000012431 wafers Nutrition 0.000 description 18
- 238000002791 soaking Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 125000005496 phosphonium group Chemical group 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2096—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- 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
- C11D3/36—Organic compounds containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses an application of a cleaning solution after chemical mechanical polishing. The application of the cleaning solution in cleaning a semiconductor device after chemical mechanical polishing is specifically disclosed, and the cleaning solution comprises the following components in parts by mass: 0.01 to 25 percent of strong base, 0.01 to 30 percent of alcohol amine, 0.001 to 1 percent of antioxidant, 0.01 to 0.1 percent of copper complex, 0.01 to 10 percent of corrosion inhibitor, 0.01 to 10 percent of chelating agent, 0.01 to 5 percent of surfactant and 28.9 to 89.9 percent of water, wherein the sum of the mass fractions of the components is 100 percent; the copper complex is a 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex. The cleaning solution has the effects of cleaning, corrosion inhibition and BTA removal.
Description
Technical Field
The invention relates to application of a cleaning solution after chemical mechanical polishing.
Background
Metal materials such as copper, aluminum, tungsten, etc. are commonly used as conductive line materials in integrated circuits. Chemical Mechanical Polishing (CMP) is a major technique for wafer planarization in the fabrication of devices. The metal chemical mechanical polishing solution generally contains abrasive particles, a complexing agent, a metal corrosion inhibitor, an oxidizing agent, and the like. The abrasive particles are mainly silicon dioxide, aluminum oxide, aluminum-doped or aluminum-coated silicon dioxide, cerium dioxide, titanium dioxide, polymer abrasive particles, and the like. After the metal CMP process, the wafer surface is contaminated with metal ions and abrasive particles themselves in the slurry, which can affect the electrical characteristics of the semiconductor and the reliability of the device. The residues of these metal ions and abrasive particles can affect the flatness of the wafer surface, which can degrade device performance and affect subsequent processing or device operation. Therefore, it is very necessary to remove metal ions, metal corrosion inhibitors and abrasive particles remaining on the wafer surface after the metal CMP process, to improve the hydrophilicity of the cleaned wafer surface, and to reduce surface defects.
In the development process of the cleaning solution after CMP at present, how to consider cleaning, corrosion inhibition and BTA removal is a great technical difficulty in the synergistic development of the cleaning solution, the corrosion inhibition and the BTA removal. The present invention is a technical result obtained in the process of solving this technical problem.
Disclosure of Invention
The invention aims to solve the technical problem that the prior art lacks a post-CMP cleaning solution with cleaning, corrosion inhibition and BTA (BTA removal) effects, so that the invention provides an application of the post-CMP cleaning solution. The cleaning solution has the effects of cleaning, corrosion inhibition and BTA removal.
The present invention mainly solves the above-mentioned problems by the following technical means.
The invention provides an application of a cleaning solution in cleaning a semiconductor device after chemical mechanical polishing; the cleaning solution comprises the following raw materials in percentage by mass: 0.01 to 25 percent of strong base, 0.01 to 30 percent of alcohol amine, 0.001 to 1 percent of antioxidant, 0.01 to 0.1 percent of copper complex, 0.01 to 10 percent of corrosion inhibitor, 0.01 to 10 percent of chelating agent, 0.01 to 5 percent of surfactant and 28.9 to 89.9 percent of water, wherein the sum of the mass fractions of the components is 100 percent; the copper complex is a 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex.
In the application, the molecular formula of the copper complex is [ Cu (NO) 3 ) 2 (C 15 H 13 N 5 ) 2 ]In which C is 15 H 13 N 5 Is ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and the molecular structural formula is as follows:
in the application, the semiconductor device is a copper wafer.
In such applications, the strong base is preferably present in a mass fraction of 1% to 20%, more preferably 5% to 15%, for example 5% or 15%.
In the application, the mass fraction of the alcohol amine is preferably 1% to 10%, more preferably 5% to 8%, for example 8%.
In the application, the mass fraction of the antioxidant is preferably 0.002% to 0.1%, more preferably 0.005% to 0.01%, for example 0.01%.
In the application, the mass fraction of the copper complex is preferably 0.01% to 0.05%, more preferably 0.01% to 0.015%, for example 0.01% or 0.015%.
In such applications, the mass fraction of the corrosion inhibitor is preferably 0.1% to 1%, more preferably 0.5% to 0.8%, for example 0.8%.
In such applications, the chelating agent is preferably present in an amount of 0.1% to 1%, more preferably 0.3% to 0.9%, for example 0.9% by mass.
In such applications, the surfactant is preferably present in an amount of 0.1% to 1%, more preferably 0.2% to 0.7%, for example 0.7% by mass.
In the application, the strong base is conventional in the field, preferably one or more of quaternary ammonium base, quaternary phosphonium base and guanidine compound, and more preferably quaternary ammonium base.
The quaternary ammonium base is preferably tetraalkyl quaternary ammonium base and/or quaternary ammonium base having a hydroxyl substituent on the alkyl group, more preferably tetraalkyl quaternary ammonium base.
The tetraalkyl quaternary ammonium hydroxide is preferably tetramethyl ammonium hydroxide and/or tetrapropyl ammonium hydroxide, more preferably tetramethyl ammonium hydroxide.
The quaternary ammonium base having a hydroxyl substituent on the alkyl group is preferably one or more of choline, (2-hydroxyethyl) trimethylammonium hydroxide and tris (2-hydroxyethyl) methylammonium hydroxide.
The quaternary phosphonium base is preferably a tetraalkyl quaternary phosphonium base and/or a quaternary phosphonium base having a hydroxyl substituent on the alkyl group.
The tetraalkyl quaternary phosphonium base is preferably tetrabutyl phosphine oxide.
The guanidine compound is preferably tetramethyl guanidine.
In the application, the alcohol amine is conventional in the field, and is preferably monoethanolamine.
In the application, the antioxidant is an antioxidant which is conventional in the field, and is preferably ascorbic acid.
In the application, the corrosion inhibitor is a conventional corrosion inhibitor in the field, and is preferably 2-mercaptobenzothiazole.
In the application, the chelating agent is a conventional chelating agent in the field, and is preferably malonic acid.
In the application, the surfactant is a conventional surfactant in the field, preferably an ionic surfactant or a nonionic surfactant, more preferably a nonionic surfactant, such as dodecyl benzene sulfonic acid.
In the application, preferably, the raw materials of the cleaning solution consist of the following components in percentage by mass: 0.01 to 25 percent of strong base, 0.01 to 30 percent of alcohol amine, 0.001 to 1 percent of antioxidant, 0.01 to 0.1 percent of copper complex, 0.01 to 10 percent of corrosion inhibitor, 0.01 to 10 percent of chelating agent, 0.01 to 5 percent of surfactant and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent.
In the application, in a preferred scheme, the raw materials of the cleaning solution can consist of the components shown in any one of the following schemes:
scheme 1:15 percent of tetramethylammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.015 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid, and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 2:15 percent of tetramethylammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.01 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid, and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 3:15 percent of tetramethylammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.05 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid, and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 4:5 percent of tetramethylammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.01 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid, and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 5:15% of choline, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.1% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid and water, wherein the balance is the sum of the mass fractions of the components is 100%;
scheme 6:15% of tetrapropylammonium hydroxide, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.015% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid, and water, wherein the balance is the sum of the mass fractions of the components is 100%;
scheme 7:15 percent of (2-hydroxyethyl) trimethyl ammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.015 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 8:15 percent of tris (2-hydroxyethyl) methyl ammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.015 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 9:15% of tetrabutyl hydrogen phosphine oxide, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.015% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid, and the balance of water, wherein the sum of the mass fractions of the components is 100%;
scheme 10:15% of tetramethylguanidine, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.015% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid and water to make up the balance, wherein the sum of the mass fractions of the components is 100%.
In the application, the cleaning solution can be prepared by the following preparation method, and the preparation method comprises the following steps: mixing the raw materials of the cleaning solution.
In the application, in the preparation method, the mixing is preferably performed by adding the solid component in the raw material components into the liquid component and uniformly stirring.
In the application, the temperature of the mixing in the preparation method is preferably room temperature.
In the application, in the preparation method, preferably, after the mixing, the operations of shaking and filtering are further included, the purpose of shaking is to fully mix the raw material components, and the shaking speed and the time are not limited. Filtration was performed to remove insoluble matter.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: provides the application of the cleaning solution after the chemical mechanical polishing. The cleaning solution disclosed by the invention has better cleaning capability, better corrosion inhibition effect, stronger BTA removing capability and better stability, and can realize the effects of cleaning, corrosion inhibition and BTA removing at the same time.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, the cleaning solution was prepared by the following steps: mixing the corresponding raw materials.
In the following examples, the specific operation temperature is not limited, and all the operations are carried out at room temperature.
I. Examples of the preparation method of cleaning solution
1. Preparation of copper complexes
The copper complex is 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex with a molecular formula of [ Cu (NO) 3 ) 2 (C 15 H 13 N 5 ) 2 ]In which C is 15 H 13 N 5 Is ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and the molecular structural formula is as follows:
the copper complex is prepared by a preparation method in a patent CN106188103B, and the concrete embodiment of the patent is shown in the specification; the ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) and copper nitrate are used as raw materials, and the reaction molar ratio of the ligand to the copper nitrate is 1:1. Wherein, the ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) is also prepared by adopting the method in patent CN106188103B, and the copper nitrate is commercially available.
2. Examples of the preparation method of cleaning solution
The raw material components in the table 1 are uniformly mixed according to the mass fraction in the table, and the balance is made up by using water. Wherein, the mixing is generally to add the solid component in the raw material components into the liquid component and stir uniformly. The mixing is generally to add the solid components in the raw material components into the liquid components and stir the mixture evenly. The temperature of the mixing is room temperature. After the mixing, the operations of shaking and filtering are further generally included. The purpose of shaking is to fully mix the raw material components, and the shaking speed and time are not limited. Filtration was performed to remove insoluble matter.
In tables 1 and 3 below, the component species in each example also included water.
TABLE 1 component classes in the examples
In Table 1, A represents a 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex.
TABLE 2 Mass fractions of the respective raw material components
The "balance" in the table is the mass percentage of 100% minus the other components except water in each example.
Comparative examples 1 to 3
TABLE 3 raw material composition of cleaning solution
TABLE 4 Mass fractions of the respective raw material components
The "balance" in the table is the mass percentage of 100% minus the other components except water in each example.
Effects of the embodiment
1. Preparation of copper wafers:
1. pretreatment: for 8 inch Cu plated wafers (copper plating thickness about 1 um), 10% was adopted 2 SO 4 Treating at 25 deg.C for 2min;
2. cleaning with pure water and drying with nitrogen;
2. polishing:
the polishing machine is 8' Mirra, the rotating speed of the polishing disk and the polishing head is 93/87rpm, the flow rate of the polishing solution is 150ml/min, the polishing pad used for copper polishing is IC1010, and the polishing pad used for barrier layer polishing is Fujibo H7000. The copper polishing solution was AEP U3000 and the barrier layer polishing solution was TCU2000H4. The prepared copper wafer is subjected to a polishing process.
3. The testing steps are as follows:
detection of ER
The test method comprises the following steps:
1. cutting the polished copper wafer into square pieces of 3cm by 3 cm;
2. measuring the thickness of the copper wafer and the functional relation of the resistivity of the copper wafer by adopting a four-point probe instrument to generate a regression curve, and determining the functional relation of the thickness of the copper and the resistivity for calculating the corrosion rate of the copper;
3. soaking 50ml of cleaning solution at 25 ℃ for 1min for corrosion;
4. and measuring the resistance by a four-point probe instrument, then calculating the thickness change of the metal before and after corrosion, and calculating the corrosion rate.
(II) surface corrosion detection
The test method comprises the following steps:
1. cutting the polished copper wafer into 3 cm-by-3 cm square pieces;
2. soaking in cleaning solution at 25 deg.C for 1min for corrosion;
3. the copper wafers after etching were subjected to Atomic Force Microscope (AFM) testing and RMS values thereof were measured.
(III) cleaning Capacity detection
The test method comprises the following steps:
1. cutting the polished copper wafer into 3 cm-by-3 cm square pieces;
2. soaking and cleaning in cleaning solution at 25 deg.C for 2min;
3. and (5) observing under SEM.
(IV) BTA removal capability
The detection method 1:
1. cutting the polished copper wafer into 3 cm-by-3 cm square pieces;
2. treating with 3% citric acid at 25 deg.C for 2min; soaking the copper sheet in 1+1 nitric acid solution, treating at 25 ℃ for 2min, and testing the thickness of the copper by using a surface profiler;
3. cleaning with pure water and drying with nitrogen;
4. Cu-BTA film formation: soaking the treated copper sheet in 3% hydrogen peroxide +0.5% BTA +20ppm sulfuric acid solution at 25 ℃ for 10min;
5. removal of BTA: different cleaning solutions are respectively used for soaking the copper sheet with the BTA film (soaking for 1min at 25 ℃), and the thickness is measured by a profilometer to represent the BTA removing effect.
The detection method 2 comprises the following steps:
1. cutting the polished copper wafer into 3 cm-by-3 cm square pieces;
2. treating with 3% citric acid at 25 deg.C for 2min; then testing the contact angle of the deionized water;
3. cleaning with pure water and drying with nitrogen;
4. Cu-BTA film formation: soaking the treated copper sheet in 3% hydrogen peroxide +0.5% BTA +20ppm sulfuric acid solution at 25 ℃ for 10min; testing the contact angle of deionized water;
5. BTA removal: soaking the copper sheet with the BTA film in a cleaning solution (soaking for 2min at 25 ℃), and testing the contact angle of deionized water;
(V) solution stability test
0.4 liters of the cleaning solution was poured into a 0.5L plastic container, 0.1 liters of the remaining was filled with nitrogen, and the following changes in the placement were observed for 4 days, 7 days, and 1 month:
1. a change in color of the solution;
2. the generation of bubbles;
3. a change in pH;
4. the change of the copper corrosion rate (the detection method is the same as the above);
5. AFM measures changes in surface roughness RMS (as described above).
TABLE 5 Effect of freshly prepared solutions
TABLE 6 Effect of the solutions left for 4 days, 7 days and 1 month (30 days)
As can be seen from the effect comparative examples 1-3 and the effect examples 1-10, the cleaning solution of the present invention has improved performance in various aspects by adding the specific copper complex. The cleaning solution disclosed by the invention has the advantages of low corrosivity, good cleaning effect, strong BTA (BTA removal) capability and good long-acting stability for cleaning a copper wafer after CMP (chemical mechanical polishing).
Claims (5)
1. The application of the cleaning solution in cleaning a semiconductor device after chemical mechanical polishing is characterized in that the raw materials of the cleaning solution comprise the following components in percentage by mass: 5 to 15 percent of strong base, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.01 to 0.1 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid and 0.7 percent of dodecylbenzene sulfonic acid, and the balance of water, wherein the sum of the mass fractions of the components is 100 percent; the strong base is one or more of tetramethylammonium hydroxide, tetrapropylammonium hydroxide, choline, (2-hydroxyethyl) trimethylammonium hydroxide, tris (2-hydroxyethyl) methylammonium hydroxide, tetrabutylphosphine oxide and tetramethylguanidine, and the molecular formula of the copper complex is [ Cu (NO) 3 ) 2 (C 15 H 13 N 5 ) 2 ]In which C is 15 H 13 N 5 Is ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and the molecular structural formula is as follows:
。
2. the use of claim 1, wherein the semiconductor device is a copper wafer.
3. The use of claim 1, wherein the cleaning solution comprises a composition according to any of the following schemes:
scheme 1:15 percent of tetramethylammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.015 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid, and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 2:15 percent of tetramethylammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.01 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid, and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 3:15 percent of tetramethylammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.05 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid, and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 4:5% of tetramethylammonium hydroxide, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.01% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid, and water for balancing, wherein the sum of the mass fractions of the components is 100%;
scheme 5:15% of choline, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.1% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid and water, wherein the balance is the sum of the mass fractions of the components is 100%;
scheme 6:15% of tetrapropylammonium hydroxide, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.015% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid, and water, wherein the balance is the sum of the mass fractions of the components is 100%;
scheme 7:15 percent of (2-hydroxyethyl) trimethyl ammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.015 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 8:15 percent of tris (2-hydroxyethyl) methyl ammonium hydroxide, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.015 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent;
scheme 9:15% of tetrabutyl hydrogen phosphine oxide, 8% of monoethanolamine, 0.01% of ascorbic acid, 0.015% of copper complex, 0.8% of 2-mercaptobenzothiazole, 0.9% of malonic acid, 0.7% of dodecylbenzene sulfonic acid, and the balance of water, wherein the sum of the mass fractions of the components is 100%;
scheme 10:15 percent of tetramethylguanidine, 8 percent of monoethanolamine, 0.01 percent of ascorbic acid, 0.015 percent of copper complex, 0.8 percent of 2-mercaptobenzothiazole, 0.9 percent of malonic acid, 0.7 percent of dodecylbenzene sulfonic acid and water to make up the balance, wherein the sum of the mass fractions of the components is 100 percent.
4. The use according to claim 1, wherein the cleaning solution is prepared by a preparation method comprising the steps of: and mixing the raw materials of the cleaning solution.
5. The use of claim 4, wherein said mixing is by adding the solid component of said feedstock components to the liquid component and stirring the mixture to homogeneity;
and/or, the temperature of the mixing is room temperature;
and/or the preparation method further comprises the operations of shaking and filtering.
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| JP2004022855A (en) * | 2002-06-18 | 2004-01-22 | Shibaura Mechatronics Corp | Process for producing semiconductor device |
| WO2009058275A1 (en) * | 2007-10-29 | 2009-05-07 | Ekc Technology, Inc. | Methods of post chemical mechanical polishing and wafer cleaning using amidoxime compositions |
| CN106188103B (en) * | 2016-07-14 | 2017-10-13 | 河南中医学院 | A kind of azacyclo- transition metal copper complex containing multiple coordination sites, preparation method and application |
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