CN102096345A - Thick-film photoresist cleaning solution and cleaning method thereof - Google Patents
Thick-film photoresist cleaning solution and cleaning method thereof Download PDFInfo
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- CN102096345A CN102096345A CN2009102003183A CN200910200318A CN102096345A CN 102096345 A CN102096345 A CN 102096345A CN 2009102003183 A CN2009102003183 A CN 2009102003183A CN 200910200318 A CN200910200318 A CN 200910200318A CN 102096345 A CN102096345 A CN 102096345A
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Abstract
The invention discloses thick-film photoresist cleaning solution and a cleaning method thereof. The photoresist cleaning solution comprises dimethyl sulfoxide, potassium hydroxide, aryl alcohol, alcohol amine and a metal corrosion inhibitor. The photoresist cleaning solution can be used in a wider temperature range from 30 to 90 DEG C, is used for removing thicker photoresist on a metal, a metal alloy or a dielectric medium and other substrates in a semiconductor manufacturing process, and is particularly suitable for removing high-crosslinking degree negative photoresist with the thickness of over 100 mu m. Meanwhile, the photoresist cleaning solution has extremely weak corrosion on copper, tin, lead and other metals, does not damage chip patterns and substrates, and has good application prospect in the fields of microelectronics, such as semiconductor chip cleaning and the like.
Description
Technical field
The present invention relates to a kind of thick film photolithography glue cleaning fluid and cleaning method thereof of low etching property.
Background technology
In common semiconductor fabrication process,, utilize wet method or dry etching to carry out figure transfer after the exposure by going up the mask that forms photoresist on surfaces such as silicon dioxide, Cu metals such as (copper) and low-k materials.Implant in the technology (bumping technology) at the wafer microballoon, also need photoresist (photoresist) to form mask, this mask needs to remove after microballoon is successfully implanted equally, but because this photoresist is thicker, often removes comparatively difficulty fully.Improving removal effect method comparatively commonly used is to adopt to prolong soak time, raising soaking temperature and adopt more to be rich in aggressive solution, but this regular meeting causes the corrosion of wafer substrate and the corrosion of microballoon, thereby causes the remarkable reduction of wafer yield.
At present, the photoresist cleaning fluid mainly is made up of polar organic solvent, highly basic and/or water etc., by immersing semiconductor wafer in the cleaning fluid or utilizing cleaning fluid flushing semiconductor wafer, removes the photoresist on the semiconductor wafer.
JP1998239865 is by Tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO) (DMSO), 1,3 '-dimethyl-2-imidazolidinone (DMI) and water etc. are formed alkaline cleaning fluid, wafer is immersed in this cleaning fluid the thick film photolithography glue more than the 20 μ m that remove under 50～100 ℃ on metal and the dielectric substrate.Its corrosion to the semiconductor wafer base material is slightly high, and can not remove the photoresist on the semiconductor wafer, cleansing power deficiency fully.
US5529887 forms alkaline cleaning fluid by potassium hydroxide (KOH), alkylene glycol monoalkyl ether, soluble fluoride and water etc., wafer is immersed in this cleaning fluid, at the thick film photolithography glue of removing under 40～90 ℃ on metal and the dielectric substrate.Its corrosion to the semiconductor wafer base material is higher.
WO2006/056298A1 utilizes by Tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO) (DMSO), and ethylene glycol (EG) and water are formed alkaline cleaning fluid, are used to clean the photoresist of 50～100 micron thickness, simultaneously metallic copper are not had corrosion substantially.
US6040117 utilizes by TMAH, dimethyl sulfoxide (DMSO) (DMSO), 1,3 '-dimethyl-2-imidazolidinone (DMI) and water etc. are formed alkaline cleaning fluid, wafer is entered in this cleaning fluid the thick film photolithography glue more than the 20 μ m that remove under 50～100 ℃ on metal and the dielectric substrate.
In sum, the photoresist that the cleaning fluid of existing photoresist is higher to thickness, special in the cleansing power deficiency of thickness, perhaps stronger to semiconductor wafer pattern and base material corrosivity greater than the photoresist of 100 μ m, there is bigger defective.
Summary of the invention
The technical problem to be solved in the present invention is exactly that the cleansing power that exists at existing thick film photolithography glue cleaning fluid is not enough or to semiconductor wafer pattern and the stronger defective 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 the technical scheme that is adopted: a kind of cleaning fluid that is used for thick film photolithography glue, this cleaning fluid comprises dimethyl sulfoxide (DMSO), potassium hydroxide, aryl alcohol, hydramine, metal corrosion inhibitor.
Among the present invention, what the content of described dimethyl sulfoxide (DMSO) was preferable is mass percent 20～98.79%, and better is mass percent 30～95%.
Among the present invention, what the content of described potassium hydroxide was preferable is mass percent 0.1～10%, and better is mass percent 0.1～3%.
Among the present invention, described aryl alcohol preferable for being selected from phenmethylol, phenylethyl alcohol, benzhydrol, o-benzyl alcohol, p-aminophenyl methyl alcohol, methylbenzyl alcohol, dimethylphenylcarbinol, trimethylbenzene methanol, phthalyl alcohol, isophthalic alcohol, the terephthalyl alcohol one or more, better for being selected from phenmethylol, the pure and mild methylbenzyl alcohol of O-phthalic one or more.What the content of described aryl alcohol was preferable is mass percent 1～50%, and better is mass percent 1～30%.Described aryl alcohol can obviously increase the solubleness of potassium hydroxide in dimethyl sulfoxide (DMSO).
Among the present invention, described hydramine preferable for being selected from monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, diglycolamine and the AEEA one or more, better for being selected from monoethanolamine, diglycolamine, triethanolamine and the methyldiethanolamine one or more.That the content of described hydramine is preferable is mass percent 0.1～50wt%, and that better is mass percent 0.5～40wt%.
Among the present invention, described metal corrosion inhibitor is the salt of benzotriazole or derivatives thereof.Its structural formula is as follows:
Wherein: R is hydrogen, C6 with interior alkyl, C6 with interior hydroxyalkyl, C6 with interior ether and C6 with interior ammonia (amine) base; M is alkali metal ion or alkaline-earth metal ions, preferred sodium, potassium ion.
The benefit of selecting the salt of benzotriazole or derivatives thereof for use is to give full play to the effect of corrosion inhibition of benzotriazole or derivatives thereof to metallic copper and tin lead etc., simultaneously can avoid the potassium hydroxide in benzotriazole or derivatives thereof and the system to react, can generate the water of trace in the alkali in the consumption system.Consuming alkali can influence the removal of photoresistance or residue, and the water of trace can cause corrosion of metal, the especially corrosion of metallic microspheres simultaneously.That described metal corrosion inhibitor content is preferable is mass percent 0.01～5wt%, and that better is mass percent 0.1～3wt%.
Photoresist cleaning fluid among the present invention can be used to clean the thick film photolithography glue of removing on the semiconductor wafer, particularly the photoresist of the above thickness of 100 μ m in bigger temperature range (between 30～90 ℃).Cleaning method can be with reference to following steps: the semiconductor wafer that will contain photoresist immerses in the cleaning fluid, utilizes constant temperature oscillator slowly to vibrate under 30～90 ℃, dries up with high pure nitrogen behind deionized water wash then.
Agents useful for same of the present invention and raw material are all commercially available to be got.Among the present invention, the described clean-out system that is used for thick film photolithography glue is mixed and can be made by top described component.
Good effect of the present invention is: cleaning fluid of the present invention adopts aryl alcohol as dissolution with solvents potassium hydroxide, and aryl alcohol has the better protect effect to metallic copper simultaneously; Adopt the protective agent of hydramine as metallic microspheres (bump); Adopt metal corrosion inhibitor, help further suppressing corrosion of metal.Therefore cleaning fluid of the present invention is strong and lower to semiconductor wafer pattern and base material corrosivity to thick film photolithography glue cleansing power.
Embodiment
Further set forth the present invention below by embodiment.Can obtain cleaning fluid of the present invention according to the set of dispense in the table than even mixing.
The component of the clean-out system among table 1 embodiment 1～25 and content
Table 2 part embodiment and comparative example's prescription
Annotate: NA does not add this component.
In order to further specify effect of the present invention and principle, the spy has disposed the solution in the table 2, sees table 2 for details.Of particular note Comparative Examples 1 ' can not form uniform solution in table 2, and the solubleness of this explanation KOH in dimethyl sulfoxide is less.Comparative Examples 2 ' shows that adding aryl alcohol is that phenmethylol can improve the solubleness of KOH in system, can form uniform solution.In order further to investigate the cleaning situation of this based cleaning liquid, the present invention has adopted following technological means: (thickness is about 120 microns to be about to contain negativity esters of acrylic acid photoresist, and through overexposure and etching) semiconductor wafer (salient point encapsulation wafer) immerse in the clean-out system, under 30～90 ℃, utilize constant temperature oscillator with about 60 rev/mins vibration frequency vibration 30～150 minutes, behind deionized water wash, dry up then with high pure nitrogen.The cleaning performance of photoresist and cleaning fluid are as shown in table 3 to the corrosion situation of wafer.
The wafer of table 3. comparative example and part embodiment cleans situation
Corrosion situation: ◎ does not have corrosion substantially; The cleaning situation: ◎ removes fully;
Zero slightly corrosion; Zero small portion of residual;
The △ moderate corrosion; The more remnants of △;
* heavy corrosion.* abundant residues.
As can be seen from Table 3, Comparative Examples 2 ' is compared with Comparative Examples 1 ', aryl alcohol be phenmethylol except improving the solubleness of KOH in system, also help inhibition to metallic copper corrosion.Comparative Examples 3 ' is compared with Comparative Examples 2 ', and the adding of hydramine helps the protection to metallic microspheres as can be seen, but the corrosion of metallic copper is had increase slightly.Comparative Examples 4 ' is compared with Comparative Examples 3 ', and the corrosion of metallic copper is suppressed, but photoresistance is removed ability drop, and the metallic microspheres corrosion increases.This is because methyl benzotriazazole and potassium hydroxide react, and has reduced the alkalescence of system, so photoresistance is removed ability drop, the minor amount of water that reaction simultaneously produces has been aggravated the corrosion of metallic microspheres.Embodiment 26 compares with Comparative Examples 4 ', owing to adopted triazazole kali salt of methyl benzo, has kept under the inhibition situation to the metallic copper corrosion, has strengthened photoresistance and has removed ability, and metallic microspheres is subjected to further protection simultaneously.Other further test shows cleaning fluid of the present invention has excellent cleaning effect to thick film photolithography glue, and the serviceability temperature scope is wide, simultaneously metallic copper and metallic microspheres etc. is had the effect of corrosion inhibition preferably.
Claims (11)
1. thick film photolithography glue cleaning fluid, it comprises: dimethyl sulfoxide (DMSO), potassium hydroxide, aryl alcohol, hydramine, metal corrosion inhibitor.
2. cleaning fluid according to claim 1 is characterized in that described metal corrosion inhibitor is the salt of benzotriazole or derivatives thereof.
3. as cleaning fluid as described in the claim 2, it is characterized in that the structural formula of described metal corrosion inhibitor is as follows:
Wherein: R is hydrogen, C6 with interior alkyl, C6 with interior hydroxyalkyl, C6 with interior ether or C6 with interior ammonia (amine) base; M is alkali metal ion or alkaline-earth metal ions.
4. as cleaning fluid as described in the claim 3, it is characterized in that described M is sodion or potassium ion.
5. cleaning fluid as claimed in claim 1 is characterized in that, the quality percentage composition of described dimethyl sulfoxide (DMSO) is: 20-98.79%; The quality percentage composition of described potassium hydroxide is: 0.1-10%; The quality percentage composition of described aryl alcohol is: 1-50%; The quality percentage composition of described hydramine is: 0.1-50%; The quality percentage composition of described metal corrosion inhibitor is: 0.01-5%.
6. as cleaning fluid as described in the claim 5, it is characterized in that the quality percentage composition of described dimethyl sulfoxide (DMSO) is: 30-95%; The quality percentage composition of described potassium hydroxide is: 0.1-3%; The quality percentage composition of described aryl alcohol is: 1-30%; The quality percentage composition of described hydramine is: 0.5-40%; The quality percentage composition of described metal corrosion inhibitor is: 0.1-3%.
7. cleaning fluid as claimed in claim 1, it is characterized in that described aryl alcohol is to be selected from phenmethylol, phenylethyl alcohol, benzhydrol, o-benzyl alcohol, p-aminophenyl methyl alcohol, methylbenzyl alcohol, dimethylphenylcarbinol, trimethylbenzene methanol, phthalyl alcohol, isophthalic alcohol and the terephthalyl alcohol one or more.
8. as cleaning fluid as described in the claim 7, it is characterized in that described aryl alcohol is to be selected from phenmethylol, the pure and mild methylbenzyl alcohol of O-phthalic one or more.
9. cleaning fluid according to claim 1, it is characterized in that described hydramine is to be selected from monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, diglycolamine and the AEEA one or more.
10. as cleaning fluid as described in the claim 9, it is characterized in that described hydramine is to be selected from monoethanolamine, diglycolamine, triethanolamine and the methyldiethanolamine one or more.
11. utilize the cleaning method of each described cleaning fluid cleaning thick film photoresist of claim 1～10, it is characterized in that, described cleaning method can carry out with reference to following steps: the semiconductor wafer that will contain photoresist immerses in the cleaning fluid, under 30～90 ℃, utilize constant temperature oscillator slowly to vibrate, behind deionized water wash, dry up then with high pure nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102003183A CN102096345A (en) | 2009-12-11 | 2009-12-11 | Thick-film photoresist cleaning solution and cleaning method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102003183A CN102096345A (en) | 2009-12-11 | 2009-12-11 | Thick-film photoresist cleaning solution and cleaning method thereof |
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| CN102096345A true CN102096345A (en) | 2011-06-15 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103605270A (en) * | 2013-10-31 | 2014-02-26 | 合肥中南光电有限公司 | Photoresist water-base silicon chip cleaning fluid and preparation method thereof |
| CN107085358A (en) * | 2017-06-23 | 2017-08-22 | 昆山欣谷微电子材料有限公司 | For removing the photoresist lift off liquid containing back chip metalization layer |
| CN107085357A (en) * | 2017-06-23 | 2017-08-22 | 昆山欣谷微电子材料有限公司 | A kind of photoresist lift off liquid |
| CN115318717A (en) * | 2022-08-05 | 2022-11-11 | 华虹半导体(无锡)有限公司 | Method for removing residual glue on heating plate PI of baking unit |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101187788A (en) * | 2006-11-17 | 2008-05-28 | 安集微电子（上海）有限公司 | Low etching relative thick photoresist cleaning liquor |
| CN101201557A (en) * | 2006-12-15 | 2008-06-18 | 安集微电子（上海）有限公司 | Detergent for cleaning thick film photoresist |
| CN101364056A (en) * | 2007-08-10 | 2009-02-11 | 安集微电子（上海）有限公司 | Detergent for photo resist |
-
2009
- 2009-12-11 CN CN2009102003183A patent/CN102096345A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101187788A (en) * | 2006-11-17 | 2008-05-28 | 安集微电子（上海）有限公司 | Low etching relative thick photoresist cleaning liquor |
| CN101201557A (en) * | 2006-12-15 | 2008-06-18 | 安集微电子（上海）有限公司 | Detergent for cleaning thick film photoresist |
| CN101364056A (en) * | 2007-08-10 | 2009-02-11 | 安集微电子（上海）有限公司 | Detergent for photo resist |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103605270A (en) * | 2013-10-31 | 2014-02-26 | 合肥中南光电有限公司 | Photoresist water-base silicon chip cleaning fluid and preparation method thereof |
| CN103605270B (en) * | 2013-10-31 | 2016-08-17 | 合肥中南光电有限公司 | A kind of water base silicon chip cleaning liquid of photoresist and preparation method thereof |
| CN107085358A (en) * | 2017-06-23 | 2017-08-22 | 昆山欣谷微电子材料有限公司 | For removing the photoresist lift off liquid containing back chip metalization layer |
| CN107085357A (en) * | 2017-06-23 | 2017-08-22 | 昆山欣谷微电子材料有限公司 | A kind of photoresist lift off liquid |
| CN115318717A (en) * | 2022-08-05 | 2022-11-11 | 华虹半导体(无锡)有限公司 | Method for removing residual glue on heating plate PI of baking unit |
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Application publication date: 20110615 |