CN104570628A - Low-metal-etching photoresist stripping liquid and application thereof - Google Patents

Low-metal-etching photoresist stripping liquid and application thereof Download PDF

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Publication number
CN104570628A
CN104570628A CN201310513168.8A CN201310513168A CN104570628A CN 104570628 A CN104570628 A CN 104570628A CN 201310513168 A CN201310513168 A CN 201310513168A CN 104570628 A CN104570628 A CN 104570628A
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liquid
photoresist lift
silane
photoresist
methyl
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CN104570628B (en
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刘江华
刘兵
彭洪修
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Anji Microelectronics Shanghai Co Ltd
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Anji Microelectronics Shanghai Co Ltd
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Abstract

The invention discloses low-metal-etching photoresist stripping liquid and application thereof. The low-metal-etching photoresist stripping liquid the following components: (a) quaternary amine hydroxide, (b) alcohol amine, (c) a solvent, (d) a star copolymer with pigment adsorption groups and (e) silane with a specific structure. According to the low-metal-etching photoresist stripping liquid, the corrosion rate to metal can be effectively reduced, and particularly metallic aluminum are hardly corroded; meanwhile, photoresist and residues of the photoresist on a wafer can be effectively removed, so that the low-metal-etching photoresist stripping liquid has a good application prospect.

Description

The photoresist lift off liquid of the low etching of a kind of metal and application thereof
Technical field
The invention discloses photoresist lift off liquid and the application thereof of the low etching of a kind of metal.
Background technology
In semiconductor components and devices manufacture 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 the photoresist that removing is residual.Require to remove unwanted photoresist completely in the process that this photoresist is removed, any base material can not be corroded simultaneously, especially strictly control the corrosion of metal aluminum bronze.
At present, photoresist lift off liquid, primarily of compositions such as polar organic solvent, highly basic and/or water, by immersing in stripper by semiconductor wafer or utilizing stripper to rinse semiconductor wafer, removes the photoresist on semiconductor wafer.As JP1998239865 discloses a kind of stripper 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 stripper, 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 stripper by potassium hydroxide (KOH), alkylene glycol monoalkyl ether, soluble fluoride and water etc. again, is immersed by wafer in this stripper, removes the photoresist in metal and dielectric substrate at 40 ~ 90 DEG C.The corrosion of this stripper to semiconductor wafer substrate is higher.Such as WO2006/056298A1 utilizes by Tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO) (DMSO) again, and ethylene glycol (EG) and water form alkaline stripper, for cleaning the photoresist of micron thickness, simultaneously to metallic copper no corrosion.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 lift off liquid is the privileged direction that such photoresist lift off liquid makes great efforts to improve.Generally speaking, the cleansing power improving alkaline photoresist lift off liquid mainly by improve stripper alkalescence, select more efficiently dicyandiamide solution, improve operating temperature and extend that running time several aspect realizes.But improving the alkalescence of stripper and operating temperature and extending scavenging period often increases corrosion of metal.Under normal circumstances, if master metal silver, tin, lead and the copper four kinds of metals related in salient point encapsulation field.In recent years, improve yield to reduce costs further, some packaging and testing manufacturers start the corrosion that requirement photoresist lift off liquid also can suppress metallic aluminium further simultaneously.In order to adapt to new situation, a class photoresist removal ability must be developed strong, simultaneously also can to the substantially free from corrosion stripper of metallic aluminium.
Summary of the invention
The object of the invention is to provide a kind of stripper and the composition thereof of effectively removing photoetching glue residue.This stripper is while effectively removing the photoetching glue residue on wafer, by a kind of star copolymer with pigment adsorption group and containing the silane of ad hoc structure composite to base material as the no corrosion such as metallic aluminium, copper, can with the direct rinsing of water and due to larger corrosion can not be caused to metal especially aluminium after to wafer cleaning.Therefore this novel stripper has a good application prospect at microelectronics such as metal cleaning and cleaning semiconductor chips.
This novel stripper contains: a) quaternary ammonium hydroxide (b) hydramine (c) solvent (d) is with the star copolymer of pigment adsorption group, it is characterized in that the silane also containing ad hoc structure.
I. quaternary ammonium hydroxide 0.1-8%; Preferred 0.5-6%
Ii. hydramine 0.1-20%, preferred 0.5-10%
Iii. the silane 0.1 ~ 3% of ad hoc structure, preferred 0.05-1%
Iv. with the star copolymer 0.01 ~ 5% of pigment adsorption group, preferred 0.05-3%
V. surplus is organic solvent (64%-99.69%).
Above-mentioned content is mass percentage content; The stripper of this removal photoetching glue residue does not contain azanol, fluoride, oxygenant, and abrasive grains.
In the present invention, this 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, this hydramine is preferably one or more in monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, N-diethyl ethanolamine, N-(2-amino-ethyl) monoethanolamine and diglycolamine.One in preferred monoethanolamine, triethanolamine or its potpourri.
In the present invention, this silane coupling agent structural formula is as follows:
Wherein X is the one in reactive group acyloxy, hydroxyl, sulfydryl, glycidyl ether oxygen base, alkoxy, and n is 1-3, Y1, Y2 and Y3 is methyl or hydrolyzable groups, and hydrolyzable groups is methoxyl, ethoxy, acyloxy, butoxy isopropoxy.Wherein at least independently contain 2 hydrolyzable groups in Y1, Y2 and Y3.The silane used is preferably γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen ylmethyl dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, γ-glycydoxy methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl, γ-methacryloxypropyl three isopropoxy silane, γ-methacryloxymethyl trimethoxy silane, γ-methacryloxymethyl triethoxysilane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloyloxypropyl methyl dimethoxysilane, acryloyloxymethyl trimethoxy silane, 3-seven fluorine isopropoxide propyl trimethoxy silane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, thiopurine methyltransferase methyldiethoxysilane, mercapto hydroxypropyl methyl dimethoxysilane, 3-mercapto propyl group three butoxy silane, 2-mercaptoethyl triethoxysilane, 3-Octanoylthio propyl-triethoxysilicane, two-[3-(triethoxysilicane) propyl group]-disulfide, two-[3-(triethoxysilicane) propyl group]-tetrasulfide, benzoyloxy propyl trimethoxy silicane, acetoxy-methyl trimethoxy silane, Acetoxvethyl trimethoxy silane, acetoxy-methyl triethoxysilane, acetyloxypropyl trimethoxy silane, acetoxy-methyl triethoxysilane, 3-trifluoroacetyl oxygen base propyl trimethoxy silicane, one or more in methylol triethoxysilane.
In the present invention, the described star copolymer with pigment adsorption group refers to the star-type polymer of the pigment affinity groups containing hydroxyl, amino or carboxyl.The so-called star copolymer with pigment adsorption group is preferably the polyacrylate star copolymer containing pigment affinity groups in the present invention; The so-called polyacrylate star-type polymer with pigment adsorption group refers to the polyacrylate star copolymer containing hydroxyl, amino etc.Namely use acrylic ester monomer, as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, maleic anhydride, the star copolymer of synthesis such as (methyl) hydroxy-ethyl acrylate or acrylamide monomers etc.; Or the star copolymer of other vinyl monomer and above-mentioned monomer.Be preferably the binary star copolymer of polyacrylic acid star copolymer, styrene and hydroxy-ethyl acrylate, acrylic acid, maleic anhydride and the star-like copolymerization system of polystyrene ternary, the bipolymer of the binary star copolymer of methyl acrylate and hydroxy-ethyl acrylate, acrylic acid and maleic acid, acrylic acid with and the binary star copolymer of hydroxy-ethyl acrylate, acrylic acid and butyl acrylate and acrylamide ternary star copolymer.
In the present invention, this organic solvent is preferably one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and alcohol ether; This sulfoxide is preferably one or more in dimethyl sulfoxide (DMSO) and first ethyl-sulfoxide; This sulfone is preferably one or more in methyl sulfone, sulfolane; This imidazolidinone is preferably one or more in 2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone; This pyrrolidone is preferably one or more in 1-METHYLPYRROLIDONE and N-cyclohexyl pyrrolidone; This imidazolone is preferably DMI; This acid amides is preferably one or more in dimethyl formamide and dimethyl acetamide; This alcohol ether is preferably one or more in diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether.
Stripper in the present invention, can photoetching glue residue at 25 DEG C to 80 DEG C on cleaning wafer.Concrete grammar is as follows: immersed by the wafer containing photoetching glue residue in the stripper 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: stripper of the present invention is while effectively removing the photoetching glue residue on wafer, for base material as the no corrosion such as metallic aluminium, copper, with the direct rinsing of water and due to larger corrosion can not be caused to metal especially aluminium, the action pane of wafer rinsing can be added after to wafer cleaning.Therefore this novel stripper has a good application prospect at microelectronics such as metal cleaning and cleaning semiconductor chips.
Agents useful for same of the present invention and raw material are all commercially.Stripper 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 and comparative example cleaning fluid and content
Effect example
In order to investigate the cleaning situation of such stripper further, present invention employs following technological means: implant the wafer containing photoetching glue residue after technique convexity ball has been electroplated by wafer microballoon, immerse respectively in stripper 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 photoetching glue residue and the corrosion condition of stripper to wafer as shown in table 2.Wherein embodiment 5(1), the formula of (2) is identical with the formula in embodiment 5, but implementation condition (such as cleaning temperature) is different.
The wafer cleaning situation of table 2 section Example and comparative example
Embodiment Cleaning temperature (DEG C) Scavenging period (min) Metallic aluminium corrosion condition Metallic copper corrosion condition Wafer cleaning result
2 25 150
3 40 120
4 50 80
5(1) 45 60
5(2) 70 30
7 30 110
9 35 90
10 80 80
12 55 50
13 65 40
14 80 30
15 60 30
16 50 70
16 75 30
17 65 80
Comparative example 1 45 60
Comparative example 2 45 60
Comparative example 3 45 60
Comparative example 4 70 60 ×
Comparative example 5 70 60 ×
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, stripper 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, have good inhibiting effect to the corrosion of metallic aluminium and copper, serviceability temperature scope is wide simultaneously.As can be seen from comparative example 1 and embodiment 5 (1): under the condition that other component is the same and operating conditions is identical, in embodiment 5 (1), the silane of described structure can be composite with star-type polymer, thus can be good at the corrosion suppressing metallic aluminium and copper, and the silane containing alkyl structure described in comparative example 1 can not be composite with the polymkeric substance of star topology, thus similar effect cannot be reached.
As can be seen from comparative example 2 and embodiment 5 (1): under the condition that other component is the same and operating conditions is identical, due to can not be well composite with star-shape polymer product containing amino structure silane described in comparative example 2, well metal erosion can not be suppressed equally.
From the contrast of comparative example 3 and comparative example 2, although can find out that the content increasing amino structure silane can suppress metal erosion, the increase of such silane contents simultaneously can impact cleaning, and remaining photoresist is increased.
Compared with 5 (2), when identical with consumption at a higher temperature, the corrosion of comparative example 4 and comparative example 5 pairs of aluminium is comparatively serious, also has impact to the cleaning of photoresist simultaneously.To sum up, describe this star copolymer with pigment adsorption group and jointly deposit the corrosion control effect that can play preferably in case metallic aluminium at the silane with the application's ad hoc structure.Demonstrate further by with the star copolymer of pigment adsorption group and the silane of a small amount of ad hoc structure composite, just can more efficiently control corrosion of metal, and efficient photoresist cleansing power can be reached.
To sum up, positive progressive effect of the present invention is: stripper of the present invention by with the star copolymer of pigment adsorption group and the silane of a small amount of described structure composite to base material as the no corrosion such as metallic aluminium and copper; Effectively can remove photoetching glue residue simultaneously, 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 (21)

1. a photoresist lift off liquid for the low etching of metal, comprises quaternary ammonium hydroxide, hydramine, solvent, with the radial copolymer of pigment adsorption group, it is characterized in that, also contains the silane of having structure one or more:
Wherein X is the one in reactive group acyloxy, hydroxyl, sulfydryl, glycidyl ether oxygen base, alkoxy, and n is 1-3, Y 1, Y 2and Y 3for methyl or hydrolyzable groups, wherein, described hydrolyzable groups is methoxyl, ethoxy, acyloxy, butoxy, isopropoxy, and Y 1, Y 2and Y 3in at least independently containing 2 described hydrolyzable groups.
2. photoresist lift off liquid as claimed in claim 1, it is characterized in that, described silane is γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen ylmethyl dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, γ-glycydoxy methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl, γ-methacryloxymethyl trimethoxy silane, γ-methacryloxymethyl triethoxysilane, γ-methacryloxymethyl three isopropoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloyloxypropyl methyl dimethoxysilane, acryloyloxymethyl trimethoxy silane, 3-seven fluorine isopropoxide propyl trimethoxy silane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, thiopurine methyltransferase methyldiethoxysilane, mercapto hydroxypropyl methyl dimethoxysilane, 3-mercapto propyl group three butoxy silane, 2-mercaptoethyl triethoxysilane, 3-Octanoylthio propyl-triethoxysilicane, two-[3-(triethoxysilicane) propyl group]-disulfide, two-[3-(triethoxysilicane) propyl group]-tetrasulfide, benzoyloxy propyl trimethoxy silicane, acetoxy-methyl trimethoxy silane, Acetoxvethyl trimethoxy silane, acetoxy-methyl triethoxysilane, acetyloxypropyl trimethoxy silane, acetoxy-methyl triethoxysilane, 3-trifluoroacetyl oxygen base propyl trimethoxy silicane, one or more in methylol triethoxysilane.
3. photoresist lift off liquid as claimed in claim 1, it is characterized in that, the content of described silane is mass percent 0.1 ~ 3%.
4. photoresist lift off liquid as claimed in claim 3, it is characterized in that, the content of described silane is mass percent 0.05-1%.
5. photoresist lift off liquid as claimed in claim 1, it is characterized in that, described quaternary ammonium hydroxide is one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cetyltrimethylammonium hydroxide and benzyltrimethylammonium hydroxide.
6. photoresist lift off liquid as claimed in claim 1, it is characterized in that, the content of quaternary ammonium hydroxide is mass percent 0.1-8%.
7. photoresist lift off liquid as claimed in claim 6, it is characterized in that, the content of quaternary ammonium hydroxide is mass percent 0.5-6%.
8. photoresist lift off liquid as claimed in claim 1, it is characterized in that, described hydramine is one or more in monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, N-diethyl ethanolamine, N-(2-amino-ethyl) monoethanolamine and diglycolamine.
9. photoresist lift off liquid as claimed in claim 1, it is characterized in that, described alcohol amine content is 0.1-20%.
10. photoresist lift off liquid as claimed in claim 9, it is characterized in that, described alcohol amine content is mass percent 0.5-10%.
11. photoresist lift off liquid as claimed in claim 1, is characterized in that, the described radial copolymer with pigment adsorption group is the star polymer of the pigment affinity groups containing hydroxyl, amino or carboxyl.
12. photoresist lift off liquid as claimed in claim 11, is characterized in that, the described radial copolymer with pigment adsorption group is polyacrylate radial copolymer.
13. photoresist lift off liquid as claimed in claim 12, is characterized in that, the radial copolymer that the described radial copolymer with pigment adsorption group is acrylic ester monomer and/or synthesizes with vinyl monomer.
14. photoresist lift off liquid as claimed in claim 13, it is characterized in that, the described radial copolymer with pigment adsorption group be the binary radial copolymer of the binary radial copolymer of polyacrylic acid radial copolymer, styrene and hydroxy-ethyl acrylate, methyl acrylate and hydroxy-ethyl acrylate, acrylic acid and and the binary radial copolymer of hydroxy-ethyl acrylate or the ternary radial copolymer of acrylic acid and butyl acrylate and acrylamide in one or more.
15. photoresist lift off liquid as claimed in claim 1, is characterized in that, the content of the described star copolymer with pigment adsorption group is mass percent 0.01 ~ 5%.
16. photoresist lift off liquid as claimed in claim 15, is characterized in that, the content of the described star copolymer with pigment adsorption group is mass percent 0.05-3%.
17. photoresist lift off liquid as claimed in claim 1, is characterized in that, described organic solvent is one or more in sulfoxide, sulfone, imidazolidinone, pyrrolidone, imidazolone, acid amides and alcohol ether.
18. photoresist lift off liquid as claimed in claim 17, 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 is 2-imidazolidinone and/or 1,3-dimethyl-2-imidazolidinone; Described pyrrolidone is 1-METHYLPYRROLIDONE and/or N-cyclohexyl pyrrolidone; Described imidazolone is DMI; Described acid amides is dimethyl formamide and/or dimethyl acetamide; Described alcohol ether is diethylene glycol monobutyl ether and/or dipropylene glycol monomethyl ether.
19. photoresist lift off liquid as claimed in claim 1, is characterized in that, the content of described organic solvent is mass percent 64%-99.69%.
The photoresist of 20. 1 kinds of photoresist lift off liquid as described in any one of claim 1-19 on removal wafer and the application of residue thereof.
The photoresist of 21. 1 kinds of silane as described in any one of claim 1-19 on removal wafer and the application of residue thereof.
CN201310513168.8A 2013-10-25 2013-10-25 Metal low-etching photoresist stripping liquid and application thereof Active CN104570628B (en)

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Cited By (1)

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CN112540515A (en) * 2020-12-16 2021-03-23 江苏艾森半导体材料股份有限公司 Photoresist stripping liquid and preparation method and application thereof

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CN102566331A (en) * 2010-12-21 2012-07-11 安集微电子(上海)有限公司 Cleaning fluid for thick-film photoresist

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CN112540515A (en) * 2020-12-16 2021-03-23 江苏艾森半导体材料股份有限公司 Photoresist stripping liquid and preparation method and application thereof
CN112540515B (en) * 2020-12-16 2023-11-21 江苏艾森半导体材料股份有限公司 Photoresist photoresist stripping solution and preparation method and application thereof

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