CN109976110A - A kind of cleaning solution - Google Patents
A kind of cleaning solution Download PDFInfo
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- CN109976110A CN109976110A CN201711439631.3A CN201711439631A CN109976110A CN 109976110 A CN109976110 A CN 109976110A CN 201711439631 A CN201711439631 A CN 201711439631A CN 109976110 A CN109976110 A CN 109976110A
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- Prior art keywords
- cleaning solution
- fluoride
- acid
- variety
- cleaning
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- 238000004140 cleaning Methods 0.000 title claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- -1 alkyl polyols Chemical class 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 26
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 4
- 150000003851 azoles Chemical class 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229940031098 ethanolamine Drugs 0.000 claims description 3
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 3
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 claims description 3
- MVPRCWFLPDNGNR-UHFFFAOYSA-N 2-[amino(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(N)CCO MVPRCWFLPDNGNR-UHFFFAOYSA-N 0.000 claims description 2
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-UHFFFAOYSA-N 0.000 claims description 2
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017665 NH4HF2 Inorganic materials 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- VYSYZMNJHYOXGN-UHFFFAOYSA-N ethyl n-aminocarbamate Chemical compound CCOC(=O)NN VYSYZMNJHYOXGN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- WFJRIDQGVSJLLH-UHFFFAOYSA-N methyl n-aminocarbamate Chemical compound COC(=O)NN WFJRIDQGVSJLLH-UHFFFAOYSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- DKACXUFSLUYRFU-UHFFFAOYSA-N tert-butyl n-aminocarbamate Chemical compound CC(C)(C)OC(=O)NN DKACXUFSLUYRFU-UHFFFAOYSA-N 0.000 claims description 2
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims 1
- RLNZSUSARYWGKS-UHFFFAOYSA-N 2,2,2-trihydroxyethylazanium fluoride Chemical compound [F-].OC(C[NH3+])(O)O RLNZSUSARYWGKS-UHFFFAOYSA-N 0.000 claims 1
- RSFDFESMVAIVKO-UHFFFAOYSA-N 3-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S)=C1 RSFDFESMVAIVKO-UHFFFAOYSA-N 0.000 claims 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229940102253 isopropanolamine Drugs 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 239000010949 copper Substances 0.000 abstract description 17
- 239000004065 semiconductor Substances 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 238000001020 plasma etching Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The present invention relates to a kind of cleaning solutions, contain: fluoride, organic amine, alkyl polyols, metal resist and water.Cleaning solution cleaning ability of the invention is strong, can effectively remove plasma etching residues during manufacture of semiconductor, especially removes copper removal Ma Shige technique post-ash residue, while low-k low-k material (BD1, BD2) can be effectively protected.The present invention is suitable for batch immersion type, batch rotating spraying formula cleaning way, is particularly suitable for the high revolving cleaning way of revolving speed monolithic, has larger action pane, has a good application prospect in microelectronic fields such as cleaning semiconductor chips.
Description
Technical field
The present invention relates to cleaning solution technical field more particularly to a kind of cleaning solutions in semiconductor fabrication.
Background technique
In semiconductor components and devices manufacturing process, coating, exposure and the imaging of photoresist layer manufacture to the pattern of component
It says and is necessary processing step.Patterned last (i.e. after the coating of photoresist layer, imaging, ion implantation and etching) into
Before the next processing step of row, the photoresistive polymer that either residue of photoresist layer material is still hardened through ion bombardment is all needed
Thoroughly remove.With the raising of semiconductor processing technology level, manufactured electronic component density also constantly increases on unit wafer
Add, each conductor width and spacing constantly reduce, and replace traditional silica material not with low dielectric constant films (low-k material)
RC delay can be only reduced, while power consumption and signal cross-talk can also be reduced.In addition, in semiconductor element manufacturing field, with
The diminution of size, Cu dual Damascene technology processing procedure be also more and more widely used.Therefore it is applicable in the art of semiconductor manufacturing
In the cleaning solution of metallic copper and low-k low-k dielectric material also in the exploitation of more and more input researchs.Can
Low-k low-k dielectric material, nonmetallic materials and metal material can be protected while effectively removing etch residue again
Cleaning solution it is just more and more important.
The residue contained after the coating, imaging and etching of Cu dual Damascene technology photoresist layer mainly has: organic matter
Residual, inorganic residue and oxide residual, for these residues cleaning commonly use in the prior art amine cleaning solution and
Fluorides cleaning solution.Existing amine cleaning solution generally uses temperature higher (> 60 DEG C), does not control low-k usually
The protection problem of (low-k material).Although the cleaning solution of fluoride class can carry out under lower temperature (room temperature is to 50 DEG C)
Cleaning, but still have the shortcomings that various.For example, the corrosion of metal and non-metallic substrate cannot be controlled simultaneously, clean
It is easy to cause the change of channel characteristics size afterwards, thus change semiconductor structure, the corrosion control for common nonmetallic materials
While be difficult to ensure that low-k material is not attacked；The based cleaning liquid makees metallic copper frequently with traditional benzotriazole (BTA)
Corrosion inhibitor, although the etch-rate of metallic copper is smaller, traditional azole corrosion inhibitor (BTA) is not only difficult to degrade pair
Biosystem not environmentally, and is readily adsorbed in copper surface after cleaning, leads to the pollution of integrated circuit, can cause circuit
Interior unpredictalbe deficiencies in electrical conductivity.
US8,357,646 disclose the cleaning solution not fluorine-containing containing azanol, use BTA as the corrosion inhibitor of copper, though
Right protecting effect is preferable, but not can solve the attack problem of low-k material；It is mainly chain hydramine that CN10034623, which is disclosed a kind of,
And the composition and method for being used to remove the resist compatible with copper based on glycol solvent, the composition address only copper
Etching problem, can not achieve to nonmetallic and low-k material protection.US8,481,472 discloses a kind of for removal pair
The high aqueous fluorine-containing acidic cleaning solution of copper dual damascene process residue, the cleaning liquid water content are more than 70%, control solution
It is undesirable for the residue removal effect of organic species although metal and nonmetallic can be protected simultaneously for acid condition.
Therefore, in order to overcome the defect of existing cleaning solution, new cleaning requirement, such as protection low-k material are adapted to
Material, environment is more friendly, overcomes metal corrosion inhibitor adsorption, low defect level, low etching rate and is suitable for monolithic
It machine-washes clear mode etc., it would be highly desirable to seek new cleaning solution.
Summary of the invention
To solve the above problems, containing the present invention provides a kind of cleaning solution: fluoride, organic amine, alkyl are polynary
Alcohol, metal resist and water.Cleaning solution cleaning ability of the invention is strong, and plasma is carved during can effectively removing manufacture of semiconductor
Residue is lost, especially removes copper removal Ma Shige technique post-ash residue, while low-k low-k can be effectively protected
Material (BD1, BD2).The present invention is suitable for batch immersion type, batch rotating spraying formula cleaning way, is particularly suitable for high revolving speed
The revolving cleaning way of monolithic has larger action pane, has in microelectronic fields such as cleaning semiconductor chips good
Application prospect.
The present invention provides a kind of cleaning solution comprising fluoride, organic amine, alkyl polyols, metal resist and water.
Wherein it is preferred to not contain azanol and oxidant in the cleaning solution.
Preferably, the fluoride includes the salt that hydrogen fluoride and/or hydrogen fluoride and alkali are formed；It is further preferred that the fluorine
Compound includes hydrogen fluoride (HF), ammonium fluoride (NH4F), ammonium acid fluoride (NH4HF2), Methanaminium, N,N,N-trimethyl-, fluoride (N (CH3)4) and three hydroxyl second F
Base ammonium fluoride (N (CH2OH)3HF one of) or a variety of.
Preferably, the content of the fluoride is preferably mass percent 0.01~25%.
Preferably, the organic amine includes one of organic amine of hydroxyl, amino and carboxyl or a variety of；More preferably
Ground, the organic amine of the hydroxyl include hydramine；The amino-containing organic amine includes organic polyamine；It is described carboxylic
Organic amine includes the organic acid of amino；It is further preferred that the hydramine includes ethanol amine, diethanol amine, triethanolamine, isopropyl
Hydramine, N, one of N- dimethylethanolamine and N methyldiethanol amine or a variety of；The organic polyamine includes divinyl three
One of amine, pentamethyl-diethylenetriamine and polyethylene polyamine are a variety of；The organic acid includes 2- amion acetic acid, 2- amino
Benzoic acid, iminodiacetic acid, one of nitrilotriacetic acid and ethylenediamine tetra-acetic acid or a variety of；It is further preferred that described have
Machine amine includes one of pentamethyl-diethylenetriamine, iminodiacetic acid and triethanolamine or a variety of.
Preferably, the mass percent concentration of the organic amine is 10~50%.
Preferably, the alkyl polyols include 1,2-PD, glycerine, 1,4-butanediol, hexylene glycol, pentanediol,
One of diethylene glycol (DEG), dipropylene glycol are a variety of.
Preferably, the mass percent concentration of the alkyl polyols is 5~35%.
Preferably, the metal resist include one of sulfydryl azole compounds and diazanyl derivatives quasi-compound or
It is a variety of；It is further preferred that the sulfydryl azole compounds are without including 2- dimercaptothiodiazole, 2- amido-1,3,4-thiadiazoles, 3- mercapto
Yl benzoic acid and 4- mercaptobenzoic acid；The diazanyl derivatives quasi-compound includes methyl hydrazinocarboxylate, paradibenzoic acid, hydrazine
Base benzyl formate, ethyl carbazate, tert-butyl carbazate, 2- hydroxyethylhydrazine, 2,2'- hydrazono- diethanol, ethoxy second
One of diamines is a variety of.
Preferably, the mass percent concentration of the metal resist is 0.001~5%；It is further preferred that the metal
The mass percent concentration of resist is 0.01-3%.
Compared with prior art, the technical advantages of the present invention are that:
1) cleaning solution cleaning ability of the invention is strong, and plasma etching remains during can effectively removing manufacture of semiconductor
Object especially removes copper removal Ma Shige technique post-ash residue；
2) low-k low-k material (BD1, BD2) can be effectively protected in the present invention, be suitable for batch immersion type,
Batch rotating spraying formula cleaning way is particularly suitable for the high revolving cleaning way of revolving speed monolithic；
3) cleaning solution in the present invention, cleaning plasma etching residue, the present invention can have at 25 DEG C to 50 DEG C
Larger action pane has a good application prospect in microelectronic fields such as cleaning semiconductor chips.
Specific embodiment
Below with reference to table and specific embodiment, advantage of the invention is elaborated.
Agents useful for same and raw material of the present invention are commercially available.According to each component and its content cited in table 1, mix to
Substantially uniformity can then obtain meeting the preferred embodiment of the present invention, specific as shown in table 1.
Table 1 meets the component and content of the preferred embodiment of the present invention and its comparative example
The present invention by metal (Cu) bare silicon wafer as at 40 DEG C, after rotating 10min with the revolving speed of 400rpm/min, through going
Ionized water rinsing, then dried up with high pure nitrogen, the corrosion rate for then testing metal (Cu) blank (is cleaned with monolithic in industry
Rate of metal corrosion is lower thanTo meet the requirements)；By BD1 and BD2 bare silicon wafer as 30min is impregnated at 40 DEG C, pass through
Deionized water rinsing after dried up with high pure nitrogen after as in 300 DEG C of Muffle furnaces toast 30min after, measure BD1 and BD2 corrosion speed
Rate (is lower than with meeting nonmetallic corrosion rateTo meet the requirements), while observing surface variation；By Damascus work
Metal duct wafer in skill containing plasma etching residues is placed under high speed rotation cleaning way, at 25 DEG C to 50 DEG C with
1.5min is rotated under 400rpm/min revolving speed, is dried up after deionized water rinses with high pure nitrogen, the cleaning effect of observation residual also
Fruit.And obtain the cleaning effect of residue and as shown in table 2 to metal and nonmetallic corrosion condition.
The cleaning effect of table 2, the embodiment of the present invention and its comparative example
Note: in table 2, BD1 and BD2 are low medium (low-k) material of different value of K.
| Symbol | Low-k degree of impairment |
| ◎ | Color surface is unchanged |
| ○ | Only color change |
| △ | Only rough surface |
| × | Color surface changes |
From Table 2, it can be seen that the cleaning solution obtained using the formula of comparative example 1, wafer Damascus work after cleaning
Skill metal duct broadens；And under other components and the identical situation of content, in addition it is added to the embodiment 6 of metal resist simultaneously
There is not the problem of metal passage broadens.
And from comparative example 2 and embodiment 6 as can be seen that under other components and its identical situation of content, comparative example 2
In be not used alkyl polyols cleaning solution, occur low-k material corrosion rate increase and the underproof problem in surface.And it is real
It applies in example 6, supplements and be added to alkyl polyols, the corrosion rate of metal and low-k material is slow, and after cleaning, free of surface defects.
Therefore, it can be seen that add alkyl polyols in the composition containing fluoride, organic amine and metal resist, acquisition it is clear
Washing lotion can effectively control metal and nonmetallic corrosion rate, while low-k material can be effectively protected, from cleaning solution
Damage.
In addition, from comparative example 3 with embodiment 10 it can also be seen that under other components and its identical situation of content, not
The cleaning solution of alkyl polyols is added the problem of low-k surface damage occur.
From comparative example 4 and embodiment 14 can with it is further seen that, the cleaning solution of alkyl polyols is replaced with common solvent, clearly
After washing, there is the problem of BD2 surface damage.It is molten compared to other to further demonstrate alkyl polyols cited in the present invention
Agent can effectively control the corrosion rate of low-k low-k material, asking for low-k surface damage occur after avoiding cleaning
Topic.
It can be seen that cleaning solution of the present invention to introduce effective metal anti-further combined with the cleaning effect of other embodiments
While losing agent control metal erosion problem, low-k material can be effectively protected by further quoting alkyl polyols, effectively
Solve the protection problem of low-k low-k material in Cu dual Damascene technology.
To sum up, cleaning solution of the invention to semiconductor be made used in metal (such as Cu) and low dielectric low-k material
Material will not corrode substantially, and the corrosion rate of metal and low-k low-k material is full under industry monolithic cleaning condition
Foot requires.Meanwhile cleaning solution of the invention does not damage low-k material while guaranteeing cleaning effect.
It should be noted that the embodiment of the present invention has preferable implementation, and not the present invention is made any type of
Limitation, any one skilled in the art change or are modified to possibly also with the technology contents of the disclosure above equivalent effective
Embodiment, as long as without departing from the content of technical solution of the present invention, it is to the above embodiments according to the technical essence of the invention
Any modification or equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (15)
1. a kind of cleaning solution, which is characterized in that including fluoride, organic amine, alkyl polyols, metal resist and water,
Azanol and oxidant are not contained in the cleaning solution.
2. cleaning solution as described in claim 1, which is characterized in that
The fluoride includes the salt that hydrogen fluoride and/or hydrogen fluoride and alkali are formed.
3. cleaning solution as claimed in claim 3, which is characterized in that
The fluoride includes hydrogen fluoride (HF), ammonium fluoride (NH4F), ammonium acid fluoride (NH4HF2), Methanaminium, N,N,N-trimethyl-, fluoride (N (CH3)4) and trihydroxyethyl ammonium fluoride (N (CH F2OH)3HF one of) or a variety of.
4. cleaning solution as described in claim 1, which is characterized in that
The content of the fluoride is preferably mass percent 0.01~25%.
5. cleaning solution as described in claim 1, which is characterized in that
The organic amine includes one of organic amine of hydroxyl, amino and carboxyl or a variety of.
6. cleaning solution as claimed in claim 6, which is characterized in that
The organic amine of the hydroxyl includes hydramine；The amino-containing organic amine includes organic polyamine；
The carboxylic organic amine includes the organic acid of amino.
7. cleaning solution as claimed in claim 7, which is characterized in that
The hydramine includes ethanol amine, diethanol amine, triethanolamine, isopropanolamine, N, N- dimethylethanolamine and N- methyl two
One of ethanol amine is a variety of；The organic polyamine includes diethylenetriamine, pentamethyl-diethylenetriamine and polyethylene polyamine
One of or it is a variety of；The organic acid includes 2- amion acetic acid, 2- aminobenzoic acid, iminodiacetic acid, nitrilotriacetic acid and
One of ethylenediamine tetra-acetic acid is a variety of.
8. cleaning solution as claimed in claim 8, which is characterized in that
The organic amine includes one of pentamethyl-diethylenetriamine, iminodiacetic acid and triethanolamine or a variety of.
9. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the organic amine is 10~50%.
10. cleaning solution as described in claim 1, which is characterized in that
The alkyl polyols include 1,2- propylene glycol, glycerine, 1,4- butanediol, hexylene glycol, pentanediol, diethylene glycol (DEG), a contracting
One of dipropylene glycol is a variety of.
11. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the alkyl polyols is 5~35%.
12. cleaning solution as described in claim 1, it is characterised in that the metal resist includes sulfydryl azole compounds and hydrazine
One of radical derivative class compound is a variety of.
13. cleaning solution as claimed in claim 12, which is characterized in that
The sulfydryl azole compounds are without including 2- dimercaptothiodiazole, 2- amido-1,3,4-thiadiazoles, 3- mercaptobenzoic acid and 4-
Mercaptobenzoic acid；The diazanyl derivatives quasi-compound include methyl hydrazinocarboxylate, paradibenzoic acid, hydrazino benzyl formate,
One of ethyl carbazate, tert-butyl carbazate, 2- hydroxyethylhydrazine, 2,2'- hydrazono- diethanol, hydroxyethyl ethylenediamine
Or it is a variety of.
14. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the metal resist is 0.001~5%.
15. cleaning solution as claimed in claim 14, which is characterized in that
The mass percent concentration of the metal resist is 0.01-3%.
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|---|---|---|---|
| CN201711439631.3A CN109976110A (en) | 2017-12-27 | 2017-12-27 | A kind of cleaning solution |
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| Application Number | Priority Date | Filing Date | Title |
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Citations (4)
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|---|---|---|---|---|
| JP2006261432A (en) * | 2005-03-17 | 2006-09-28 | Nissan Chem Ind Ltd | Composition of semiconductor cleaning solution including hydrazine and cleaning method |
| WO2007056919A1 (en) * | 2005-11-15 | 2007-05-24 | Anji Microelectronics (Shanghai) Co., Ltd | Aqueous cleaning composition |
| US20100163788A1 (en) * | 2006-12-21 | 2010-07-01 | Advanced Technology Materials, Inc. | Liquid cleaner for the removal of post-etch residues |
| CN102399648A (en) * | 2010-09-10 | 2012-04-04 | 安集微电子（上海）有限公司 | Fluorine-containing cleaning solution |
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2017
- 2017-12-27 CN CN201711439631.3A patent/CN109976110A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006261432A (en) * | 2005-03-17 | 2006-09-28 | Nissan Chem Ind Ltd | Composition of semiconductor cleaning solution including hydrazine and cleaning method |
| WO2007056919A1 (en) * | 2005-11-15 | 2007-05-24 | Anji Microelectronics (Shanghai) Co., Ltd | Aqueous cleaning composition |
| US20100163788A1 (en) * | 2006-12-21 | 2010-07-01 | Advanced Technology Materials, Inc. | Liquid cleaner for the removal of post-etch residues |
| CN102399648A (en) * | 2010-09-10 | 2012-04-04 | 安集微电子（上海）有限公司 | Fluorine-containing cleaning solution |
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