CN101126053A - Cleaning liquid composition for plasma etching residues in semi-conductor industry - Google Patents
Cleaning liquid composition for plasma etching residues in semi-conductor industry Download PDFInfo
- Publication number
- CN101126053A CN101126053A CNA200610030170XA CN200610030170A CN101126053A CN 101126053 A CN101126053 A CN 101126053A CN A200610030170X A CNA200610030170X A CN A200610030170XA CN 200610030170 A CN200610030170 A CN 200610030170A CN 101126053 A CN101126053 A CN 101126053A
- Authority
- CN
- China
- Prior art keywords
- cleaning liquid
- liquid composition
- acetate
- buffer solution
- inhibitor
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 73
- 239000007788 liquid Substances 0.000 title claims abstract description 58
- 239000004065 semiconductor Substances 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 title claims description 51
- 238000001020 plasma etching Methods 0.000 title abstract 3
- 239000003112 inhibitor Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000872 buffer Substances 0.000 claims abstract description 5
- -1 PETEOS Chemical compound 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 23
- 239000012964 benzotriazole Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 11
- 239000011976 maleic acid Substances 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 239000012062 aqueous buffer Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims 2
- 229940043376 ammonium acetate Drugs 0.000 claims 2
- 235000019257 ammonium acetate Nutrition 0.000 claims 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 229910052719 titanium Inorganic materials 0.000 abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000007798 antifreeze agent Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 20
- 239000010936 titanium Substances 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 12
- 230000002000 scavenging effect Effects 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- CKKXWJDFFQPBQL-UAIGNFCESA-N diazanium;(z)-but-2-enedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)\C=C/C([O-])=O CKKXWJDFFQPBQL-UAIGNFCESA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- PINFZJSTBDUCPF-UHFFFAOYSA-N [Si](=O)=O.C[Si](C)(C)C Chemical compound [Si](=O)=O.C[Si](C)(C)C PINFZJSTBDUCPF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
- 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
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
- C11D7/261—Alcohols; Phenols
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a cleaning liquid combination used for removing plasma-etching residue in semiconductor industry. The cleaning liquid comprises amount of solvent used for effectively washing, buffer aqueous solution, fluoride, antifreeze agent, polymer inhibitor. The cleaning liquid combination of the invention can effectively clean plasma-etching residue in semiconductor industry without eroding SiO2, PETEOS, silicon, low medium material and some metals such as Ti, Al and Cu.
Description
Technical field
The present invention relates to a kind of cleaning liquid composition, relate in particular to the cleaning liquid composition that is used for semi-conductor industry ionic medium etch residue.
Background technology
In the semiconductor components and devices manufacturing processed, the coating of photoresist layer, exposure and imaging are necessary process steps to the pattern manufacturing of components and parts.Before last (promptly after coating, imaging, ion implantation and the etching at photoresist layer) of patterning carried out next processing step, the residue of photoresist layer material need thoroughly be removed.Can sclerosis photoresist layer polymkeric substance in doping step intermediate ion bombardment, thus therefore making photoresist layer become to be difficult for dissolving more is difficult to remove.So far the general two-step approach (dry ashing and wet etching) of using is removed this layer photoresistance tunic in semi-conductor industry.The first step utilizes dry ashing to remove the major part of photoresist layer (PR); Second step utilized composite corrosion inhibitor wet etching/cleaning to remove and wash remaining photoresist layer.In the cleaning process in second step, composite corrosion inhibitor can only be removed polymkeric substance photoresist layer and inorganic residue, and can not attack infringement metal level such as aluminium lamination.
Typical scavenging solution has following several in the prior art: amine scavenging solution, semi-aqueous amido (non-azanol class) scavenging solution and fluorochemical based cleaning liquid.Wherein preceding two based cleaning liquids need at high temperature to clean, generally between 60 ℃ to 80 ℃; And existing fluorochemical based cleaning liquid still exists various shortcomings, and for example following patent: US 6,593,282, US 6,828,289, US 5,972, and 862, US 6,592,433 and US 6,773,873 disclose various cleaning liquid compositions, as US 6,828,289 disclosed cleaning liquid compositions comprise: acidic buffer, organic polar solvent, fluorine-containing material and water, and the pH value is between 3～7, acidic buffer wherein is made up of organic carboxyl acid or polyprotonic acid and pairing ammonium salt, and proportion of composing is between 10: 1 to 1: 10, but emphasizes to contain ethylene glycol.As US 5,698,503 disclose fluorine-containing scavenging solution, but make spent glycol in a large number, and the viscosity of its scavenging solution and surface tension are all very big, thereby influence cleaning performance.As US 5,972,862 disclose the cleaning combination of fluorine-containing material, and it comprises that fluorine-containing material, weak acid and weak base such as ammonium salt form damping fluid, organic polar solvent, and pH is 7～11, and cleaning performance is not very effective, has various problem.This based cleaning liquid can not be controlled metal and nonmetallic etch-rate usually simultaneously, causes the change of channel characteristics size after the cleaning easily, thereby changes semiconductor structure; And because its big etch-rate, the cleaning operation window is very little, can cause various negative impacts in operating process.
The inhibitor that prior art is used has pyrocatechol, hydroxyquinol, on the one hand because these inhibitor can not be controlled the etch-rate of metal and oxide compound simultaneously; It has strong effect to the environment and the mankind on the other hand.
Although therefore disclosed some cleaning liquid compositions, but need and need more recently to prepare a class more suitably cleaning combination or system, adapt to new cleaning requirement, more friendly such as environment, low defect level, low etching rate and big action pane.
Summary of the invention
The objective of the invention is in order how to solve safety, healthy and effectively clean semi-conductor industry ionic medium etch residue, and a kind of cleaning liquid composition safely and effectively is provided.
The present invention is a kind of cleaning liquid composition that is used for semi-conductor industry ionic medium etch residue, and it comprises solvent, aqueous buffer solution, fluorochemical, polymer inhibitor and the antifreezing agent that cleans significant quantity.
Wherein, described cleaning liquid composition also comprises micromolecular inhibitor.
The preferred weight percent content of described cleaning liquid composition is:
(a) solvent 50%～85%
(b) aqueous buffer solution 10%～46%
(c) fluorochemical 0.05%～3%
(d) polymer inhibitor 0.0001%～10%
(e) micromolecular inhibitor 0%～10%
(f) antifreezing agent 0.0001%～10%
Solvent of the present invention comprises N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl formamide or tetramethylene sulfone.
Aqueous buffer solution of the present invention comprises the acetate and the ammonium acetate salt buffer aqueous solution.
Described acetate and acetate ammonium salt weight percent in aqueous buffer solution preferably is 5%～60%;
Weight percent more preferably is 10%～50%;
Weight percent is most preferably 20%～40%.
Fluorochemical preferably is NH
4F, HF or NH
4HF
2
Polymer inhibitor of the present invention is preferably for poly-carboxyl ether, polymaleic anhydride, polyacrylic acid, polymethyl acrylic acid and/or contain the homopolymer of carboxyl and/or contain the multipolymer of carboxyl; The described multipolymer that contains carboxyl preferably is carboxylic copolyether, vinylformic acid and maleic acid, vinylbenzene and acrylic copolymer, vinylbenzene and maleic acid and/or vinyl cyanide and maleic acid and their ammonium salt, sylvite and/or sodium salt.
The weight percent of described polymkeric substance preferably is 0.01%～3%.
Micromolecular inhibitor of the present invention preferably is a benzotriazole (BTA).
Antifreezing agent of the present invention preferably is an ethylene glycol (G).
The polymer inhibitor of cleaning liquid composition of the present invention comprises and contains the carboxylic group polymer that it can be as corrosion inhibitor, tensio-active agent, sequestrant.It has better suitable environment and effect than traditional inhibitor such as pyrocatechol, hydroxyquinol.And polymer inhibitor can be simultaneously to metal with nonmetally play the good effect of corrosion inhibition.Meanwhile this system is as safe as a house to environment, health.
The a spot of antifreezing agent ethylene glycol of cleaning liquid composition, this is very little to solution surface tension and soltion viscosity influence, and can not influence the cleaning effect of wafer.
Positive progressive effect of the present invention is: cleaning liquid composition of the present invention can play a role in the bigger scope of temperature, generally in room temperature to 45 ℃ scope, and can be used for very wide field, such as batch immersion type/batch rotary/monolithic is rotary.Simultaneously, cleaning liquid composition has less metal and electric Jie's material etching rate.
Cleaning liquid composition of the present invention is clean metal and semiconductor fabrication ionic medium etch residue effectively also, and can not corrode SiO
2, ion strengthens tetraethoxysilane silicon-dioxide (PETEOS), silicon, low dielectric material and some metallicses (as Ti, A1, Cu).For semi-conductor industry, cleaning liquid composition of the present invention can use in immersion in batches, batch rotation and monolithic rotary processor.
Description of drawings
Fig. 1 is the SEM figure that has the metal wire of titanium/titanium nitride/aluminium/titanium/titanium nitride/silicon oxide structure before cleaning;
Fig. 2 is the SEM figure that has the metal wire of titanium/titanium nitride/aluminium/titanium/titanium nitride/silicon oxide structure before cleaning;
Fig. 3 is that 25 ℃ of metal wires with titanium/titanium nitride/aluminium/titanium/titanium nitride/silicon oxide structure are schemed with the SEM of scavenging solution cleaning after 15 minutes among the embodiment 1;
Fig. 4 is that 25 ℃ of metal wires with titanium/titanium nitride/aluminium/titanium/titanium nitride/silicon oxide structure are schemed with the SEM of scavenging solution cleaning after 15 minutes among the embodiment 1;
Fig. 5 has the section SEM figure that ion strengthens relevant passage in the metal wire of tetramethylsilane silicon-dioxide/high-density plasma method silicon-dioxide/titanium/titanium nitride/constructed of aluminium before 25 ℃ of cleanings;
Fig. 6 be 25 ℃ clean 15 minutes with scavenging solution among the embodiment 1 after, have the section SEM figure that ion strengthens relevant passage in the metal wire of tetramethylsilane silicon-dioxide/high-density plasma method silicon-dioxide/titanium/titanium nitride/constructed of aluminium;
Fig. 7 be 30 ℃ clean 30 minutes with scavenging solution among the embodiment 1 after, have the section SEM figure that ion strengthens relevant passage in the metal wire of tetramethylsilane silicon-dioxide/high-density plasma method silicon-dioxide/titanium/titanium nitride/constructed of aluminium;
Fig. 8 be 30 ℃ clean 30 minutes with scavenging solution among the embodiment 1 after, have the section SEM figure of relevant passage in the metal wire of high-density plasma method silicon-dioxide/titanium/titanium nitride/constructed of aluminium.
Embodiment
Embodiment 1
The component of cleaning liquid composition 1: N-Methyl pyrrolidone 60wt%, DI 28.44wt%, NH
4F 1.25wt%, Ac 1.56wt%, AcNH
47.8wt%, benzotriazole (BTA) 0.3wt%, ammonium polyacrylate (molecular weight is 600), 0.15wt%, G 0.5wt%.
Embodiment 2
The component of cleaning liquid composition 2: N-Methyl pyrrolidone 50wt%, DI 26.3wt%, NH
4F 3wt%, Ac 5.1wt%, AcNH
412.4wt%, benzotriazole (BTA) 0wt%, ammonium polyacrylate (molecular weight is 600), 0.3wt%, G 0.2wt%.
Embodiment 3
The component of cleaning liquid composition 3: N-Methyl pyrrolidone 85wt%, DI 8wt%, NH
4F0.05wt%, Ac 1wt%, AcNH
41wt%, benzotriazole (BTA) 0.94wt%, ammonium polyacrylate (molecular weight is 600), 00.01wt%, G 4wt%.
Embodiment 4
The component of cleaning liquid composition 4: dimethyl sulfoxide (DMSO) 52wt%, DI 0.34wt%, NH
4HF
22wt%, Ac 7.6wt%, AcNH
438wt%, vinylformic acid and maleic acid (molecular weight is 1500), 0.01wt%, G 0.05wt%.
The component of cleaning liquid composition 5: tetramethylene sulfone 85wt%, DI 4.3499wt%, NH
4HF
20.05wt%, Ac 1.5wt%, AcNH
49wt%, vinylbenzene and acrylic copolymer (molecular weight is 5000), 0.1wt%, G 0.0001wt%.
The component of cleaning liquid composition 6: tetramethylene sulfone 55wt%, DI 14.43wt%, NH
4HF
20.5wt%, Ac 1.82wt%, AcNH
418.2wt%, vinyl cyanide and maleic acid ammonium salt (molecular weight is 2000), 0.05wt%, G 10wt%.
Embodiment 7
The component of cleaning liquid composition 7: tetramethylene sulfone 52wt%, DI 15.95wt%, NH
4HF
23wt%, Ac 8wt%, AcNH
420wt%, polymaleic anhydride (molecular weight is 600), 0.05wt%, G 1wt%.
Embodiment 8
The component of cleaning liquid composition 8: tetramethylene sulfone 60wt%, DI 14.9wt%, NH
4HF
20.1wt%, Ac 6wt%, AcNH
412wt%, vinylformic acid and maleic acid ammonium salt (molecular weight is 800), 1wt%, G 6wt%.
Embodiment 9
The component of cleaning liquid composition 9: tetramethylene sulfone 65wt%, DI 7.9wt%, NH
4HF
20.5wt%, Ac 6.5wt%, AcNH
410wt%, vinylformic acid and maleic acid (molecular weight is 700), 10wt%, G 0.1wt%.
Embodiment 10
The component of cleaning liquid composition 10: tetramethylene sulfone 55wt%, DI 18.7wt%, NH
4HF
20.1wt%, Ac 6wt%, AcNH
420wt%, vinylformic acid and maleic acid (molecular weight is 2000), 0.1wt%, G 0.1wt%.
The component of cleaning liquid composition 11: dimethyl sulfoxide (DMSO) 52wt%, DI 0.24wt%, NH
4HF
22wt%, Ac 7.6wt%, AcNH
438wt%, benzotriazole (BTA) 0.1wt%, vinylformic acid and maleic acid (molecular weight is 1500), 0.01wt%, G 0.05wt%.
Embodiment 12
The component of cleaning liquid composition 12: tetramethylene sulfone 85wt%, DI 3.3499wt%, NH
4HF
20.05wt%, Ac2.5wt%, AcNH
48wt%, benzotriazole (BTA) 1wt%, vinylbenzene and acrylic copolymer (molecular weight is 2000), 0.1wt%, G 0.0001wt%.
Embodiment 13
The component of cleaning liquid composition 13: tetramethylene sulfone 55wt%, DI 10.43wt%, NH
4HF
20.5wt%, Ac 1.82wt%, AcNH
418.2wt%, benzotriazole (BTA) 4wt%, vinyl cyanide and maleic acid ammonium salt (molecular weight is 1500), 0.05wt%, G 10wt%.
Embodiment 14
The component of cleaning liquid composition 14: tetramethylene sulfone 52wt%, DI 10.95wt%, NH
4HF
23wt%, Ac8wt%, AcNH
420wt%, benzotriazole (BTA) 5wt%, polymaleic anhydride (molecular weight is 600), 0.05wt%, G 1wt%.
Embodiment 15
The component of cleaning liquid composition 15: tetramethylene sulfone 60wt%, DI 14.9wt%, NH
4HF
20.1wt%, Ac 6wt%, AcNH
412wt%, vinylformic acid and maleic acid ammonium salt (molecular weight is 1200), 1wt%, G 6wt%.
Embodiment 16
The component of cleaning liquid composition 16: tetramethylene sulfone 65wt%, DI 6.9wt%, NH
4HF
20.5wt%, Ac 6.5wt%, AcNH
410wt%, benzotriazole (BTA) 1wt%, vinylformic acid and maleic acid (molecular weight is 1500), 10wt%, G 0.1wt%.
Embodiment 17
The component of cleaning liquid composition 17: tetramethylene sulfone 55wt%, DI 8.7wt%, NH
4HF
20.1wt%, Ac 6wt%, AcNH
420wt%, benzotriazole (BTA) 10wt%, poly-carboxyl ether (molecular weight is 5000), 0.1wt%, G 0.1wt%.
Embodiment 18
Etching rate when under different substances, differing temps, forming with scavenging solution among the embodiment 1
| Raw material | 25℃(A/Min) | 30℃(A/Min) | 35℃(A/Min) | |||
| 1 st 30min | 2 nd 30min | 1 st 30min | 2 nd 30min | 1 st 30min | 2 nd 30min | |
| Tetraethoxysilane silicon-dioxide | 0.75 | 1.10 | 0.99 | 1.14 | 1.54 | 1.46 |
| High-density plasma method oxide compound | 0.23 | 0.38 | 0.43 | 0.54 | 0.69 | 0.70 |
| Al | 2.67 | 0.68 | 4.07 | 0.70 | 1.74 | 1.73 |
| W | 0.20 | 0.05 | 0.26 | 0.10 | 0.31 | 0.21 |
Effect embodiment 1
Electron microscope observation is the result show: after using cleaning liquid composition of the present invention, the effect after metal and passage clean is fine.Shown in Fig. 3～8, etch residue has been removed, and compare with Fig. 1～2, and solution does not corrode other metals again.
Claims (14)
1. a cleaning liquid composition that is used for semi-conductor industry ionic medium etch residue is characterized in that: comprise the solvent, aqueous buffer solution, fluorochemical, polymer inhibitor and the antifreezing agent that clean significant quantity.
2. cleaning liquid composition according to claim 1 is characterized in that: described cleaning liquid composition also comprises micromolecular inhibitor.
3. cleaning liquid composition according to claim 2 is characterized in that: described cleaning liquid composition weight percent content is:
(a) solvent 50%～85%
(b) aqueous buffer solution 10%～46%
(c) fluorochemical 0.05%～3%
(d) polymer inhibitor 0.0001%～10%
(e) micromolecular inhibitor 0%～10%
(f) antifreezing agent 0.0001%～10%
4. according to each described cleaning liquid composition of claim 1 to 3, it is characterized in that: described solvent is N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl formamide or tetramethylene sulfone.
5. according to each described cleaning liquid composition of claim 1 to 3, it is characterized in that: described aqueous buffer solution is the acetate and the ammonium acetate salt buffer aqueous solution.
6. cleaning liquid composition according to claim 5 is characterized in that: the weight percent in aqueous buffer solution of described acetate and acetate ammonium salt is 5%～60%.
7. cleaning liquid composition according to claim 6 is characterized in that: the weight percent in aqueous buffer solution of described acetate and ammonium acetate is 10%～50%.
8. cleaning liquid composition according to claim 7 is characterized in that: the weight percent in aqueous buffer solution of described acetate and ammonium acetate is 20%～40%.
9. according to each described cleaning liquid composition of claim 1 to 3, it is characterized in that: described fluorochemical is NH
4F, HF or NH
4HF
2
10. according to each described cleaning liquid composition of claim 1 to 3, it is characterized in that: described polymer inhibitor is for poly-carboxyl ether, polymaleic anhydride, polyacrylic acid, polymethyl acrylic acid and/or contain the homopolymer of carboxyl and/or contain the multipolymer of carboxyl.
11. cleaning liquid composition according to claim 10 is characterized in that: the described multipolymer that contains carboxyl is carboxylic copolyether, vinylformic acid and maleic acid, vinylbenzene and acrylic copolymer, vinylbenzene and maleic acid and/or vinyl cyanide and maleic acid and their ammonium salt, sylvite and/or sodium salt.
12. according to each described cleaning liquid composition of claim 1 to 3, it is characterized in that: the weight percent of described polymer inhibitor is 0.01～3%.
13. according to each described cleaning liquid composition of claim 1 to 3, it is characterized in that: described micromolecular inhibitor is a benzotriazole.
14. according to each described cleaning liquid composition of claim 1 to 3, it is characterized in that: described antifreezing agent is an ethylene glycol.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610030170XA CN101126053A (en) | 2006-08-17 | 2006-08-17 | Cleaning liquid composition for plasma etching residues in semi-conductor industry |
| PCT/CN2007/002476 WO2008022560A1 (en) | 2006-08-17 | 2007-08-17 | Compositions for removal of etching residues |
| CN2007800274194A CN101490627B (en) | 2006-08-17 | 2007-08-17 | Compositions for removal of etching residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610030170XA CN101126053A (en) | 2006-08-17 | 2006-08-17 | Cleaning liquid composition for plasma etching residues in semi-conductor industry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101126053A true CN101126053A (en) | 2008-02-20 |
Family
ID=39094190
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200610030170XA Pending CN101126053A (en) | 2006-08-17 | 2006-08-17 | Cleaning liquid composition for plasma etching residues in semi-conductor industry |
| CN2007800274194A Expired - Fee Related CN101490627B (en) | 2006-08-17 | 2007-08-17 | Compositions for removal of etching residues |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800274194A Expired - Fee Related CN101490627B (en) | 2006-08-17 | 2007-08-17 | Compositions for removal of etching residues |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN101126053A (en) |
| WO (1) | WO2008022560A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101957563A (en) * | 2009-07-13 | 2011-01-26 | 安集微电子（上海）有限公司 | Fluorine-containing plasma etching residue cleaning solution |
| WO2012031453A1 (en) * | 2010-09-10 | 2012-03-15 | 安集微电子（上海）有限公司 | Fluoride-containing cleaning liquid |
| CN101958225B (en) * | 2009-07-14 | 2012-07-25 | 中芯国际集成电路制造(上海)有限公司 | Quartz changed board cleaning method |
| CN104813451A (en) * | 2012-11-28 | 2015-07-29 | 富士胶片株式会社 | Method for etching semiconductor substrate and method for manufacturing semiconductor device |
| CN105676600A (en) * | 2016-04-06 | 2016-06-15 | 东莞市广华化工有限公司 | Anti-corrosion alkaline developing solution |
| CN109108032A (en) * | 2018-06-25 | 2019-01-01 | 上海华力微电子有限公司 | A kind of unproductive method for cleaning wafer |
| WO2021227119A1 (en) * | 2020-05-13 | 2021-11-18 | Tcl华星光电技术有限公司 | Method for manufacturing display panel |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6828289B2 (en) * | 1999-01-27 | 2004-12-07 | Air Products And Chemicals, Inc. | Low surface tension, low viscosity, aqueous, acidic compositions containing fluoride and organic, polar solvents for removal of photoresist and organic and inorganic etch residues at room temperature |
| US7166419B2 (en) * | 2002-09-26 | 2007-01-23 | Air Products And Chemicals, Inc. | Compositions substrate for removing etching residue and use thereof |
| PT1828848E (en) * | 2004-12-10 | 2010-05-21 | Mallinckrodt Baker Inc | Non-aqueous, non-corrosive microelectronic cleaning compositions containing polymeric corrosion inhibitors |
| CN1982426B (en) * | 2005-12-16 | 2011-08-03 | 安集微电子（上海）有限公司 | Slow-releasing agent system for cleaning semiconductor chip |
-
2006
- 2006-08-17 CN CNA200610030170XA patent/CN101126053A/en active Pending
-
2007
- 2007-08-17 CN CN2007800274194A patent/CN101490627B/en not_active Expired - Fee Related
- 2007-08-17 WO PCT/CN2007/002476 patent/WO2008022560A1/en active Application Filing
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101957563A (en) * | 2009-07-13 | 2011-01-26 | 安集微电子（上海）有限公司 | Fluorine-containing plasma etching residue cleaning solution |
| CN101957563B (en) * | 2009-07-13 | 2014-09-24 | 安集微电子（上海）有限公司 | Fluorine-containing plasma etching residue cleaning solution |
| CN101958225B (en) * | 2009-07-14 | 2012-07-25 | 中芯国际集成电路制造(上海)有限公司 | Quartz changed board cleaning method |
| WO2012031453A1 (en) * | 2010-09-10 | 2012-03-15 | 安集微电子（上海）有限公司 | Fluoride-containing cleaning liquid |
| CN104813451A (en) * | 2012-11-28 | 2015-07-29 | 富士胶片株式会社 | Method for etching semiconductor substrate and method for manufacturing semiconductor device |
| US9514958B2 (en) | 2012-11-28 | 2016-12-06 | Fujifilm Corporation | Etching method of semiconductor substrate, and method of producing semiconductor device |
| CN105676600A (en) * | 2016-04-06 | 2016-06-15 | 东莞市广华化工有限公司 | Anti-corrosion alkaline developing solution |
| CN109108032A (en) * | 2018-06-25 | 2019-01-01 | 上海华力微电子有限公司 | A kind of unproductive method for cleaning wafer |
| WO2021227119A1 (en) * | 2020-05-13 | 2021-11-18 | Tcl华星光电技术有限公司 | Method for manufacturing display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101490627A (en) | 2009-07-22 |
| CN101490627B (en) | 2011-08-24 |
| WO2008022560A1 (en) | 2008-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1381663B1 (en) | Cleaning compositions | |
| CN102399648B (en) | Fluorine-containing cleaning solution | |
| TWI233942B (en) | Lactam compositions for cleaning organic and plasma etched residues for semiconductor devices | |
| CN101290482A (en) | Cleaning fluid for cleaning plasma etching residue | |
| CN101126053A (en) | Cleaning liquid composition for plasma etching residues in semi-conductor industry | |
| CN101214485B (en) | Method for cleaning anodic oxidation part surface in polysilicon etching cavity | |
| JP2002543272A (en) | Composition for cleaning organic and plasma-etched residues for semiconductor devices | |
| CN102047184A (en) | Cleaning solution of plasma etching residues | |
| JP7022100B2 (en) | Post-etching residue cleaning composition and its usage | |
| KR102405631B1 (en) | Semiconductor element cleaning solution that suppresses damage to tantalum-containing materials, and cleaning method using same | |
| CN1966636B (en) | Cleaning liquid composition | |
| CN101955852A (en) | Cleaning solution for plasma etching residues | |
| CN101412949A (en) | Cleaning liquid for plasma etching residue | |
| CN101827927B (en) | A plasma etching residues cleaning solution | |
| CN102827707A (en) | Plasma etching residue cleaning fluid | |
| CN104900481B (en) | The method for cleaning pad | |
| JP4690725B2 (en) | Stripper solution for removing residual polymer during semiconductor production, use thereof and method for removing residual polymer using the same | |
| KR20180041936A (en) | Etchant composition for etching metal layer | |
| KR101132084B1 (en) | Cleaning compositions with very low dielectric etch rates | |
| CN102569023B (en) | A kind of cleaning method reducing metal erosion | |
| WO2012029938A1 (en) | Photoresist residue and polymer residue removing liquid composition | |
| US20040175964A1 (en) | Aqueous cleaning composition containing copper-specific corrosion inhibitor | |
| KR102321217B1 (en) | Post etch residue cleaning compositions and methods of using the same | |
| KR100916353B1 (en) | Cleaning composition for semiconductor device and cleaning method of semiconductor device using the same | |
| CN109971565A (en) | A kind of fluorine-containing cleaning solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20080220 |