CN102566332B - A kind of thick film photolithography glue cleaning fluid - Google Patents
A kind of thick film photolithography glue cleaning fluid Download PDFInfo
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- CN102566332B CN102566332B CN201010620005.6A CN201010620005A CN102566332B CN 102566332 B CN102566332 B CN 102566332B CN 201010620005 A CN201010620005 A CN 201010620005A CN 102566332 B CN102566332 B CN 102566332B
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Abstract
The invention discloses a kind of cleaning fluid be applicable to compared with thick photoresist cleaning of low etching property.The photoresist cleaning fluid of this low etching property contains: potassium hydroxide, solvent, hydramine, organic phenol, benzoic acid and derivant thereof or its esters and polycarboxylic acid corrosion inhibiter.This photoresist clean-out system may be used for removing the photoresist in metal, metal alloy or dielectric substrate and other residue, for metals such as copper, aluminium, tin, lead, silver, there is lower etch-rate simultaneously, have a good application prospect at microelectronics such as cleaning semiconductor chips.
Description
Technical field
The present invention relates to a kind of photoresist clean-out system, particularly relate to the photoresist clean-out system of thicker (thickness is greater than 100 microns).
Background technology
In common semiconductor fabrication process, by forming the mask of photoresist on the surface at metal and low-k materials etc. such as silicon dioxide, Cu (copper), Graphic transitions is carried out after exposure, after obtaining the circuitous pattern needed, before carrying out next process, need to peel off residual photoresist.Such as, implant in technique (bumpingtechnology) at wafer microballoon, need photoresist to form mask, this mask needs equally to remove after microballoon is successfully implanted, but due to this photoresist thicker, remove normal comparatively difficulty completely.Improving method that removal effect comparatively commonly uses is adopt to extend soak time, improve soaking temperature and adopt and be more rich in aggressive solution, but this often can cause the corrosion of wafer substrate and the corrosion of microballoon, thus causes the remarkable reduction of wafer yield.
At present, photoresist cleaning fluid, primarily of compositions such as polar organic solvent, highly basic and/or water, by immersing in cleaning fluid by semiconductor wafer or utilizing cleaning fluid to rinse semiconductor wafer, removes the photoresist on semiconductor wafer.Wherein its conventional highly basic mainly inorganic metal oxyhydroxide (as potassium hydroxide etc.) and organic hydroxide as tetramethyl oxyammonia etc.
If JP1998239865 is by Tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO) (DMSO), 1, the composition such as 3-dimethyl-2-imidazolidinone (DMI) and water alkaline cleaning fluid, wafer is immersed in this cleaning fluid, at 50 ~ 100 DEG C, remove the thick film photolithography glue of more than 20 μm in metal and dielectric substrate.It is slightly high to the corrosion of semiconductor wafer substrate, and can not remove the photoresist on semiconductor wafer completely, and cleansing power is not enough; WO2006/056298A1 utilizes by Tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol (EG) and water composition alkaline cleaning fluid, for cleaning the photoresist of 50 ~ 100 micron thickness, simultaneously to metallic copper no corrosion; CN200610118465.2 reports the alkaline compositions containing potassium hydroxide, dimethyl sulfoxide (DMSO), phenmethylol and monoethanolamine, the thick film photolithography glue in metal and dielectric substrate can be removed at 45 ~ 65 DEG C, but when operating temperature improves further, the problem of metal erosion can be there is.Such as US5529887 forms alkaline cleaning fluid by potassium hydroxide (KOH), alkylene glycol monoalkyl ether, soluble fluoride and water etc. again, wafer is immersed in this cleaning fluid, at 40 ~ 90 DEG C, remove the thick film photolithography glue in metal and dielectric substrate.It is higher to the corrosion of semiconductor wafer substrate.
As can be seen here, more efficiently metal corrosion inhibitor is found and the stronger dicyandiamide solution of cleansing power is the privileged direction that such photoresist cleaning fluid makes great efforts to improve.
Summary of the invention
The technical problem to be solved in the present invention is exactly that the cleansing power that exists for existing thick film photolithography glue cleaning fluid is not enough or to semiconductor wafer pattern and the stronger defect of base material corrosivity, and provides a kind of strong and to semiconductor wafer pattern and the lower photoresist clean-out system of base material corrosivity to thick film photolithography glue cleansing power.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of cleaning fluid for thick film photolithography glue, and this cleaning fluid contains (a) potassium hydroxide (b) solvent (c) hydramine (d) organic phenol (e) benzoic acid and derivant thereof or its esters (f) polycarboxylic acid corrosion inhibiter.Wherein, the content of each component is as follows:
I. potassium hydroxide 0.1-6wt%;
Ii. solvent 30-98wt%;
Iii. hydramine, 1-55wt%;
Iv. organic phenol 0.0001-10wt%, preferred 0.005-2wt%;
V. benzoic acid and derivant thereof or its esters 0.01-1wt%, preferred 0.05-1wt%.
Vi. polycarboxylic acid corrosion inhibiter 0.0001-2%, preferred 0.005-0.6%.
Solvent described in the present invention can be selected from sulfoxide, sulfone, pyrrolidone, imidazolidinone, imidazolone, alcohol, ether, acid amides one or more.Wherein, described sulfoxide is preferably dimethyl sulfoxide (DMSO); Described sulfone is preferably sulfolane; Described pyrrolidone is preferably 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, NHP, N-cyclohexyl pyrrolidone; Described imidazolidinone is preferably 1,3-dimethyl-2-imidazolidinone; Described imidazolone is preferably DMI (DMI); Described acid amides is preferably dimethyl formamide, dimethyl acetamide; Described alcohol is propylene glycol, diethylene glycol, dipropylene glycol preferably; Described ether is preferably propylene glycol monomethyl ether, dipropylene glycol monomethyl ether.
Hydramine described in the present invention is one or more in monoethanolamine, diethanolamine, triethanolamine, n-propanol amine, isopropanolamine, 2-(lignocaine) ethanol, ethyldiethanolamine and diglycolamine.Having of hydramine is beneficial to the solubleness of raising potassium hydroxide in system, and is conducive to the protection of metallic microspheres.
Organic phenol described in the present invention is preferably one or more in phenol and its derivatives, resorcinol and derivant thereof and phloroglucin and derivant thereof.Wherein said phenol and its derivatives is preferably phenol, methylphenol, metoxyphenol, tert-butyl phenol; Described resorcinol and derivant thereof are preferably resorcinol, 5-methyl-m-phenylene diphenol, 5-methoxyl-resorcinol, the 5-tert-butyl group-resorcinol; Described phloroglucin and derivant thereof are preferably phloroglucin, methylresorcinol triphenol and butyl phloroglucin.
Benzoic acid described in the present invention and derivant thereof or its esters are preferably one or more in benzoic acid, Potassium Benzoate, Sodium Benzoate, methyl benzoic acid, methyl benzoic acid potassium, methyl benzoic acid sodium, methoxy benzoic acid, methoxy benzoic acid potassium and methoxy benzoic acid sodium.
Polycarboxylic acid corrosion inhibiter described in the present invention is preferably polyacrylic acid or its multipolymer, polymethylacrylic acid or its multipolymer, polyacrylic acid alcohol amine salt, polymethylacrylic acid alcohol amine salt, polyoxyethylene-modified polyacrylic acid or derivatives thereof, polyoxyethylene-modified polymethylacrylic acid or derivatives thereof, poly-epoxy succinic acid, poly-aspartate, carboxylic polycaprolactone and/or carboxylic polylactide; Better is polyacrylic acid, polymethylacrylic acid, polyacrylic acid alcohol amine salt, polymethylacrylic acid alcohol amine salt, carboxylic polycaprolactone and/or carboxylic polylactide.The molecular weight (Mn) of described polycarboxylic acid corrosion inhibiter is preferably 500 ~ 20000, and better is 1000 ~ 10000.The content of described polycarboxylic acid corrosion inhibiter is preferably mass percent 0.0001-2%, preferred 0.005-0.6%.The described Corrosion behavior of polycarboxylic acid corrosion inhibiter to aluminium goes out good inhibiting effect.
Remarkable result of the present invention is, low etching property thick film photolithography glue cleaning fluid of the present invention, can at room temperature to 90 DEG C the photoresist of cleaning more than 100 μm thickness, and due to wherein containing organic phenol, benzoic acid and derivant thereof or its esters and polycarboxylic acid corrosion inhibiter ternary built system, can effectively suppress the corrosions of metal such as copper, aluminium, tin, lead, silver simultaneously, thus reduce the corrosion of base material.Concrete grammar is as follows: the photoresist clean-out system semiconductor wafer containing photoresist being immersed the low etching property in the present invention, after soaking the suitable time, dries up after taking out washing with high pure nitrogen at room temperature to 90 DEG C.
Embodiment
The present invention is set forth further below by embodiment.
The component of the clean-out system in each embodiment of table 1 (Examples) and content
In order to investigate the cleaning situation of this based cleaning liquid further, present invention employs following technological means: the semiconductor wafer (salient point encapsulation wafer) be about to containing negativity esters of acrylic acid photoresist (thickness is about 120 microns) immerses in clean-out system, at 25 ~ 90 DEG C, utilize constant temperature oscillator with the vibration frequency of about 60 revs/min vibration 15 ~ 120 minutes, then dry up with high pure nitrogen after deionized water washing.The cleaning performance of photoresist and the corrosion condition of cleaning fluid to wafer as shown in table 2.
Table 2 embodiment is to wafer cleaning situation
| corrosion condition: | ◎ no corrosion; | cleaning situation: | ◎ removes completely; | |
| zero slightly corrodes; | zero is a small amount of remaining; | |||
| △ moderate corrosion; | the more remnants of △; | |||
| × heavy corrosion. | × abundant residues. |
As can be seen from Table 2, cleaning fluid of the present invention has good cleaning performance to thick film photolithography glue, and serviceability temperature scope is wide, can effectively suppress the corrosions of metal such as copper, aluminium, tin, lead, silver simultaneously.
To sum up, the innovation of hinge structure of the present invention is:
1) have employed hydramine as dissolution with solvents potassium hydroxide, and as the protective agent of metallic microspheres (bump);
2) have employed organic phenol, benzoic acid and derivant thereof or its esters, polycarboxylic acid corrosion inhibiter ternary built system, can effectively suppress the corrosions of metal such as copper, aluminium, tin, lead, silver simultaneously.
Claims (13)
1. a thick film photolithography glue cleaning fluid, this cleaning fluid is made up of potassium hydroxide, solvent, hydramine, organic phenol, benzoic acid and derivant thereof or its esters and polycarboxylic acid corrosion inhibiter.
2. cleaning fluid as claimed in claim 1, it is characterized in that, the content of each component is as follows:
A, potassium hydroxide 0.1-6wt%;
B, solvent 30-98wt%;
C, hydramine 1-55wt%;
D, organic phenol 0.0001-10wt%;
E, benzoic acid and derivant thereof or its esters 0.01-1wt%;
F, polycarboxylic acid corrosion inhibiter 0.0001-2wt%.
3. cleaning fluid as claimed in claim 2, it is characterized in that, the content of described organic phenol is 0.005-2wt%, and the content of described benzoic acid and derivant or its esters is 0.05-1wt%, and the content of described polycarboxylic acid corrosion inhibiter is 0.005-0.6wt%.
4. cleaning fluid as claimed in claim 1, is characterized in that, described solvent be selected from sulfoxide, sulfone, pyrrolidone, imidazolidinone, imidazolone, alcohol, ether, acid amides one or more.
5. cleaning fluid as claimed in claim 4, it is characterized in that, described sulfoxide is dimethyl sulfoxide (DMSO); Described sulfone is sulfolane; Described pyrrolidone is 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, NHP and/or N-cyclohexyl pyrrolidone; Described imidazolidinone is 1,3-dimethyl-2-imidazolidinone; Described imidazolone is DMI; Described acid amides is dimethyl formamide and/or dimethyl acetamide; Described alcohol is propylene glycol, diethylene glycol and/or dipropylene glycol; Described ether is propylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether.
6. cleaning fluid as claimed in claim 1, it is characterized in that, described hydramine is for being selected from one or more in monoethanolamine, diethanolamine, triethanolamine, n-propanol amine, isopropanolamine, 2-(lignocaine) ethanol, ethyldiethanolamine and diglycolamine.
7. cleaning fluid as claimed in claim 1, is characterized in that, described organic phenol is be selected from one or more in phenol and its derivatives, resorcinol and derivant thereof and phloroglucin and derivant thereof.
8. cleaning fluid as claimed in claim 7, is characterized in that, described phenol and its derivatives be selected from phenol, methylphenol, metoxyphenol and tert-butyl phenol one or more; Described resorcinol and derivant thereof be selected from resorcinol, 5-methyl-m-phenylene diphenol, 5-methoxyl-resorcinol and the 5-tert-butyl group-resorcinol one or more; Described phloroglucin and derivant thereof are phloroglucin, methylresorcinol triphenol and/or butyl phloroglucin.
9. cleaning fluid as claimed in claim 1, it is characterized in that, described benzoic acid and derivant thereof or its esters are be selected from one or more in benzoic acid, Potassium Benzoate, Sodium Benzoate, methyl benzoic acid, methyl benzoic acid potassium, methyl benzoic acid sodium, methoxy benzoic acid, methoxy benzoic acid potassium and methoxy benzoic acid sodium.
10. cleaning fluid as claimed in claim 1, it is characterized in that, described polycarboxylic acid corrosion inhibiter be selected from polyacrylic acid or its multipolymer, polymethylacrylic acid or its multipolymer, polyacrylic acid alcohol amine salt, polymethylacrylic acid alcohol amine salt, polyoxyethylene-modified polyacrylic acid or derivatives thereof, polyoxyethylene-modified polymethylacrylic acid or derivatives thereof, poly-epoxy succinic acid, poly-aspartate, carboxylic polycaprolactone and carboxylic polylactide one or more.
11. cleaning fluids as claimed in claim 10, it is characterized in that, described polycarboxylic acid corrosion inhibiter be selected from polyacrylic acid, polymethylacrylic acid, polyacrylic acid alcohol amine salt, polymethylacrylic acid alcohol amine salt, carboxylic polycaprolactone and carboxylic polylactide one or more.
12. cleaning fluids as claimed in claim 1, it is characterized in that, the molecular weight of described polycarboxylic acid corrosion inhibiter is 500 ~ 20000.
13. cleaning fluids as claimed in claim 12, it is characterized in that, the molecular weight of described polycarboxylic acid corrosion inhibiter is 1000 ~ 10000.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010620005.6A CN102566332B (en) | 2010-12-30 | 2010-12-30 | A kind of thick film photolithography glue cleaning fluid |
| TW100145440A TW201224138A (en) | 2010-12-10 | 2011-12-09 | Thick-film photoresist stripper solution |
| PCT/CN2011/002055 WO2012075686A1 (en) | 2010-12-10 | 2011-12-09 | Thick-film photoresist stripper solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010620005.6A CN102566332B (en) | 2010-12-30 | 2010-12-30 | A kind of thick film photolithography glue cleaning fluid |
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| CN102566332A CN102566332A (en) | 2012-07-11 |
| CN102566332B true CN102566332B (en) | 2016-04-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3862072A4 (en) * | 2018-10-04 | 2022-07-06 | Sumitomo Chemical Company Limited | Composition useful for production of acidic gas separation membrane |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104330959B (en) * | 2014-10-25 | 2018-04-10 | 江阴市化学试剂厂有限公司 | Photoresist lift off liquid and preparation method thereof |
| CN105116696A (en) * | 2015-10-10 | 2015-12-02 | 蓝思科技（长沙）有限公司 | Photoresist stripper and application thereof |
| CN106919011B (en) * | 2015-12-25 | 2021-12-17 | 安集微电子科技（上海）股份有限公司 | Hydroxylamine stripping cleaning solution rich in water |
| CN109456858A (en) * | 2018-11-07 | 2019-03-12 | 天津津航技术物理研究所 | A kind of optical cement remover and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101364056A (en) * | 2007-08-10 | 2009-02-11 | 安集微电子（上海）有限公司 | Detergent for photo resist |
| CN101412948A (en) * | 2007-10-19 | 2009-04-22 | 安集微电子（上海）有限公司 | Cleaning agent for plasma etching residue |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4538286B2 (en) * | 2004-09-14 | 2010-09-08 | トヨタ自動車株式会社 | Mold cleaning method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101364056A (en) * | 2007-08-10 | 2009-02-11 | 安集微电子（上海）有限公司 | Detergent for photo resist |
| CN101412948A (en) * | 2007-10-19 | 2009-04-22 | 安集微电子（上海）有限公司 | Cleaning agent for plasma etching residue |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3862072A4 (en) * | 2018-10-04 | 2022-07-06 | Sumitomo Chemical Company Limited | Composition useful for production of acidic gas separation membrane |
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Effective date of registration: 20160928 Address after: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Patentee after: Anji Microelectronics (Shanghai) Co., Ltd. Address before: 201203, room 5, building 3000, 613-618 East Avenue, Zhangjiang hi tech park, Shanghai, Pudong New Area Patentee before: Anji Microelectronics (Shanghai) Co., Ltd. |
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Address after: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Patentee after: Anji microelectronic technology (Shanghai) Limited by Share Ltd Address before: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Patentee before: Anji Microelectronics (Shanghai) Co., Ltd. |