CN104238287A - Cleaning solution for removing photoresist residues - Google Patents
Cleaning solution for removing photoresist residues Download PDFInfo
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- CN104238287A CN104238287A CN201310245600.XA CN201310245600A CN104238287A CN 104238287 A CN104238287 A CN 104238287A CN 201310245600 A CN201310245600 A CN 201310245600A CN 104238287 A CN104238287 A CN 104238287A
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Abstract
The invention discloses a cleaning solution for removing photoresist residues and composition of the cleaning solution. The cleaning solution for removing photoresist residues contains quaternary aluminum hydroxide, alcohol amine, a solvent and silane. The cleaning solution can be used for more effectively removing photoresist residues on wafers, is basically noncorrosive to metal copper, aluminum and the like and has a wide application prospect in the field such as semiconductor chip cleaning.
Description
Technical field
The present invention relates to a kind of cleaning fluid for removing photoresistance residue.
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; Such as US5529887 discloses and forms alkaline cleaning fluid by potassium hydroxide (KOH), alkylene glycol monoalkyl ether, soluble fluoride and water etc. again, is immersed by wafer in this cleaning fluid, removes the photoresist in metal and dielectric substrate at 40 ~ 90 DEG C.It is higher to the corrosion of semiconductor wafer substrate.Such as US5480585 discloses a kind of cleaning fluid containing non-aqueous system again, and its composition is monoethanolamine, sulfolane or dimethyl sulfoxide and catechol, can remove the photoresist in metal and dielectric substrate, to metal no corrosion at 40 ~ 120 DEG C.Such as US2005119142 discloses a kind of non-aqueous cleaning fluid of polymkeric substance, dipropylene glycol alkyl ether, 1-METHYLPYRROLIDONE and methyl isobutyl ketone containing alkoxy again.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.In order to adapt to new situation, a class photoresist removal ability must be developed strong, the cleaning fluid of metallic aluminium compatibility.
Summary of the invention
The object of the invention is to provide a kind of cleaning fluid and the composition thereof of effectively removing photoresistance residue.This cleaning fluid, while effectively removing the 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: quaternary ammonium hydroxide, hydramine, solvent and silane.Wherein the concentration of quaternary ammonium hydroxide is mass percent 0.1-6%; Preferred 0.5-3.5%; The concentration of hydramine is mass percent 0.1-30%, preferred 0.5-20%; The concentration of silane is mass percent 0.1 ~ 8%, preferred 0.5-5%; Surplus is organic solvent.
Due to azanol, the use of fluoride is comparatively dangerous and exist environment and pollute, and oxygenant can cause the Oxidative inactivation of all kinds of material in cleaning fluid.Therefore, the cleaning fluid of above-mentioned removal photoresistance residue is not containing azanol, fluoride and oxygenant.Similarly, it will be appreciated by persons skilled in the art that in this cleaning fluid and also do not comprise 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.
In the present invention, described silane is preferably the silane containing alkoxy, is preferably one or more in tetramethoxy-silicane, tetraethoxysilane, trimethoxymethylsila,e, trimethoxy ethylsilane, trimethoxy propyl silane, dimethoxydimethylsilane, dimethoxy diethylsilane, triethoxy methyl silicane and (3-aminopropyl) triethoxysilane.
In the present invention, organic solvent is preferably one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and alcohol ether; Sulfoxide is preferably one or more in dimethyl sulfoxide (DMSO) and first ethyl-sulfoxide; Sulfone is preferably one or more in methyl sulfone, sulfolane; Imidazolidinone is preferably one or more in 2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone; Pyrrolidone is preferably one or more in 1-METHYLPYRROLIDONE and N-cyclohexyl pyrrolidone; Imidazolone is preferably DMI; Acid amides is preferably one or more in dimethyl formamide and dimethyl acetamide; 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 residue at 25 DEG C to 80 DEG C on cleaning wafer.Concrete grammar is as follows: immersed by the wafer containing photoresistance 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 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.
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 and comparative example cleaning fluid and content
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 2.
The wafer cleaning situation of table 2 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 2, cleaning fluid of the present invention is implanted to wafer microballoon the wafer containing photoresistance 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 1 and embodiment 9: under the condition that other component is the same and operating conditions is identical, although both do not find out significant difference to the cleaning of photoresist, the corrosion of comparative example 1 pair of metallic aluminium and copper suppresses do not have embodiment 9 good.The contrast of comparative example 2 and embodiment 14, demonstrates adding of silane further, is conducive to the suppression of metallic aluminium and copper corrosion.
To sum up, positive progressive effect of the present invention is: cleaning fluid of the present invention more efficiently can remove photoetching glue residue under similarity condition; Simultaneously for base material as the no corrosion such as metallic aluminium and copper, have a good application prospect in fields such as cleaning semiconductor chips.
Should be understood that, % 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 (14)
1., for removing a cleaning fluid for photoresistance residue, containing quaternary ammonium hydroxide, hydramine, solvent, is characterized in that, described cleaning fluid includes silane.
2. cleaning fluid as claimed in claim 1, it 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.
3. cleaning fluid as claimed in claim 1, it is characterized in that, one or more for being selected from monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, N-diethyl ethanolamine, N-(2-amino-ethyl) monoethanolamine and diglycolamine of described hydramine.
4. cleaning fluid as claimed in claim 1, it is characterized in that, described silane is the silane containing alkoxy.
5. cleaning fluid as claimed in claim 4, it is characterized in that, described silane be selected from tetramethoxy-silicane, tetraethoxysilane, trimethoxymethylsila,e, trimethoxy ethylsilane, trimethoxy propyl silane, dimethoxydimethylsilane, dimethoxy diethylsilane, triethoxy methyl silicane and (3-aminopropyl) triethoxysilane one or more.
6. cleaning fluid as claimed in claim 1, is characterized in that, described organic solvent be selected from sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and alcohol ether one or more.
7. cleaning fluid as claimed in claim 6, is characterized in that, described sulfoxide is one or more in dimethyl sulfoxide (DMSO) and first ethyl-sulfoxide; One or more comparatively in methyl sulfone, sulfolane of described sulfone; Described imidazolidinone is one or more in 2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone; Described pyrrolidone is one or more in 1-METHYLPYRROLIDONE and N-cyclohexyl pyrrolidone; Described imidazolone is DMI; Described acid amides is one or more in dimethyl formamide and dimethyl acetamide; Described alcohol ether is one or more in diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether.
8. cleaning fluid as claimed in claim 1, it is characterized in that, the concentration of described quaternary ammonium hydroxide is mass percent 0.1-6%.
9. cleaning fluid as claimed in claim 8, it is characterized in that, the concentration of described quaternary ammonium hydroxide is mass percent 0.5-3.5%.
10. cleaning fluid as claimed in claim 1, it is characterized in that, the concentration of described hydramine is mass percent 0.1-30%.
11. cleaning fluids as claimed in claim 10, is characterized in that, the concentration of described hydramine is mass percent 0.5-20%.
12. cleaning fluids as claimed in claim 1, is characterized in that, the concentration of described silane is mass percent 0.01 ~ 8%.
13. cleaning fluids as claimed in claim 12, is characterized in that, the concentration of described silane is mass percent 0.5-5%.
14. cleaning fluids as claimed in claim 1, is characterized in that, described cleaning fluid is not containing azanol, fluoride and oxygenant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245600.XA CN104238287A (en) | 2013-06-20 | 2013-06-20 | Cleaning solution for removing photoresist residues |
| TW103118224A TW201500865A (en) | 2013-06-20 | 2014-05-26 | Cleaning composition for photoresist residue removal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245600.XA CN104238287A (en) | 2013-06-20 | 2013-06-20 | Cleaning solution for removing photoresist residues |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104238287A true CN104238287A (en) | 2014-12-24 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310245600.XA Pending CN104238287A (en) | 2013-06-20 | 2013-06-20 | Cleaning solution for removing photoresist residues |
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| CN (1) | CN104238287A (en) |
| TW (1) | TW201500865A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776532A (en) * | 2004-06-15 | 2006-05-24 | 气体产品与化学公司 | Composition for removal of residual material from substrate and method using the composition |
| CN101078892A (en) * | 2006-05-26 | 2007-11-28 | 气体产品与化学公司 | Composition and method for photoresist removal |
| CN101286017A (en) * | 2007-04-13 | 2008-10-15 | 安集微电子（上海）有限公司 | Thick film photoresist cleaning agent |
| CN101373339A (en) * | 2007-08-23 | 2009-02-25 | 安集微电子（上海）有限公司 | Cleaning agent of thick film photoresist |
| CN102286304A (en) * | 2010-06-17 | 2011-12-21 | 陆兴艳 | Hard water resistance water-soluble cutting fluid |
| CN103003923A (en) * | 2010-07-16 | 2013-03-27 | 高级技术材料公司 | Aqueous cleaner for the removal of post-etch residues |
-
2013
- 2013-06-20 CN CN201310245600.XA patent/CN104238287A/en active Pending
-
2014
- 2014-05-26 TW TW103118224A patent/TW201500865A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776532A (en) * | 2004-06-15 | 2006-05-24 | 气体产品与化学公司 | Composition for removal of residual material from substrate and method using the composition |
| CN101078892A (en) * | 2006-05-26 | 2007-11-28 | 气体产品与化学公司 | Composition and method for photoresist removal |
| CN101286017A (en) * | 2007-04-13 | 2008-10-15 | 安集微电子（上海）有限公司 | Thick film photoresist cleaning agent |
| CN101373339A (en) * | 2007-08-23 | 2009-02-25 | 安集微电子（上海）有限公司 | Cleaning agent of thick film photoresist |
| CN102286304A (en) * | 2010-06-17 | 2011-12-21 | 陆兴艳 | Hard water resistance water-soluble cutting fluid |
| CN103003923A (en) * | 2010-07-16 | 2013-03-27 | 高级技术材料公司 | Aqueous cleaner for the removal of post-etch residues |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201500865A (en) | 2015-01-01 |
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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 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 Applicant before: Anji Microelectronics (Shanghai) Co., Ltd. |
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Application publication date: 20141224 |
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