CN104678719A - Photoresist cleaning liquid with extremely-low corrosion to metals - Google Patents
Photoresist cleaning liquid with extremely-low corrosion to metals Download PDFInfo
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- CN104678719A CN104678719A CN201310624949.4A CN201310624949A CN104678719A CN 104678719 A CN104678719 A CN 104678719A CN 201310624949 A CN201310624949 A CN 201310624949A CN 104678719 A CN104678719 A CN 104678719A
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- cleaning fluid
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Abstract
The invention discloses photoresist cleaning liquid for removing the photoresist residues and with extremely-low corrosion to metals and composition thereof. The photoresist cleaning liquid contains (a) quaternary ammonium hydroxide; (b) alkylol amine; (c) solvent; (d) C4-C6 polyhydric alcohol; and (e) thiazole derivative. The photoresist cleaning liquid disclosed by the invention has the advantages that the photoresist photoresistance residues on wafers can be effectively removed, and the corrosion to metals such as copper and aluminium is ultra-low; and the application prospect in the fields of cleaning of semiconductor chips and the like is good.
Description
Technical field
The invention discloses a kind of photoresist cleaning fluid to metal pole low corrosion.
Background technology
In common semiconductor fabrication process, by forming the mask of photoresist on the surface of some materials, after exposure, carrying out Graphic transitions, after obtaining the figure needed, before carrying out next process, needing to peel off residual photoresist.Require in this process to remove unwanted photoresist completely, any base material can not be corroded simultaneously.
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.
As JP1998239865 discloses a kind of cleaning fluid of Aquo System, its composition is Tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO) (DMSO), 1,3 '-dimethyl-2-imidazolidinone (DMI) and water.Wafer is immersed in this cleaning fluid, at 50 ~ 100 DEG C, remove the photoresist 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;
US5091103 discloses 1-METHYLPYRROLIDONE, 1, the cleaning fluid of 2-propylene glycol and Tetramethylammonium hydroxide, the photoresist crossing (hard bake) through high bake temperature is removed at 105 ~ 125 DEG C, it is characterized in that not containing water, operating temperature is high, once cleaning fluid is mixed into water, it all rises to the corrosion rate of metallic aluminium and copper.
This cleaning fluid can be applicable to the cleaning of positive photoresist and negative photoresist simultaneously.Along with the fast development of semiconductor, the particularly development of convex ball encapsulation field, to the cleaning requirement also corresponding raising of photoetching glue residue; Mainly in unit area, number of pins (I/O) gets more and more, and the removal of photoresist also becomes more and more difficult.As can be seen here, finding more efficiently photoresist cleaning fluid is the privileged direction that such photoresist cleaning fluid makes great efforts to improve.Generally speaking, the cleansing power improving alkaline photoresist cleaning fluid mainly by improve cleaning fluid alkalescence, select more efficiently dicyandiamide solution, improve operating temperature and extend that running time several aspect realizes.But improving the alkalescence of cleaning fluid and operating temperature and extending scavenging period often increases corrosion of metal.Generally speaking, if master metal silver, tin, lead and the copper four kinds of metals related in salient point encapsulation field.Recently, in order to reduce costs raising yield further, some packaging and testing manufacturers start the corrosion that requirement photoresist cleaning fluid also can suppress metallic aluminium further.
As can be seen here, find and more effectively suppress metal erosion suppressing method and efficient photoresist removal ability to be the privileged direction that such photoresist cleaning fluid makes great efforts to improve.
Summary of the invention
The object of the invention is to provide a kind of photoresist cleaning fluid having a pole low corrosion to metal effectively to remove cleaning fluid and the application thereof of photoresistance residue.This cleaning fluid, while effectively removing the photoresist photoresistance residue on wafer, for base material as the no corrosion such as metallic aluminium, copper, has a good application prospect in fields such as cleaning semiconductor chips.
This Novel washing liquid contains: a) quaternary ammonium hydroxide; (b) hydramine; (c) solvent; (d) C
4-C
6polyvalent alcohol; (e) thiazole; Wherein
I. quaternary ammonium hydroxide 0.1-6%; Preferred 0.5-3.5%
Ii. hydramine 0.1-30%, preferred 0.5-20%;
Iii. C
4-C
6polyvalent alcohol 0.1 ~ 10%, 0.1 ~ 5%, preferably 0.5 ~ 3%;
Iv. thiazole 0.1 ~ 5%, preferred 0.5-2.5%;
V. surplus is organic solvent (49-99.6%).
Above-mentioned content is mass percentage content; The cleaning fluid of removal photoresistance photoetching glue residue involved in the present invention is not containing azanol, fluoride, oxygenant and abrasive grains.
In the present invention, quaternary ammonium hydroxide be selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cetyltrimethylammonium hydroxide and benzyltrimethylammonium hydroxide one or more.
In the present invention, hydramine is preferably monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, N-diethyl ethanolamine, N-(2-amino-ethyl) monoethanolamine and diglycolamine.Preferred monoethanolamine, triethanolamine and composition thereof.
C in the present invention
4-C
6polyvalent alcohol be selected from threose, arabinose, wood sugar, ribose, ribulose, xylulose, glucose, mannose, galactose, Tagatose, allose, altrose, idose, talose, sorbose, psicose, fructose, threitol, erythrite, ribitol, arabite, xylitol, talitol, sorbierite, sweet mellow wine, iditol and galactitol one or several.
In the present invention, thiazole is for being selected from 2,5-bis-(uncle-molybdenum didodecyl dithiophosphate)-1,3,4-thiadiazoles, 2,5-dimercapto-1,3,4-thiadiazoles, 5-(2-chlorophenylmethyl sulfo-)-2-sulfydryl-1,3,4-thiadiazoles, 2,5-two (octyl group two sulfo-) thiadiazoles, 2-mercaptobenzothiazole, 2-dimercaptothiodiazole, 2-amino-1,3,4-thiadiazoles, 2-sulfydryl-5-methyl isophthalic acid, 3,4-thiadiazoles, 5-methyl-2-dimercaptothiodiazole, 2,1,3-diazosulfide, thiazolamine.
In the present invention, organic solvent is preferably one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and alcohol ether; Described sulfoxide is preferably one or more in dimethyl sulfoxide (DMSO) and first ethyl-sulfoxide; Described sulfone is preferably one or more in methyl sulfone, sulfolane; Described imidazolidinone is preferably one or more in 2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone; Described pyrrolidone is preferably one or more in 1-METHYLPYRROLIDONE and N-cyclohexyl pyrrolidone; Described imidazolone is preferably DMI; Described acid amides is preferably one or more in dimethyl formamide and dimethyl acetamide; Described alcohol ether is preferably one or more in diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether.
Cleaning fluid in the present invention, can photoresistance photoetching glue residue at 25 DEG C to 80 DEG C on cleaning wafer.Concrete grammar is as follows: immersed by the wafer containing photoresistance photoetching glue residue in the cleaning fluid in the present invention, after soaking the suitable time, dries up after taking out rinsing with high pure nitrogen at 25 DEG C to 80 DEG C.
Positive progressive effect of the present invention is: cleaning fluid of the present invention, while effectively removing the photoresist photoresistance residue on wafer, for base material as the no corrosion such as metallic aluminium, copper, has a good application prospect in fields such as cleaning semiconductor chips.
Agents useful for same of the present invention and raw material are all commercially.Cleaning fluid of the present invention can be obtained by the simple Homogeneous phase mixing of mentioned component.
Embodiment
Set forth advantage of the present invention further below by specific embodiment, but protection scope of the present invention is not only confined to following embodiment.
Agents useful for same of the present invention and raw material are all commercially.Cleaning fluid of the present invention can be obtained by the simple Homogeneous phase mixing of mentioned component.
The component of table 1 embodiment cleaning fluid and content
The component of table 2 comparative example cleaning fluid and content
Effect example
In order to investigate the cleaning situation of this based cleaning liquid further, present invention employs following technological means: implant the wafer containing photoresistance residue after technique convexity ball has been electroplated by wafer microballoon, immerse respectively in cleaning fluid at 25 DEG C to 80 DEG C, utilize constant temperature oscillator with the vibration frequency of about 60 revs/min vibration 30 ~ 120 minutes, then dry up with high pure nitrogen after rinsing.The cleaning performance of photoresistance residue and the corrosion condition of cleaning fluid to wafer as shown in table 3.
The wafer cleaning situation of table 3 section Example and comparative example
| 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 3, cleaning fluid of the present invention is implanted to wafer microballoon the wafer containing photoetching glue residue after technique convexity ball has been electroplated and is had good cleaning performance, and serviceability temperature scope is wide.As can be seen from comparative example 8-1 and embodiment 8: in comparative example 8-1, thiazole does not add, the amount do not added all is added C
4-C
6polyvalent alcohol on, other component is the same and under the condition that operating conditions is identical, what demonstrate thiazole adds the suppression being conducive to metallic aluminium and copper corrosion, although both do not find out significant difference to the cleaning of photoresist, the corrosion of comparative example 8-1 to metallic aluminium and copper suppresses do not have embodiment 8 good.The contrast of comparative example 8-2 and embodiment 8: C in comparative example 8-2
4-C
6the amount that do not add of polyvalent alcohol, be all added on thiazole, demonstrate C
4-C
6polyvalent alcohol add the suppression being conducive to metallic aluminium and copper corrosion, but comparative example 8-2 suppresses do not have embodiment 8 good equally to the corrosion of metallic aluminium and copper.Known by the effect example of above-mentioned comparative example 8-1,8-2 and embodiment 8, C
4-C
6polyvalent alcohol and thiazole there is composite effect between the two, both match and can suppress the corrosion of metallic copper and aluminium better.The contrast of comparative example 8-3 and embodiment 8, demonstrates thiazole and C
4-C
6polyvalent alcohol when not adding, more serious to corrosion of metal.The contrast of comparative example 8-4 and embodiment 8, demonstrates C
4-C
6the addition of polyvalent alcohol exceed certain limit, although have ultralow corrosion to metal, very large on the cleaning impact of photoresist, have a large amount of photoresist to remain.Comparative example 16-1,16-2,16-3,16-4 can find out with embodiment 16: embodied identical rule with comparative example 8-1,8-2,8-3,8-4 and embodiment 8.
To sum up, positive progressive effect of the present invention is: cleaning fluid of the present invention, under similarity condition, in certain concentration range, passes through C
4-C
6polyvalent alcohol and the binary built of thiazole, more effectively can remove photoetching glue residue; Simultaneously for base material as the no corrosion such as metallic aluminium and copper, particularly metallic aluminium.Have a good application prospect in fields such as cleaning semiconductor chips.
Should be understood that, wt% of the present invention all refers to mass percentage.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (12)
1. a photoresist cleaning fluid, is characterized in that, comprises quaternary ammonium hydroxide, hydramine, solvent, C
4?C
6polyvalent alcohol, thiazole.
2. cleaning fluid as claimed in claim 1, is characterized in that: the content of described quaternary ammonium hydroxide is 0.1 ?6wt%, and described alcohol amine content is 0.1 ?30wt%, described C
4?C
6polyol amount be 0.1 ?10wt%, described thiazole content be 0.1 ?5wt%, described solvent is surplus.
3. cleaning fluid as claimed in claim 2, is characterized in that: the content of described quaternary ammonium hydroxide is 0.5 ?3.5wt%, and described alcohol amine content is 0.5 ?20wt%, described C
4?C
6the content of polyvalent alcohol be 0.1 ~ 5wt%, described thiazole content be 0.5 ?2.5wt%, described solvent is surplus.
4. cleaning fluid as claimed in claim 3, is characterized in that: described C
4?C
6the content of polyvalent alcohol be 0.5 ?3wt%.
5. cleaning fluid as claimed in claim 1, is characterized in that: described quaternary ammonium hydroxide be selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cetyltrimethylammonium hydroxide and benzyltrimethylammonium hydroxide one or more.
6. cleaning fluid as claimed in claim 1, it is characterized in that, described hydramine is selected from monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, N-diethyl ethanolamine, N-(2-amino-ethyl) monoethanolamine and diglycolamine.
7. cleaning fluid as claimed in claim 6, it is characterized in that, described hydramine is monoethanolamine, triethanolamine and composition thereof.
8. cleaning fluid as claimed in claim 1, is characterized in that, described C
4?C
6polyvalent alcohol be selected from threose, arabinose, wood sugar, ribose, ribulose, xylulose, glucose, mannose, galactose, Tagatose, allose, altrose, idose, talose, sorbose, psicose, fructose, threitol, erythrite, ribitol, arabite, xylitol, talitol, sorbierite, sweet mellow wine, iditol and galactitol one or several.
9. cleaning fluid as claimed in claim 1, it is characterized in that, described thiazole is selected from 2, 5-bis-(uncle-molybdenum didodecyl dithiophosphate)-1, 3, 4-thiadiazoles, 2, 5-dimercapto-1, 3, 4-thiadiazoles, 5-(2-chlorophenylmethyl sulfo-)-2-sulfydryl-1, 3, 4-thiadiazoles, 2, two (the octyl group two sulfo-) thiadiazoles of 5-, 2-mercaptobenzothiazole, 2-dimercaptothiodiazole, 2-amino-1, 3, 4-thiadiazoles, 2-sulfydryl-5-methyl isophthalic acid, 3, 4-thiadiazoles, 5-methyl-2-dimercaptothiodiazole, 2, 1, 3-diazosulfide, one or more in thiazolamine.
10. cleaning fluid as claimed in claim 1, is characterized in that, described solvent is one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and alcohol ether.
11. cleaning fluids as claimed in claim 10, is characterized in that, described sulfoxide is dimethyl sulfoxide (DMSO) and/or first ethyl-sulfoxide; Described sulfone is methyl sulfone and/or sulfolane; Described imidazolidinone be 2 ?imidazolidinone and/or 1,3 ?Er Jia Ji ?2 ?imidazolidinone; Described pyrrolidone be N ?methyl pyrrolidone and/or N ?cyclohexyl pyrrolidone; Described imidazolone be 1,3 ?Er Jia Ji ?2 ?imidazolone; Described acid amides is dimethyl formamide and/or dimethyl acetamide; Described alcohol ether is diethylene glycol monobutyl ether and/or dipropylene glycol monomethyl ether.
12. 1 kinds of cleaning fluids as described in any one of claim 1 ?11 are removing except the application in the photoresist photoresistance residue on wafer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310624949.4A CN104678719A (en) | 2013-11-28 | 2013-11-28 | Photoresist cleaning liquid with extremely-low corrosion to metals |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310624949.4A CN104678719A (en) | 2013-11-28 | 2013-11-28 | Photoresist cleaning liquid with extremely-low corrosion to metals |
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|---|---|
| CN104678719A true CN104678719A (en) | 2015-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310624949.4A Pending CN104678719A (en) | 2013-11-28 | 2013-11-28 | Photoresist cleaning liquid with extremely-low corrosion to metals |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106292207A (en) * | 2015-06-10 | 2017-01-04 | 安集微电子科技(上海)有限公司 | A kind of photoresistance residual washing liquid |
| CN106919013A (en) * | 2015-12-28 | 2017-07-04 | 安集微电子（上海）有限公司 | A kind of cleaning fluid of the removal photoresistance residue of low etching |
| CN108255027A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子（上海）有限公司 | A kind of photoresist cleaning solution |
Citations (4)
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|---|---|---|---|---|
| US5846695A (en) * | 1996-04-12 | 1998-12-08 | Mitsubishi Gas Chemical Company, Inc. | Removing agent composition for a photoresist and process for producing a semiconductor integrated circuit |
| CN101364056A (en) * | 2007-08-10 | 2009-02-11 | 安集微电子（上海）有限公司 | Detergent for photo resist |
| CN101750914A (en) * | 2008-12-05 | 2010-06-23 | 安集微电子（上海）有限公司 | Photoresist detergent composition |
| CN102399648A (en) * | 2010-09-10 | 2012-04-04 | 安集微电子（上海）有限公司 | Fluorine-containing cleaning solution |
-
2013
- 2013-11-28 CN CN201310624949.4A patent/CN104678719A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846695A (en) * | 1996-04-12 | 1998-12-08 | Mitsubishi Gas Chemical Company, Inc. | Removing agent composition for a photoresist and process for producing a semiconductor integrated circuit |
| CN101364056A (en) * | 2007-08-10 | 2009-02-11 | 安集微电子（上海）有限公司 | Detergent for photo resist |
| CN101750914A (en) * | 2008-12-05 | 2010-06-23 | 安集微电子（上海）有限公司 | Photoresist detergent composition |
| CN102399648A (en) * | 2010-09-10 | 2012-04-04 | 安集微电子（上海）有限公司 | Fluorine-containing cleaning solution |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106292207A (en) * | 2015-06-10 | 2017-01-04 | 安集微电子科技(上海)有限公司 | A kind of photoresistance residual washing liquid |
| CN106919013A (en) * | 2015-12-28 | 2017-07-04 | 安集微电子（上海）有限公司 | A kind of cleaning fluid of the removal photoresistance residue of low etching |
| CN106919013B (en) * | 2015-12-28 | 2021-12-07 | 安集微电子（上海）有限公司 | Low-etching cleaning solution for removing photoresist residues |
| CN108255027A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子（上海）有限公司 | A kind of photoresist cleaning solution |
| CN108255027B (en) * | 2016-12-28 | 2024-04-12 | 安集微电子（上海）有限公司 | Photoresist cleaning solution |
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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 Applicant after: ANJI MICROELECTRONICS TECHNOLOGY (SHANGHAI) Co.,Ltd. Address before: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Applicant before: ANJI MICROELECTRONICS TECHNOLOGY (SHANGHAI) Co.,Ltd. |
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Application publication date: 20150603 |