CN104238288A - Cleaning solution for removing photoresist residues - Google Patents
Cleaning solution for removing photoresist residues Download PDFInfo
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- CN104238288A CN104238288A CN201310245618.XA CN201310245618A CN104238288A CN 104238288 A CN104238288 A CN 104238288A CN 201310245618 A CN201310245618 A CN 201310245618A CN 104238288 A CN104238288 A CN 104238288A
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- cleaning fluid
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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 organic polyamine. The cleaning solution can be used for more effectively removing photoresist residues on wafers, is basically noncorrosive to metal copper 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; For selected system, its dicyandiamide solution is also determined; So the photoresist removal ability how improving cleaning fluid in existing system is further exactly the effort improvement direction that liquid removed by many photoresists.
Summary of the invention
The object of the invention is to provide a kind of cleaning fluid and the composition thereof of more effectively removing photoresistance residue.This cleaning fluid, while effectively removing the photoresistance residue on wafer, for base material as no corrosions such as metallic coppers, has a good application prospect in fields such as cleaning semiconductor chips.
This Novel washing liquid contains: quaternary ammonium hydroxide, hydramine, solvent and organic polyamine, and wherein the concentration of quaternary ammonium hydroxide is 0.1-6%, preferred 0.5-3.5%; The concentration of hydramine is 0.1-30%, preferred 0.5-20%; The concentration of organic polyamine is 0.01 ~ 10%, preferred 0.05-5%; Surplus is organic solvent.Above-mentioned content is mass percentage content.
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, organic polyamine is preferably one or more in diethylenetriamine, pentamethyl-diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines, six ethene seven amine and polyethylene polyamine.Preferred TEPA and the potpourri with the amine described in other thereof.
In the present invention, organic solvent is preferably one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and alcohol ether.Wherein 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, N-cyclohexyl pyrrolidone and NHP; 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 monomethyl ether, 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 more effectively can remove photoetching glue residue under similarity condition; Simultaneously for base material as no corrosions such as metallic coppers, have 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 8: under the condition that other components are the same and operating conditions is identical, the corrosion of copper suppresses do not have significant difference, but the cleaning performance of embodiment is better.The contrast of comparative example 2 and embodiment 11, demonstrates adding of organic polyamine further, is conducive to the removal of photoresist.
To sum up, positive progressive effect of the present invention is: cleaning fluid of the present invention more effectively can remove photoetching glue residue under similarity condition; Simultaneously for base material as no corrosions such as metallic coppers, 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 (13)
1., for removing a cleaning fluid for photoresistance residue, containing quaternary ammonium hydroxide, hydramine, solvent, is characterized in that, described cleaning fluid includes organic polyamine.
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 organic polyamine be selected from diethylenetriamine, pentamethyl-diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines, six ethene seven amine and polyethylene polyamine one or more.
5. 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.
6. cleaning fluid as claimed in claim 5, is characterized in that, described sulfoxide is one or more in dimethyl sulfoxide (DMSO) and first ethyl-sulfoxide; Described sulfone is one or more in methyl sulfone, sulfolane; Described imidazolidinone is one or more in 2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone; Described pyrrolidone is one or more in 1-METHYLPYRROLIDONE, N-cyclohexyl pyrrolidone and NHP; 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 monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether.
7. 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%.
8. cleaning fluid as claimed in claim 7, it is characterized in that, the concentration of described quaternary ammonium hydroxide is mass percent 0.5-3.5%.
9. cleaning fluid as claimed in claim 1, it is characterized in that, the concentration of described hydramine is mass percent 0.1-30%.
10. cleaning fluid as claimed in claim 9, it is characterized in that, the concentration of described hydramine is mass percent 0.5-20%.
11. cleaning fluids as claimed in claim 1, is characterized in that, the concentration of described organic polyamine is mass percent 0.01 ~ 10%.
12. cleaning fluids as claimed in claim 11, is characterized in that, the concentration of described organic polyamine is mass percent 0.05-5%.
13. cleaning fluids as claimed in claim 1, is characterized in that, described cleaning fluid is not containing azanol, fluoride and oxygenant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245618.XA CN104238288A (en) | 2013-06-20 | 2013-06-20 | Cleaning solution for removing photoresist residues |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245618.XA CN104238288A (en) | 2013-06-20 | 2013-06-20 | Cleaning solution for removing photoresist residues |
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| CN104238288A true CN104238288A (en) | 2014-12-24 |
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| CN201310245618.XA Pending CN104238288A (en) | 2013-06-20 | 2013-06-20 | Cleaning solution for removing photoresist residues |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107121901A (en) * | 2017-06-23 | 2017-09-01 | 昆山欣谷微电子材料有限公司 | A kind of rich water base cleaning liquid composition |
| CN107841383A (en) * | 2016-09-21 | 2018-03-27 | 仓和股份有限公司 | Half tone cleaning fluid and its application method |
| CN109778210A (en) * | 2018-08-09 | 2019-05-21 | 苏州纳勒电子科技有限公司 | It is a kind of to go film liquid on circuit board |
| CN115820351A (en) * | 2022-12-19 | 2023-03-21 | 芯越微电子材料(嘉兴)有限公司 | Semiconductor wafer substrate cleaning solution composition and application method thereof |
-
2013
- 2013-06-20 CN CN201310245618.XA patent/CN104238288A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841383A (en) * | 2016-09-21 | 2018-03-27 | 仓和股份有限公司 | Half tone cleaning fluid and its application method |
| CN107121901A (en) * | 2017-06-23 | 2017-09-01 | 昆山欣谷微电子材料有限公司 | A kind of rich water base cleaning liquid composition |
| CN109778210A (en) * | 2018-08-09 | 2019-05-21 | 苏州纳勒电子科技有限公司 | It is a kind of to go film liquid on circuit board |
| CN115820351A (en) * | 2022-12-19 | 2023-03-21 | 芯越微电子材料(嘉兴)有限公司 | Semiconductor wafer substrate cleaning solution composition and application method thereof |
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Application publication date: 20141224 |