CN108255027A - A kind of photoresist cleaning solution - Google Patents

A kind of photoresist cleaning solution Download PDF

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Publication number
CN108255027A
CN108255027A CN201611231304.4A CN201611231304A CN108255027A CN 108255027 A CN108255027 A CN 108255027A CN 201611231304 A CN201611231304 A CN 201611231304A CN 108255027 A CN108255027 A CN 108255027A
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China
Prior art keywords
cleaning solution
photoresist cleaning
photoresist
hydramine
hydroxide
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Granted
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CN201611231304.4A
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CN108255027B (en
Inventor
孙广胜
刘兵
徐海玉
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Anji Microelectronics Shanghai Co Ltd
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Anji Microelectronics Shanghai Co Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Detergent Compositions (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The present invention relates to a kind of photoresist cleaning solution, concentration includes following components by mass percentage:I. quaternary ammonium hydroxide 0.1 6%;Ii. hydramine 0.1 10%;Iii. polyalcohol 0.2~50%;Iv. phenolic compound 0.1~5%;V. surplus is organic solvent.Not silane-containing in the cleaning solution of the present invention, it is while the photoresist residue on effectively removing wafer, for the base material such as no corrosions such as metallic copper, aluminium, titanium, tungsten, gold, there is removal ability to copper oxide, have a good application prospect in fields such as cleaning semiconductor chips.

Description

A kind of photoresist cleaning solution
Technical field
The present invention relates to field of semiconductor fabrication processes more particularly to a kind of photoresist cleaning solutions.
Background technology
In general, in semiconductor fabrication process, need to form the mask of photoresist on the surface of some materials, and pass through Exposure technology carries out the transfer of figure.But after the figure needed, before carrying out next process, need to peel off Remaining photoresist.Moreover, often requiring that in this process unwanted photoresist is removed completely, while cannot corrode any Base material.
At present, photoresist cleaning solution is mainly made of polar organic solvent, highly basic and/or water etc., by by semiconductor die Piece immerses in cleaning solution or rinses semiconductor wafer using cleaning solution, removes the photoresist of semiconductor die on piece.Such as JP1998239865 discloses a kind of cleaning solution of Aquo System, and composition is tetramethylammonium hydroxide (TMAH), dimethyl Asia Sulfone (DMSO), 1,3 '-dimethyl -2- imidazolidinones (DMI) and water, chip is immersed in the cleaning solution, is removed at 50~100 DEG C 20 μm or more of photoresist on metal and dielectric substrate is removed, it is slightly higher to the corrosion of semiconductor wafer substrate, and cannot be complete The photoresist of full removal semiconductor die on piece, cleaning ability is insufficient;US5091103 discloses N-Methyl pyrrolidone, 1,2- third The cleaning solution of glycol and tetramethylammonium hydroxide removes the photoetching through high temperature baked (hard bake) at 105~125 DEG C Glue, it is characterized in that it is high not contain water, operation temperature, once cleaning solution is mixed into water, to the corrosion rate of metallic aluminium and copper on It rises, which can be suitable for the cleaning of positive photoresist and negative photoresist simultaneously.
Moreover, with the fast development of semiconductor, the development of particularly convex ball encapsulation field, to the clear of photoetching glue residue Requirement also corresponding raising is washed, number of pins (I/O) is more and more mainly on unit area, and the removal of photoresist also becomes more next It is more difficult.So as to which it is that such photoresist cleaning solution makes great efforts improved privileged direction to find more efficiently photoresist cleaning solution.
In general, the cleaning ability for improving alkaline photoresist cleaning solution is mainly by improving the alkalinity of cleaning solution, choosing It is realized with more efficiently dicyandiamide solution, raising operation temperature and extension operating time several aspects.But improve cleaning The alkalinity and operation temperature and extension scavenging period of liquid often increase to corrosion of metal.In general, it is encapsulated in salient point The metal that field is related to is mainly four kinds of silver, tin, lead and copper metals.Recently, in order to further reduce the cost raising yield, some Packaging and testing manufacturer, which starts requirement photoresist cleaning solution, can also further suppress the corrosion of metallic aluminium.Therefore, it finds more effective It is that such photoresist cleaning solution makes great efforts improved preferential side to inhibit metal erosion suppressing method and efficient photoresist removal ability To.
Invention content
The purpose of the invention is to provide a kind of cleaning solution and its composition for effectively removing photoresist residue.The cleaning Liquid is while the photoresist residue on effectively removing wafer, for base material such as metallic copper, aluminium, titanium, tungsten, gold etc. substantially without corruption Erosion, has a good application prospect in fields such as cleaning semiconductor chips.
The present invention provides a kind of photoresist cleaning solution, and concentration includes following components by mass percentage:
I. quaternary ammonium hydroxide 0.1-6%;It is preferred that 0.5-3.5%;
Ii. hydramine 0.1-10%;It is preferred that 0.1-3%;
Iii. polyalcohol 0.2~50%;It is preferred that 1-30%;
Iv. phenolic compound 0.1~5%;It is preferred that 0.3-2%;
V. surplus is organic solvent.
Wherein, the quaternary ammonium hydroxide is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl hydroxide It is one or more in ammonium, tetrabutylammonium hydroxide, cetyltrimethylammonium hydroxide and benzyltrimethylammonium hydroxide.
Wherein, the hydramine is selected from monoethanolamine, N- methylethanolamines, diethanol amine, triethanolamine, isopropanolamine, second Base diethanol amine, N, it is one or more in N- diethyl ethylene diamines, N- (2- amino-ethyls) ethanol amine and diglycolamine.It is preferred that Ground, the hydramine are selected from monoethanolamine and/or triethanolamine.
Wherein, the polyalcohol is selected from ethylene glycol, 1,2-PD, 1,4-butanediol, neopentyl glycol, two contracting diethyls two Alcohol, glycerine, threose, arabinose, xylose, ribose, ribulose, xylulose, glucose, mannose, galactolipin, tower lattice Sugar, allose, altrose, idose, talose, sorbose, psicose, fructose, threitol, erythrite, ribitol, I It is one or more in primary sugar alcohol, xylitol, talitol, sorbierite, mannitol, iditol and galactitol.
Wherein, the phenolic compound be selected from phenol, cresols, o-cresol, p-cresol, m-cresol, hydroquinone, 1,3,5-trihydroxybenzene, hydroxyquinol, catechol, resorcinol, pyrogallol, alpha-Naphthol, betanaphthol, amino phenols, adjacent pin base phenol, Between nitro base phenol, to pin base phenol, anthrol.
Wherein, the organic solvent is in sulfoxide, sulfone, imidazolidinone, pyrrolidones, imidazolone, amide and alcohol ether It is one or more.Preferably, the sulfoxide is one or more in dimethyl sulfoxide (DMSO) and first ethyl-sulfoxide;The sulfone choosing From one or more in methyl sulfone, sulfolane;The imidazolidinone is selected from 2- imidazolidinones and 1,3- dimethyl -2- imidazolidines It is one or more in ketone;The one kind or more of the pyrrolidones in N-Methyl pyrrolidone and N- cyclohexyl pyrrolidones Kind;The imidazolone is 1,3- dimethyl-2-imidazolinones;The amide is selected from dimethylformamide and dimethylacetylamide In it is one or more;The alcohol ether is one or more in diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether.
Compared with prior art, positive effect of the invention is:Not silane-containing in the cleaning solution of the present invention, this The cleaning solution of invention is while the photoresist residue on effectively removing wafer, for base material such as metallic copper, aluminium, titanium, tungsten, gold etc. No corrosion has removal ability to copper oxide.It has a good application prospect in fields such as cleaning semiconductor chips.
Specific embodiment
With reference to specific embodiment and the comparative example superiority that the present invention is further explained, wherein, the present invention is used to be tried Agent and raw material are commercially available.By mentioned component, simply uniformly mixing can be prepared by the cleaning solution of the present invention.
The component and its content of 1 embodiment of table and comparative example
Effect example
In order to further investigate the cleaning situation of the based cleaning liquid, present invention employs following technological means:I.e. by wafer Microballoon implantation technique convexity ball it is electroplated after the completion of the wafer containing photoresist residue, respectively immerse cleaning solution at 25 DEG C extremely It is vibrated 30~120 minutes with about 60 revs/min of vibration frequency using constant temperature oscillator at 80 DEG C, High Purity Nitrogen is then used after rinsing Air-blowing is done.The cleaning performance and cleaning solution of photoresist residue are as shown in table 2 to the corrosion condition of chip.
The wafer cleaning situation of 2 section Example of table
The wafer cleaning situation of 3 part comparative example of table
From table 2 it can be seen that the cleaning solution of the present invention is on the convex ball after the completion of being electroplated in wafer microballoon implantation technique Wafer containing photoresist residue has good cleaning performance, and use temperature range is wide.
Comparative example 11-1 in the comparison of embodiment 11 with, as can be seen that in embodiment 11, selecting C2-C3 and C4- from table 3 The polyalcohol compounding of C6, content is identical with the content of polyalcohol single in comparative example 11-1, and (comparative example 11-1 only contains C4-C6 Polyalcohol does not add in C2-C3 polyalcohols), but comparative example 11-1 inhibits no embodiment 11 good the corrosion of metallic aluminium and copper, therefore Comparative example 11-1 is conducive to the inhibition of metallic aluminium and copper corrosion with the addition of polyalcohol that embodiment 11 demonstrates C2-C3.It is similar Ground, C4-C6 polyalcohols do not add in comparative example 11-2, on the polyalcohol for the amount not added in all being added C2-C3, other groups Dividing the same and operating condition under the same conditions, the addition for demonstrating C4-C6 is conducive to the inhibition of metallic aluminium and copper corrosion, although Both comparative example 11-1 and 11-2 do not find out there is significant difference with embodiment 11 to the cleaning of photoresist, and the removal of copper oxide does not have There is significant difference, but comparative example 11-1 and 11-2 inhibits good without embodiment 11 to the corrosion of metallic aluminium and copper.By above-mentioned right Ratio 11-1,11-2 and the effect example of embodiment 11 are it is found that C2-C3 polyalcohols and C4-C6 polyalcohols exist between the two The effect of compounding, the two match the corrosion that can preferably inhibit metallic copper and aluminium.Pair of comparative example 11-3 and embodiment 11 Than, demonstrate C2-C3 and C4-C6 polyalcohol be all not added in the case of, copper oxide wafer on more serious to corrosion of metal It remains.
Embodiment 7 can be seen that with comparative example 7-1,7-2,7-3 and not add in polyalcohol in comparative example 7-1, metal erosion speed Rate rises, and cleans no influence, copper oxide remains on a small quantity.Phenolic compound is not added in comparative example 7-2, on rate of metal corrosion It rises, cleans no influence, copper oxide remains on a small quantity.Polyalcohol and phenolic compound do not add in comparative example 7-3, metal erosion speed Rate rises, and cleans no influence, the more residual of copper oxide.Being used in compounding for polyalcohol and phenolic compound, can effectively remove wafer On copper oxide.
To sum up, positive effect of the invention is:The cleaning solution of the present invention is under similarity condition, in certain concentration In the range of, by being used in compounding polyalcohol and phenolic compound, it can more effectively remove photoetching glue residue;Simultaneously for The no corrosions such as base material such as metallic aluminium and copper, especially have copper oxide removing ability.In fields such as cleaning semiconductor chips It has a good application prospect.
It should be noted that the embodiment of the present invention has preferable implementation, and not the present invention is made any type of Limitation, any one skilled in the art change or are modified to possibly also with the technology contents of the disclosure above equivalent effective Embodiment, as long as without departing from the content of technical solution of the present invention, what technical spirit according to the present invention made above example Any modification or equivalent variations and modification, in the range of still falling within technical solution of the present invention.

Claims (9)

1. a kind of photoresist cleaning solution, which is characterized in that concentration is included with the following group the photoresist cleaning solution by mass percentage Point:
I. quaternary ammonium hydroxide 0.1-6%;
Ii. hydramine 0.1-10%;
Iii. polyalcohol 0.2~50%;
Iv. phenolic compound 0.1~5%;
V. surplus is organic solvent.
2. photoresist cleaning solution as described in claim 1, which is characterized in that the quaternary ammonium hydroxide is selected from tetramethyl hydrogen-oxygen Change ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, cetyltrimethylammonium hydroxide and benzyl It is one or more in base trimethylammonium hydroxide.
3. photoresist cleaning solution as described in claim 1, which is characterized in that the hydramine is selected from monoethanolamine, N- methyl second Hydramine, diethanol amine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, N- diethyl ethylene diamines, N- (2- amino-ethyls) It is one or more in ethanol amine and diglycolamine.
4. photoresist cleaning solution as claimed in claim 3, which is characterized in that the hydramine is selected from monoethanolamine and/or three second Hydramine.
5. photoresist cleaning solution as described in claim 1, which is characterized in that the polyalcohol is selected from ethylene glycol, 1,2- the third two Alcohol, 1,4-butanediol, neopentyl glycol, Diethylene Glycol, glycerine, threose, arabinose, xylose, ribose, ribulose, Xylulose, glucose, mannose, galactolipin, Tagatose, allose, altrose, idose, talose, sorbose, A Luo ketone Sugar, fructose, threitol, erythrite, ribitol, arabite, xylitol, talitol, sorbierite, mannitol, idose It is one or more in alcohol and galactitol.
6. photoresist cleaning solution as described in claim 1, which is characterized in that the phenolic compound is selected from phenol, cresols, neighbour Cresols, p-cresol, m-cresol, hydroquinone, 1,3,5-trihydroxybenzene, hydroxyquinol, catechol, even resorcinol, benzene three Phenol, alpha-Naphthol, betanaphthol, amino phenols, neighbour sell base phenol, nitro base phenol, to pin base phenol, anthrol.
7. photoresist cleaning solution as described in claim 1, which is characterized in that the organic solvent is selected from sulfoxide, sulfone, imidazolidine It is one or more in ketone, pyrrolidones, imidazolone, amide and alcohol ether.
8. photoresist cleaning solution as claimed in claim 7, which is characterized in that the sulfoxide is selected from dimethyl sulfoxide (DMSO) and the first and second bases It is one or more in sulfoxide;The sulfone is one or more in methyl sulfone, sulfolane;The imidazolidinone is selected from 2- miaows It is one or more in oxazolidone and 1,3- dimethyl -2- imidazolidinones;The pyrrolidones be selected from N-Methyl pyrrolidone and It is one or more in N- cyclohexyl pyrrolidones;The imidazolone is 1,3- dimethyl-2-imidazolinones;The amide choosing From one or more in dimethylformamide and dimethylacetylamide;The alcohol ether is selected from diethylene glycol monobutyl ether and dipropyl two It is one or more in alcohol monomethyl ether.
9. the photoresist cleaning solution as described in claim 1-8 is any, which is characterized in that the quality hundred of the quaternary ammonium hydroxide Point specific concentration is 0.5-3.5%, and the mass percent concentration of the hydramine is 0.1-3%, the mass percent of the polyalcohol A concentration of 1-30%, the mass percent concentration of the phenolic compound is 0.3-2%.
CN201611231304.4A 2016-12-28 2016-12-28 Photoresist cleaning solution Active CN108255027B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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CN104327587A (en) * 2014-10-17 2015-02-04 青岛克立克信息技术有限公司 Stable fast cleaning agent
CN104678719A (en) * 2013-11-28 2015-06-03 安集微电子科技(上海)有限公司 Photoresist cleaning liquid with extremely-low corrosion to metals
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JP2007072325A (en) * 2005-09-08 2007-03-22 Mitsui Mining & Smelting Co Ltd Method for manufacturing display device
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Publication number Priority date Publication date Assignee Title
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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