CN103513522A - Semiconductor cleaning composition - Google Patents
Semiconductor cleaning composition Download PDFInfo
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- CN103513522A CN103513522A CN201310439776.9A CN201310439776A CN103513522A CN 103513522 A CN103513522 A CN 103513522A CN 201310439776 A CN201310439776 A CN 201310439776A CN 103513522 A CN103513522 A CN 103513522A
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- China
- Prior art keywords
- ether
- list phenyl
- cleaning combination
- propylene glycol
- imidazolidinone
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- 238000004140 cleaning Methods 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title abstract description 8
- 239000004065 semiconductor Substances 0.000 title description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 12
- -1 alkyl diol aryl ether Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 51
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 41
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 38
- VTLLEYMBCVXROX-UHFFFAOYSA-N 1-(3-phenylprop-2-enyl)-4,5-dihydroimidazole Chemical compound C(C=CC1=CC=CC=C1)N1C=NCC1 VTLLEYMBCVXROX-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012062 aqueous buffer Substances 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical group CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 6
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims description 6
- MYTVHIVXHFJDBV-UHFFFAOYSA-N 5-dodecyl-2-methyl-3H-1,2-oxazole Chemical group CN1OC(=CC1)CCCCCCCCCCCC MYTVHIVXHFJDBV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 6
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 4
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 241000238370 Sepia Species 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229930016911 cinnamic acid Natural products 0.000 claims description 4
- 235000013985 cinnamic acid Nutrition 0.000 claims description 4
- 238000006210 cyclodehydration reaction Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 claims description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical compound C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 claims description 3
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- OCUJLLGVOUDECM-UHFFFAOYSA-N dipivefrin Chemical compound CNCC(O)C1=CC=C(OC(=O)C(C)(C)C)C(OC(=O)C(C)(C)C)=C1 OCUJLLGVOUDECM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000007979 citrate buffer Substances 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 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
- 239000005416 organic matter Substances 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000011176 pooling Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention provides a cleaning composition for removing photoresist residues. The composition is characterized by comprising a small-molecule inhibitor mixture, a solvent, quaternary ammonium hydroxide, citric acid/citrate buffer aqueous solution and alkyl diol aryl ether. The cleaning composition reduces the corrosion to chip patterns, metals such as aluminum and copper and nonmetal substrates such as silicon dioxide; particularly, the small-molecule inhibitor contained in the composition has excellent inhibition effect on the corrosion to metal aluminum.
Description
Technical field
The present invention relates to semi-conductor industry technical field, relate in particular to a kind of cleaning combination for photoetching glue residues such as semi-conductor industry removals.
Background technology
In common semiconductor fabrication process, by the upper mask that forms photoresist in the surfaces such as the metals such as silicon dioxide, Cu (copper) and low-k materials, after exposure, utilize wet method or dry etching to carry out figure transfer.Low temperature fast cleaning is the important directions of semiconductor wafer fabrication process development.The negative photoresist of the above thickness of 20 μ m is applied in semiconductor wafer fabrication process just gradually, and industrial most photoresist clean-out system is better to the cleansing power of positive photoresist at present, but can not thoroughly remove the negative photoresist with cross-linked structure after exposure and etching on wafer.In addition, at semiconductor wafer, carry out in the Process of Chemical Cleaning of photoresist, clean-out system often can cause the corrosion of wafer pattern and base material.Particularly utilizing chemical to remove in the process of photoresist and etch residue, metal (especially aluminium He Tongdeng compare active metal) corrosion is comparatively generally and very serious problem, often causes the remarkable reduction of wafer yield.。
At present, photoresist clean-out system is mainly comprised of polar organic solvent, highly basic and/or water etc., by semiconductor wafer being immersed in clean-out system or utilizing clean-out system to rinse semiconductor wafer, removes the photoresist on semiconductor wafer.
Patent documentation WO03104901 utilizes Tetramethylammonium hydroxide (TMAH), sulfolane (SFL), water and trans-1,2-CDTAs (CyDTA) etc. form alkaline cleaner, wafer is immersed in this clean-out system, submergence 20～30min at 50～70 ℃, removes the photoresist in metal and dielectric substrate.This alkaline cleaner is slightly high to the corrosion of semiconductor wafer base material, and can not remove the photoresist of semiconductor wafer completely, and cleansing power is not enough.
WO04059700 utilizes Tetramethylammonium hydroxide (TMAH), N-methylmorpholine-N-oxide (MO), water and 2-mercaptobenzimidazole (MBI) etc. to form alkaline cleaner, wafer is immersed in this clean-out system, submergence 15～60min at 70 ℃, removes the photoresist in metal and dielectric substrate.The cleaning temperature of this alkaline cleaner is higher, slightly high to the corrosion of semiconductor wafer base material, and cleaning speed is relatively slow, is unfavorable for improving the cleaning efficiency of semiconductor wafer.
JP1998239865 utilizes TMAH, dimethyl sulfoxide (DMSO) (DMSO), 1,3 '-dimethyl-2-imidazolidinone (DMI) and water etc. form alkaline cleaner, wafer is immersed in this clean-out system, at 50～100 ℃, remove thick film photolithography glue more than 20 μ m in metal and dielectric substrate.This alkaline cleaner is more serious to the corrosion of semiconductor wafer base material under higher cleaning temperature.
JP2001215736 utilizes TMAH, dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol (EG) and water etc. to form alkaline cleaner, and wafer is immersed in this clean-out system, removes the photoresist in metal and dielectric substrate at 50～70 ℃.This alkaline cleaner is more serious to the corrosion of semiconductor wafer base material under higher cleaning temperature.
JP2001215736 utilizes TMAH, dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol (EG) and water etc. to form alkaline cleaner, and wafer is immersed in this clean-out system, removes the photoresist in metal and dielectric substrate at 50～70 ℃.This alkaline cleaner is more serious to the corrosion of semiconductor wafer base material under higher cleaning temperature.
Above clean-out system or cleansing power are not enough, or stronger to the corrosion of semiconductor wafer base material, can not meet industrial needs.
Summary of the invention
The object of the invention is, in order to solve cleansing power deficiency and to the corrosivity of the semiconductor wafer base material stronger problem of photoresist clean-out system of the prior art to photoresist, provides a kind of have higher photoresist cleansing power and the lower corrosive photoresist cleaning combination of base material.
For solving the problems of the technologies described above, the invention provides a kind ofly for removing the cleaning combination of plasma etching residue, it comprises micromolecular inhibitor potpourri, solvent, quaternary ammonium hydroxide, citric acid/citrate aqueous buffer solution, alkyl diol aryl ether.
Wherein, the content of described citric acid/citrate aqueous buffer solution in cleaning combination is preferably mass percent 10%～50%, the content of described micromolecular inhibitor is preferably 0.5%～15%, the content of described solvent is preferably 30%～60%, and the content of described quaternary ammonium hydroxide is preferably 0.1～15%, the content of described alkyl diol aryl ether is preferably 1～15%.
Wherein, described micromolecular inhibitor potpourri is the potpourri that cinnamyl imidazoline and 2-methyl-5-dodecyl isoxazole form.
Wherein, described cinnamyl imidazoline and 2-methyl-5-dodecyl isoxazole mixing quality are than being 1:1.2～1.5.
Wherein, the preparation method of described cinnamyl imidazoline is specially:
The analytically pure diethylenetriamine of 10ml is placed in to four-hole boiling flask; be warming up to 150 ℃; splash into 3ml and analyze pure toluene, add the analytically pure cinnamic acid of 22g, under nitrogen environment, stir; be warming up to again 170 ℃ and start acidylate dehydration; after reaction 5h, be warming up to 240 ℃ and start cyclodehydration 3h, be placed on after completion of the reaction in vacuum drying chamber dry; obtain the thick cinnamyl imidazoline of sepia, reaction equation is as follows:
Wherein, described solvent can be selected from one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and ether.Wherein, described sulfoxide is preferably diethyl sulfoxide or first ethyl-sulfoxide; Described sulfone is preferably methyl sulfone, ethyl sulfone or sulfolane; Described imidazolidinone is preferably 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone or 1,3-diethyl-2-imidazolidinone; Described pyrrolidone is preferably 1-METHYLPYRROLIDONE; Described imidazolone is preferably DMI (DMI); Described acid amides is preferably dimethyl formamide; Described ether is preferably glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE or Dipropylene glycol mono-n-butyl Ether.
Wherein, described quaternary ammonium hydroxide is preferably Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH or benzyltrimethylammonium hydroxide, more preferably Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or TBAH, most preferably be Tetramethylammonium hydroxide.
Wherein, described alkyl diol aryl ether is preferably propylene glycol list phenyl ether, Isopropanediol list phenyl ether, diethylene glycol list phenyl ether, dipropylene glycol list phenyl ether, di-isopropylene glycol list phenyl ether, triethylene glycol list phenyl ether, tripropylene glycol list phenyl ether, three Isopropanediol list phenyl ethers, six condensed ethandiol list phenyl ethers, six contracting propylene glycol list phenyl ethers, six contracting Isopropanediol list phenyl ethers, propylene glycol single-benzyl ether, Isopropanediol single-benzyl ether or hexanediol list naphthyl ether, more preferably propylene glycol list phenyl ether, dipropylene glycol list phenyl ether or propylene glycol single-benzyl ether.
The present invention also provides the preparation method of above-mentioned cleaning combination, and above-mentioned each component is mixed in proportion, stirs, and obtains.
Beneficial effect of the present invention:
Cleaning combination of the present invention can comparatively promptly clean and remove the etch residue after plasma etching in metal, metal alloy or dielectric substrate, especially photoresist etch residues at room temperature to 85 ℃; Simultaneously; contained alkyl diol aryl ether and micromolecular inhibitor can form layer protecting film at wafer figure and substrate surface; stop the attack to wafer figure and base material such as halogen atom, hydroxide ion; thereby reduce to wafer figure with to metals such as aluminium and copper; and the corrosion of the non-metallic substrate such as silicon dioxide, especially its micromolecular inhibitor containing shows good inhibiting effect to the corrosion of metallic aluminium.Cleaning combination of the present invention has a good application prospect at microelectronics such as cleaning semiconductor chips.
Embodiment
The invention provides a kind ofly for removing the cleaning combination of plasma etching residue, it comprises micromolecular inhibitor potpourri, solvent, quaternary ammonium hydroxide, citric acid/citrate aqueous buffer solution, alkyl diol aryl ether.
Further preferably, described cleaning combination only consists of said components.
The content of described citric acid/citrate aqueous buffer solution in cleaning combination is preferably mass percent 10%～50%, and more preferably 30%.
The ratio of described citric acid and citrate can be carried out with any ratio as required, but must make the final cleaning combination of gained can keep homogeneous phase, and described citrate is preferably the salt that citric acid and inorganic base or quaternary ammonium hydroxide form; Wherein, inorganic base is as ammoniacal liquor and potassium hydroxide etc., and quaternary ammonium hydroxide is as Tetramethylammonium hydroxide and tetraethyl ammonium hydroxide etc.Multi-functional citric acid/citrate aqueous buffer solution not only has pooling feature, also has the ability of stronger sequestering power and cleaning inorganic residue.
The content of described micromolecular inhibitor potpourri in cleaning combination is preferably 0.5%～15%, and more preferably 10%.
Wherein, described micromolecular inhibitor potpourri is the potpourri that cinnamyl imidazoline and 2-methyl-5-dodecyl isoxazole form, and described cinnamyl imidazoline and 2-methyl-5-dodecyl isoxazole mixing quality are than being 1:1.2～1.5.
Wherein, the preparation method of described cinnamyl imidazoline is specially:
The analytically pure diethylenetriamine of 10ml is placed in to four-hole boiling flask; be warming up to 150 ℃; splash into 3ml and analyze pure toluene, add the analytically pure cinnamic acid of 22g, under nitrogen environment, stir; be warming up to again 170 ℃ and start acidylate dehydration; after reaction 5h, be warming up to 240 ℃ and start cyclodehydration 3h, be placed on after completion of the reaction in vacuum drying chamber dry; obtain the thick cinnamyl imidazoline of sepia, reaction equation is as follows:
The mass percent of described solvent is preferably mass percent 30%～60%, more preferably 40%.
In the present invention, described solvent can be selected from one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and ether.Wherein, described sulfoxide is preferably diethyl sulfoxide or first ethyl-sulfoxide; Described sulfone is preferably methyl sulfone, ethyl sulfone or sulfolane; Described imidazolidinone is preferably 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone or 1,3-diethyl-2-imidazolidinone; Described pyrrolidone is preferably 1-METHYLPYRROLIDONE; Described imidazolone is preferably DMI (DMI); Described acid amides is preferably dimethyl formamide; Described ether is preferably glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE or Dipropylene glycol mono-n-butyl Ether.
Described quaternary ammonium hydroxide is preferably Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH or benzyltrimethylammonium hydroxide, more preferably Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or TBAH, most preferably be Tetramethylammonium hydroxide.The content of described quaternary ammonium hydroxide is preferably mass percent 0.1～15%, most preferably is mass percent 10%.
Described alkyl diol aryl ether is preferably propylene glycol list phenyl ether, Isopropanediol list phenyl ether, diethylene glycol list phenyl ether, dipropylene glycol list phenyl ether, di-isopropylene glycol list phenyl ether, triethylene glycol list phenyl ether, tripropylene glycol list phenyl ether, three Isopropanediol list phenyl ethers, six condensed ethandiol list phenyl ethers, six contracting propylene glycol list phenyl ethers, six contracting Isopropanediol list phenyl ethers, propylene glycol single-benzyl ether, Isopropanediol single-benzyl ether or hexanediol list naphthyl ether, more preferably propylene glycol list phenyl ether, dipropylene glycol list phenyl ether or propylene glycol single-benzyl ether.The content of described alkyl diol aryl ether is preferably mass percent 1～15%, and more preferably mass percent 10%
Further, in described cleaning combination, can also include surfactant, the content of described surfactant is preferably mass percent 0～5%, and better is mass percent 0.05～3%.
Described surfactant is preferably polyvinyl alcohol (PVA) (PVG), polyvinylpyrrolidone (PVP) or polyoxyethylene ether (POE).The molecular weight of described surfactant is preferably 500～20000, and better is 1000～10000.
The present invention also provides the preparation method of above-mentioned cleaning combination, and above-mentioned each component is mixed in proportion, stirs, and obtains.
Below adopt embodiment to describe embodiments of the present invention in detail, to the present invention, how application technology means solve technical matters whereby, and the implementation procedure of reaching technique effect can fully understand and implement according to this.
The preparation of embodiment 1 cinnamyl imidazoline
The analytically pure diethylenetriamine of 10ml is placed in to four-hole boiling flask; be warming up to 150 ℃; splash into 3ml and analyze pure toluene; add the analytically pure cinnamic acid of 22g, under nitrogen environment, stir, then be warming up to the dehydration of 170 ℃ of beginning acidylates; after reaction 5h; be warming up to 240 ℃ and start cyclodehydration 3h, be placed on after completion of the reaction in vacuum drying chamber and be dried, obtain the thick cinnamyl imidazoline of sepia.
The preparation of embodiment 2 cleaning combinations 1
The cinnamyl imidazoline of 4g embodiment 1 preparation, 6g2-methyl-5-dodecyl isoxazole, 40gN-methyl pyrrolidone, 10g Tetramethylammonium hydroxide, 30g citric acid/ammonium citrate aqueous buffer solution (mass content of citric acid and ammonium citrate is than being 10:1), 10g propylene glycol list phenyl ether mix, stir, obtain cleaning combination 1.
Comparative example is cleaning combination relatively
40gN-methyl pyrrolidone, 10g Tetramethylammonium hydroxide, 30g citric acid/ammonium citrate aqueous buffer solution (mass content of citric acid and ammonium citrate is than being 10:1), 10g propylene glycol list phenyl ether mix, stir, obtain comparison cleaning combination.
Test 1
Washing test to foreign organic matter (fingerprint, remover waste liquid)
On glass what cleaned by ultra-pure water, arbitrarily pressing fingerprint forms after foreign organic matter (fingerprint), it is flooded 5 minutes in the chemical cleaning composite of above-described embodiment and comparative example, use afterwards optical electron microscope (LEICA commercial firm, model: FTM-200) the results are shown in table 1 after mensuration.
In addition, on glass what cleaned by ultra-pure water, be stained with after remover waste liquid, with well heater, at the temperature of 90 ℃, be dried 5 hours, in the chemical cleaning composite of above-described embodiment and comparative example, flood after 5 minutes afterwards, by optical electron microscope (LEICA commercial firm, model: FTM-200) measure, the results are shown in afterwards table 1.
Test 2
Washing test to inorganic foreign matter
On glass what cleaned by ultra-pure water, arbitrarily being stained with dust forms after inorganic foreign matter (dust), in the chemical cleaning composite of above-described embodiment and comparative example, flood 5 minutes, use afterwards optical electron microscope (LEICA commercial firm, model: FTM-200) after measurement result, be illustrated in table 1.
Observe the damage of metallic diaphragm
At room temperature, by the single aluminium base (momo-aluminiumsubstrate) cleaning by ultra-pure water, in the chemical cleaning composite of above-described embodiment and comparative example, flood 30 minutes, afterwards above-mentioned test piece is cleaned by ultra-pure water, with after nitrogen drying, with whether corroding in flying-spot microscope (SEM) check pattern, and the results are shown in table 1.
Table 1
| ? | Fingerprint | Dust | Remover waste liquid | Metal film |
| Embodiment 2 | Well | Well | Well | Well |
| Comparative example | Well | Well | Well | Bad |
In table 1, well represent that the revolution mark of foreign matter is no more than 2% of test piece area, bad expression revolution mark surpasses more than 50%.
Involved in the present invention for cleaning the chemical cleaning composite of resist remover, there is excellent cleansing power and can prevent the corrosion of metal film, and there is not the problem of the aspects such as incendivity, storage characteristics and environment, and the alcohols chemical substances such as isopropyl alcohol of using in alternative cleaning in the past, for the removal of organic and inorganic foreign matter, there is remarkable effect.
All above-mentioned these intellecture properties of primary enforcement, do not set restriction this new product of other forms of enforcement and/or new method.Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above, be only preferred embodiment of the present invention, is not the present invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (9)
1. for removing a cleaning combination for photoetching glue residue, it is characterized in that: comprise micromolecular inhibitor potpourri, solvent, quaternary ammonium hydroxide, citric acid/citrate aqueous buffer solution, alkyl diol aryl ether.
2. cleaning combination as claimed in claim 1, it is characterized in that: the content of described citric acid/citrate aqueous buffer solution in cleaning combination is preferably mass percent 10%～50%, the content of described micromolecular inhibitor is preferably 0.5%～15%, the content of described solvent is preferably 30%～60%, and the content of described quaternary ammonium hydroxide is preferably 0.1～15%, the content of described alkyl diol aryl ether is preferably 1～15%.
3. cleaning combination as claimed in claim 1 or 2, is characterized in that: described micromolecular inhibitor potpourri is the potpourri that cinnamyl imidazoline and 2-methyl-5-dodecyl isoxazole form.
4. the cleaning combination as described in claims 1 to 3, is characterized in that: described cinnamyl imidazoline and 2-methyl-5-dodecyl isoxazole mixing quality are than being 1:1.2～1.5.
5. the cleaning combination as described in claim 1 to 4, is characterized in that: the preparation method of described cinnamyl imidazoline is specially,
The analytically pure diethylenetriamine of 10ml is placed in to four-hole boiling flask; be warming up to 150 ℃; splash into 3ml and analyze pure toluene, add the analytically pure cinnamic acid of 22g, under nitrogen environment, stir; be warming up to again 170 ℃ and start acidylate dehydration; after reaction 5h, be warming up to 240 ℃ and start cyclodehydration 3h, be placed on after completion of the reaction in vacuum drying chamber dry; obtain the thick cinnamyl imidazoline of sepia, reaction equation is as follows:
6. the cleaning combination as described in claim 1 to 5, is characterized in that: described solvent can be selected from one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and ether.Wherein, described sulfoxide is preferably diethyl sulfoxide or first ethyl-sulfoxide; Described sulfone is preferably methyl sulfone, ethyl sulfone or sulfolane; Described imidazolidinone is preferably 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone or 1,3-diethyl-2-imidazolidinone; Described pyrrolidone is preferably 1-METHYLPYRROLIDONE; Described imidazolone is preferably DMI (DMI); Described acid amides is preferably dimethyl formamide; Described ether is preferably glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE or Dipropylene glycol mono-n-butyl Ether.
7. the cleaning combination as described in claim 1 to 6, it is characterized in that: described quaternary ammonium hydroxide is preferably Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH or benzyltrimethylammonium hydroxide, more preferably Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or TBAH, most preferably be Tetramethylammonium hydroxide.
8. the cleaning combination as described in claim 1 to 7, it is characterized in that: described alkyl diol aryl ether is preferably propylene glycol list phenyl ether, Isopropanediol list phenyl ether, diethylene glycol list phenyl ether, dipropylene glycol list phenyl ether, di-isopropylene glycol list phenyl ether, triethylene glycol list phenyl ether, tripropylene glycol list phenyl ether, three Isopropanediol list phenyl ethers, six condensed ethandiol list phenyl ethers, six contracting propylene glycol list phenyl ethers, six contracting Isopropanediol list phenyl ethers, propylene glycol single-benzyl ether, Isopropanediol single-benzyl ether or hexanediol list naphthyl ether, propylene glycol list phenyl ether more preferably, dipropylene glycol list phenyl ether or propylene glycol single-benzyl ether.
9. the preparation method of cleaning combination described in claim 1 to 8, is characterized in that: above-mentioned each component is mixed in proportion, stir, obtain.
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