CN113820927B - Positive photoresist stripping liquid composition - Google Patents
Positive photoresist stripping liquid composition Download PDFInfo
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- CN113820927B CN113820927B CN202111114452.9A CN202111114452A CN113820927B CN 113820927 B CN113820927 B CN 113820927B CN 202111114452 A CN202111114452 A CN 202111114452A CN 113820927 B CN113820927 B CN 113820927B
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- positive photoresist
- stripping
- photoresist
- stripping liquid
- ether
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 96
- 239000007788 liquid Substances 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 230000007797 corrosion Effects 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- 230000000149 penetrating effect Effects 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- -1 mercapto compounds Chemical class 0.000 claims description 11
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 10
- 229940005574 sodium gluconate Drugs 0.000 claims description 10
- 235000012207 sodium gluconate Nutrition 0.000 claims description 10
- 239000000176 sodium gluconate Substances 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- OQJBFFCUFALWQL-UHFFFAOYSA-N n-(piperidine-1-carbonylimino)piperidine-1-carboxamide Chemical group C1CCCCN1C(=O)N=NC(=O)N1CCCCC1 OQJBFFCUFALWQL-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IQXXEPZFOOTTBA-UHFFFAOYSA-N 1-benzylpiperazine Chemical compound C=1C=CC=CC=1CN1CCNCC1 IQXXEPZFOOTTBA-UHFFFAOYSA-N 0.000 claims description 6
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 6
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 6
- 229940091173 hydantoin Drugs 0.000 claims description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 6
- HQVFKSDWNYVAQD-UHFFFAOYSA-N n-hydroxyprop-2-enamide Chemical compound ONC(=O)C=C HQVFKSDWNYVAQD-UHFFFAOYSA-N 0.000 claims description 6
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 229920002385 Sodium hyaluronate Polymers 0.000 claims description 5
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 5
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 5
- 229940010747 sodium hyaluronate Drugs 0.000 claims description 5
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- 239000012044 organic layer Substances 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000005530 etching Methods 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 4
- 229940046307 sodium thioglycolate Drugs 0.000 description 4
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 3
- 235000010386 dodecyl gallate Nutrition 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- IIOADSXXVWNOSC-UHFFFAOYSA-N pentyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 IIOADSXXVWNOSC-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 235000010388 propyl gallate Nutrition 0.000 description 2
- 229940075579 propyl gallate Drugs 0.000 description 2
- 239000000473 propyl gallate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent 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
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
The invention provides a positive photoresist stripping liquid composition, which comprises, by weight, 5-8% of organic amine, 30-50% of organic solvent, 10-15% of corrosion inhibitor, 3-5% of complexing agent, 3-5% of surfactant, 1-5% of penetrating agent and the balance of water. The photoresist stripping liquid has the advantages of low stripping temperature, short time, small etching on an organic layer, no re-adsorption of the stripped photoresist liquid on a substrate, and good application prospect in the fields of semiconductor wafer cleaning and the like.
Description
Technical Field
The invention relates to the technical field of photoetching, in particular to a positive photoresist stripping liquid composition.
Background
The photoresist is also called photoresist, and mainly consists of three components of photosensitive resin, sensitizer and solvent. After the photosensitive resin is irradiated, the photo-curing reaction can be quickly carried out in an exposure area, so that the physical properties of the material, particularly the solubility, the affinity and the like, are obviously changed. The required micro pattern is transferred from the mask plate to the processed substrate through the processes of exposure, development, etching, diffusion, ion implantation, metal deposition and the like, and finally, the photoresist remained in the unexposed part is washed away through photoresist stripping liquid, so that the whole pattern transfer process is completed. In the typical LED chip and semiconductor die fabrication process, photoresist is required as a resist mask for pattern transfer, and the transfer process requires complete removal of the unwanted photoresist while not being able to etch any substrate.
When the photoresist stripping liquid is used for stripping and removing photoresist, a small amount of photoresist is adsorbed on the surface of a substrate in a dissolved state, and the photoresist can be quickly diluted in the subsequent water washing process, so that the photoresist is separated out and is adhered to the surface of the substrate, and the quality is finally affected. Therefore, in order to improve the yield, a stripping solution for preventing re-adsorption of photoresist has to be developed.
Disclosure of Invention
In view of this, the present invention provides a photoresist stripper that does not corrode the organic layer, has a good photoresist removing effect, and does not re-adsorb the photoresist to the surface of the substrate.
The technical scheme of the invention is realized as follows: the invention provides a positive photoresist stripping liquid composition, which comprises, by weight, 100% of organic amine 5-8%, organic solvent 30-50%, corrosion inhibitor 10-15%, complexing agent 3-5%, and the balance water; the complexing agent comprises sodium gluconate, titanium dioxide and chitosan.
On the basis of the technical scheme, preferably, the sodium gluconate: titanium dioxide: the weight ratio of the chitosan is (6-10)/(3-5)/(1-5).
On the basis of the technical scheme, preferably, the organic amine is one or two of alcohol amine and amide, and the alcohol amine is one or more of monoethanolamine, methyldiethanolamine and hydroxyethyl ethylenediamine; the amide is one or a combination of more of N-methyl pyrrolidone, N-methyl formamide, N-hydroxy acrylamide and N-phenyl maleimide.
On the basis of the technical scheme, preferably, the organic solvent is one or more of alcohol ether, piperazine and piperidine, and the alcohol ether is one or more of diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, ethylene glycol diethyl ether and ethylene glycol butyl ether; the piperazine is one or two of 1-amino-4-methylpiperazine and 1-benzyl piperazine; the piperidine is azodicarbonyl dipiperidine.
On the basis of the technical scheme, preferably, the corrosion inhibitor is one or a combination of more of gallic acid alkyl ester compounds, mercapto compounds, triazole compounds and hydantoin.
On the basis of the technical scheme, the novel modified polyester resin also preferably comprises a surfactant, wherein the surfactant is one or a combination of more of alpha-olefin sulfonate, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene and tween.
On the basis of the technical proposal, the water treatment agent also preferably comprises a penetrating agent, the penetrating agent is one or a combination of more of sodium hyaluronate, polyethylene glycol and alkali-resistant penetrating agent OEP-70.
On the basis of the technical scheme, preferably, the composition comprises, by weight, 100% of organic amine 5-8%, organic solvent 30-50%, corrosion inhibitor 10-15%, complexing agent 3-5%, surfactant 3-5%, penetrant 1-5%, and the balance water.
On the basis of the technical scheme, preferably, the photoresist stripping solution is used as follows:
S1, mixing all the reagents in the stripping liquid composition, uniformly stirring, and filtering for later use;
S2, contacting the semiconductor device with the photoresist with a positive photoresist stripping liquid composition by adopting a spraying method or an immersion method, and stripping the photoresist;
and S3, repeatedly washing the semiconductor device for 3-5 times after the stripping is finished, and finally drying the semiconductor device by using heated nitrogen.
Based on the above technical scheme, preferably, in step S2, when the photoresist is stripped, the temperature of the stripping solution is 30-60 ℃ and the stripping time is 5-30min; in the step S3, the heating temperature of nitrogen is 40-70 ℃.
Compared with the prior art, the positive photoresist stripping liquid composition has the following beneficial effects:
(1) In the stripping liquid composition, the complexation of the sodium gluconate, the titanium dioxide and the chitosan can accelerate the dissolution and the decomposition of the photoresist, and the separated photoresist is uniformly dispersed in the stripping liquid, so that the photoresist is prevented from being re-adsorbed on a substrate.
(2) The photoresist stripping liquid can penetrate into the photoresist, is convenient for stripping the photoresist, and can not excessively etch the organic layer to cause stripping marks. The stripping liquid disclosed by the invention has good water solubility and is easy to clean in the later period.
(3) The photoresist stripping liquid has low reaction temperature and short time, can reduce the evaporation of moisture and organic components, and improves the stripping speed and quality.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an etch of an organic layer with a positive photoresist stripper composition of the present invention;
FIG. 2 is a graph showing the re-adsorption effect of the positive photoresist stripper composition of the present invention on a photoresist;
Fig. 3 is a graph showing the stripping effect of the positive photoresist stripper composition of the present invention on RE layer photoresist.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1
A positive photoresist stripping liquid composition comprises, by weight, 100% of monoethanolamine 2%, hydroxyethyl ethylenediamine 1%, and N-methylpyrrolidone 2%; 10% of diethylene glycol monobutyl ether and 20% of 1-amino-4-methylpiperazine; propyl gallate 5% and sodium thioglycolate 5%; 1.8% of sodium gluconate, 0.9% of titanium dioxide, 0.3% of chitosan and the balance of water.
The positive photoresist stripping solution was used as follows:
s1, mixing all the reagents in the stripping liquid composition according to the weight percentage, uniformly stirring, and filtering for later use;
s2, heating the stripping liquid to 30 ℃, and then spraying the positive photoresist stripping liquid composition on the surface of the semiconductor device with the photoresist, so as to strip the photoresist for 30min;
S3, after the stripping is finished, washing the semiconductor device for 3 times; finally, the semiconductor device was dried using heated nitrogen gas at a nitrogen heating temperature of 40 ℃.
Example two
A positive photoresist stripping liquid composition comprises, by weight, 100% of methyldiethanolamine 3%, N-methylformamide 3%, and N-hydroxyacrylamide 2%; 10% of dipropylene glycol monomethyl ether, 20% of ethylene glycol butyl ether, 10% of 1-benzyl piperazine and 10% of azodicarbonyl dipiperidine; 5% of lauryl gallate, 5% of mercaptobenzothiazole and 5% of hydantoin; 2.5% of sodium gluconate, 1.25% of titanium dioxide, 1.25% of chitosan and the balance of water.
The positive photoresist stripping solution was used as follows:
s1, mixing all the reagents in the stripping liquid composition according to the weight percentage, uniformly stirring, and filtering for later use;
s2, heating the stripping liquid to 60 ℃, and then immersing the semiconductor device with the photoresist into the stripping liquid to strip the photoresist for 5min;
S3, after the stripping is finished, washing the semiconductor device for 5 times; finally, the semiconductor device was dried using heated nitrogen gas at a nitrogen heating temperature of 70 ℃.
Example III
A positive photoresist stripping liquid composition comprises, by weight, 100% of hydroxyethyl ethylenediamine 1%, N-phenyl maleimide 2%, N-methyl pyrrolidone 2%, and N-hydroxy acrylamide 1%; 10% of diethylene glycol monobutyl ether, 10% of ethylene glycol butyl ether, 10% of 1-amino-4-methylpiperazine and 10% of azodicarbonyl dipiperidine; 3% of gallic acid amyl ester, 3% of mercaptobenzothiazole, 4% of 1,2, 4-triazole and 2% of hydantoin; 1.86% of sodium gluconate, 1.1% of titanium dioxide and 1.1% of chitosan; 1% of alpha-olefin sulfonate and 2% of fatty alcohol polyoxyethylene ether sulfate; 0.5% of penetrating agent sodium hyaluronate and 700.5% of alkali-resistant penetrating agent OEP; the balance being water.
The positive photoresist stripping solution was used as follows:
s1, mixing all the reagents in the stripping liquid composition according to the weight percentage, uniformly stirring, and filtering for later use;
s2, heating the stripping liquid to 40 ℃, and then immersing the semiconductor device with the photoresist into the stripping liquid to strip the photoresist for 10min;
S3, after the stripping is finished, washing the semiconductor device for 4 times; finally, the semiconductor device was dried using heated nitrogen gas at a nitrogen heating temperature of 50 ℃.
Example IV
A positive photoresist stripping liquid composition comprises, by weight, 100% of methyl diethanolamine 1%, hydroxyethyl ethylenediamine 1%, N-methylpyrrolidone 2%, N-methylformamide 2%, and N-phenylmaleimide 1%; 6% of dipropylene glycol monomethyl ether, 8% of ethylene glycol diethyl ether, 10% of 1-amino-4-methylpiperazine, 6% of 1-benzylpiperazine and 6% of azodicarbonyl dipiperidine; lauryl gallate 2%, amyl gallate 2%, sodium thioglycolate 3%, mercaptobenzothiazole 3%, hydantoin 2%; 1% of sodium gluconate, 1% of titanium dioxide and 1% of chitosan; alkylphenol ethoxylates 2%, tween 202%; sodium hyaluronate 2%, polyethylene glycol 1%, and water in balance.
The positive photoresist stripping solution was used as follows:
s1, mixing all the reagents in the stripping liquid composition according to the weight percentage, uniformly stirring, and filtering for later use;
s2, heating the stripping liquid to 50 ℃, and then spraying the positive photoresist stripping liquid composition on the surface of the semiconductor device with the photoresist, so as to strip the photoresist for 20min;
S3, after the stripping is finished, washing the semiconductor device for 5 times; finally, the semiconductor device was dried using heated nitrogen gas at a nitrogen heating temperature of 60 ℃.
Example five
A positive photoresist stripping liquid composition comprises, by weight, 100% of methyl diethanolamine 0.5%, hydroxyethyl ethylenediamine 0.5%, N-methylpyrrolidone 2%, N-methylformamide 2%, N-hydroxyacrylamide 1%, N-phenylmaleimide 1%; dipropylene glycol monomethyl ether 5%, ethylene glycol diethyl ether 9%, 1-amino-4-methylpiperazine 6%, 1-benzylpiperazine 10%, azodicarbonyl dipiperidine 10%; lauryl gallate 2%, amyl gallate 1%, sodium thioglycolate 2%, mercaptobenzothiazole 2%, 1,2, 4-triazole 3% and hydantoin 4%; 2% of sodium gluconate, 1% of titanium dioxide and 1% of chitosan; 1% of alpha-olefin sulfonate, 2% of fatty alcohol polyoxyethylene ether sulfate, 1% of fatty alcohol polyoxyethylene ether, 1% of alkylphenol polyoxyethylene and 201% of tween; sodium hyaluronate 2%, polyethylene glycol 1%, alkali-resistant penetrating agent OEP-702%, and water in balance.
The positive photoresist stripping solution was used as follows:
s1, mixing all the reagents in the stripping liquid composition according to the weight percentage, uniformly stirring, and filtering for later use;
s2, heating the stripping liquid to 55 ℃, and then immersing the semiconductor device with the photoresist into the stripping liquid to strip the photoresist for 25min;
s3, after the stripping is finished, washing the semiconductor device for 5 times; finally, the semiconductor device was dried using heated nitrogen gas at a nitrogen heating temperature of 55 ℃.
Comparative example one
The first comparative example is the first example lacking complexing agent, specifically:
a positive photoresist stripping liquid composition comprises, by weight, 100% of monoethanolamine 2%, hydroxyethyl ethylenediamine 1%, and N-methylpyrrolidone 2%; 10% of diethylene glycol monobutyl ether and 20% of 1-amino-4-methylpiperazine; propyl gallate 5% and sodium thioglycolate 5%.
The method of using the positive photoresist stripper is described in example one.
Comparative example two
The second comparative example is the second example lacking corrosion inhibitor and complexing agent, and specifically comprises:
a positive photoresist stripping liquid composition comprises, by weight, 100% of methyldiethanolamine 3%, N-methylformamide 3%, and N-hydroxyacrylamide 2%; 10% of dipropylene glycol monomethyl ether, 20% of ethylene glycol butyl ether, 10% of 1-benzyl piperazine and 10% of azodicarbonyl dipiperidine.
The method of using the positive photoresist stripper is described in example two.
Experiment one organic layer damage experiment
The OLED substrate was immersed in the stripping solution at 60 ℃ and taken out every 15min, and the average value of the loss film thickness of the organic layer was measured at 5 points, and the results are shown in table 1 and fig. 1.
TABLE 1 etching/nm of organic layers by photoresist stripper
| 15min | 30min | 45min | 60min | 90min | 120min | |
| Example 1 | 47 | 98 | 150 | 193 | 323 | 522 |
| Example two | 51 | 98 | 155 | 192 | 330 | 528 |
| Example III | 49 | 92 | 148 | 187 | 321 | 520 |
| Example IV | 43 | 91 | 142 | 183 | 317 | 512 |
| Example five | 43 | 85 | 147 | 181 | 313 | 519 |
| Comparative example one | 313 | 562 | 775 | 1015 | ||
| Comparative example two | 659 | 870 | 1031 | 1344 |
Table 1 shows that the dissolution rate of PLN in the comparative example was very fast with increasing soaking time, and PLN was substantially completely dissolved at 60 min. The dissolution of PLN was slow in the examples, and only 180-190nm was dissolved at 60 min. Fig. 1 shows the etching of the organic layer under a metallographic microscope, and as can be seen in fig. 1, the stripping solution of example 1 has a slow etching rate for the organic layer, and no significant etching is seen. Comparative example 1 without complexing agent visible a significant etch at 60 min; comparative example 2 without added corrosion inhibitor and complexing agent visible a significant etch at 30 min; comparative examples 1 and 2 were severely etched at 90min, severely affecting the quality of the product. Thus, it was revealed that the stripping liquid of the present invention not only can strip the photoresist, but also does not significantly etch the organic layer.
Experimental two-stage Photonic liquid re-adsorption
A stripping solution containing a photoresist solution at a concentration of 6% was prepared, and a Mo substrate (the surface of the substrate did not contain a photoresist) was immersed in the stripping solution containing a photoresist solution at 60℃and then the substrate (the surface of the substrate remained with a photoresist-containing stripping solution) was taken out and rinsed with pure water, and the surface of the substrate was observed to adsorb a photoresist solution, and the result is shown in FIG. 2.
As can be seen from fig. 2, comparative examples 1 and 2, in which no complexing agent was added, were evident in re-adsorption of the photoresist, and the residue of the substrate photoresist after cleaning was evident; no re-adsorption of photoresist was seen in example 1. Therefore, the stripping liquid can avoid the photoresist from being re-adsorbed to the substrate, and the stripping liquid is good in water solubility and easy in later water washing.
Experiment three volatile amount experiment
100G of the stripping solutions of the examples and comparative examples were poured into 250ml beakers, and the weights thereof were measured at 60℃and 300rpm for 4 hours, 8 hours, 12 hours and 24 hours, respectively, and the results are shown in Table 2.
TABLE 2 results of volatile test/g
Table 2 shows that examples 1-4 can reduce evaporation of water and organic components, have stable components, and simultaneously have the effects of reducing etching of the organic layer and improving yield; of these, examples 4 and 5 were most effective.
Experiment of stripping Effect of four photoresists on RE layer
The OLED RE layer substrate is solidified under the conditions of 190 ℃ for 10min on a hot plate, then is peeled off by a peeling machine under the conditions of-60 ℃ and-0.3 Mpa, and the peeling liquid is selected from the peeling liquids of the embodiment and the comparative example, and the result is shown in figure 3.
As shown in FIG. 3, the stripping solution of example 5 can achieve the stripping effect for 60 seconds, and the comparative example can be stripped only after 5 minutes, which shows that the stripping solution of the invention can accelerate the dissolution and stripping of the photoresist, and the stripping efficiency is remarkably improved.
In conclusion, the positive photoresist stripping liquid composition can effectively remove photoresist and residues thereof, has no corrosion to an organic layer, and can not cause the phenomenon of photoresist re-adsorption after stripping. The photoresist has good stripping time, stripping effect and re-adsorption effect after stripping, and has good application prospect in the fields of semiconductor wafer cleaning and the like.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A positive photoresist stripper composition characterized by: the corrosion inhibitor comprises, by weight, 100% of organic amine 5-8%, organic solvent 30-50%, corrosion inhibitor 10-15%, complexing agent 3-5%, and water in balance; the complexing agent comprises sodium gluconate, titanium dioxide and chitosan;
the sodium gluconate: titanium dioxide: the weight ratio of the chitosan is (6-10), 3-5 and 1-5;
the corrosion inhibitor is one or a combination of more of gallic acid alkyl ester compounds, mercapto compounds, triazole compounds and hydantoin.
2. A positive photoresist stripper composition according to claim 1, wherein: the organic amine is one or two of alcohol amine and amide, and the alcohol amine is one or more of monoethanolamine, methyldiethanolamine and hydroxyethyl ethylenediamine; the amide is one or a combination of more of N-methyl pyrrolidone, N-methyl formamide, N-hydroxy acrylamide and N-phenyl maleimide.
3. A positive photoresist stripper composition according to claim 1, wherein: the organic solvent is one or more of alcohol ether, piperazine and piperidine, and the alcohol ether is one or more of diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, ethylene glycol diethyl ether and ethylene glycol butyl ether; the piperazine is one or two of 1-amino-4-methylpiperazine and 1-benzyl piperazine; the piperidine is azodicarbonyl dipiperidine.
4. A positive photoresist stripper composition according to claim 1, wherein: the surfactant is one or more of alpha-olefin sulfonate, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene and tween.
5. A positive photoresist stripper composition according to claim 1, wherein: the water-based emulsion also comprises a penetrating agent, wherein the penetrating agent is one or a combination of more of sodium hyaluronate, polyethylene glycol and alkali-resistant penetrating agent OEP-70.
6. A positive photoresist stripper composition according to any of claims 1-5, wherein: the composition comprises, by weight, 100% of an organic amine 5-8%, an organic solvent 30-50%, a corrosion inhibitor 10-15%, a complexing agent 3-5%, a surfactant 3-5%, a penetrating agent 1-5%, and water in balance.
7. A positive photoresist stripper composition according to any of claims 1-5, wherein: the use method of the photoresist stripping liquid comprises the following steps:
S1, mixing all the reagents in the stripping liquid composition, uniformly stirring, and filtering for later use;
S2, contacting the semiconductor device with the photoresist with a positive photoresist stripping liquid composition by adopting a spraying method or an immersion method, and stripping the photoresist;
and S3, repeatedly washing the semiconductor device for 3-5 times after the stripping is finished, and finally drying the semiconductor device by using heated nitrogen.
8. The positive photoresist stripper composition according to claim 7, wherein: in the step S2, when the photoresist is stripped, the temperature of stripping liquid is 30-60 ℃ and the stripping time is 5-30min; in the step S3, the heating temperature of nitrogen is 40-70 ℃.
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| CN105116696A (en) * | 2015-10-10 | 2015-12-02 | 蓝思科技（长沙）有限公司 | Photoresist stripper and application thereof |
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| CN103969966B (en) * | 2014-05-15 | 2015-04-15 | 京东方科技集团股份有限公司 | Method for removing photoresist |
| CN107608181A (en) * | 2017-09-14 | 2018-01-19 | 合肥惠科金扬科技有限公司 | A kind of photoresist lift off stripper for TFT LCD displays |
| CN110727181A (en) * | 2019-08-09 | 2020-01-24 | 华璞微电子科技(宁波)有限公司 | Positive photoresist stripping liquid composition |
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| CN105116696A (en) * | 2015-10-10 | 2015-12-02 | 蓝思科技（长沙）有限公司 | Photoresist stripper and application thereof |
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