CN104614954A - Photoresist-removing water-based stripping liquid composition - Google Patents
Photoresist-removing water-based stripping liquid composition Download PDFInfo
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- CN104614954A CN104614954A CN201510015034.2A CN201510015034A CN104614954A CN 104614954 A CN104614954 A CN 104614954A CN 201510015034 A CN201510015034 A CN 201510015034A CN 104614954 A CN104614954 A CN 104614954A
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Abstract
The invention relates to a photoresist stripping liquid composition which is mainly used for removing unexposed photoresist in the manufacturing process of a semiconductor device. The photoresist stripping liquid comprises the following components in percentage by mass: 20-70% of a polar solvent, 5-50% of an organic amine compound, 0.01-5% of a surfactant, 0.01-5% of a corrosion inhibitor and 10-60% of deionized water. In the process, the unexposed photoresist in the semiconductor device is removed at a low temperature, corrosion to metal of the semiconductor device is minimized, and a PI bottom film is not swelled.
Description
Technical field
The present invention relates to a kind of water system remover composition for the photoresist in semiconductor fabrication process, this stripper can effectively remove unexposed photoresist, and does not produce corrosion to semiconductor device substrates, and does not produce swelling to PI counterdie.
Background technology:
In large scale integrated circuit manufacture process, use much photoresist lift off liquid as the detersive on production line.Photoresist film is through high-temperature baking in the fabrication process, and deposition on the wafer substrates, and then is imaged as circuit pattern through exposure imaging.After the etch process, unexposed photoresist must remove from wafer protection district, thus can carry out the operation of later process.
In a manufacturing process, owing to requiring that photoresist and substrate have good adhesiveness, usually carry out high-temperature baking, make the difficulty removing remaining photoresist lift off liquid become large like this, there is the problem of metal wire corrosion simultaneously.
The alkali contained in general conventional water system stripper is inorganic alkali solution, as: 2 ~ 6% aqueous solution of NaOH, KOH, or ammoniacal liquor etc.But there is following shortcoming in it simultaneously: one attacks the metal such as copper, aluminium, makes metal wire generation corrosion cracking; When two NaOH, KOH do stripper use, although photoresist can be made to peel off from substrate, can not play good dissolution, the film slag produced after peeling off is excessive, is difficult to filter, easy blocking pipeline when recycling.As mentioned based on inorganic NaOH in Chinese patent CN 101071278, take benzotriazole as the stripper of corrosion inhibiter, but corrosion as larger in A1, Cu etc. have to metal substrate under high temperature, highly basic effect.
In addition, the amine mainly one-level such as monoethanolamine or methylethanolamine or the secondary amine in the stripper of conventional organic system.But described one-level or secondary amine have that boiling point is low forms the labile shortcoming of partial volume, and through weight and composition after a period of time because changing, stripping ability is decayed thereupon, therefore there is high expensive, remove photoresist indifferent, later stage discarded stripper such as not easily to process at the shortcoming.Meanwhile, simple organic solvent or the low water system stripper of moisture produce swelling to PI bottom popular at present, and the yield producing substrate reduces, and even scraps.In addition, described one-level or secondary amine are comparatively large due to viscosity, need, with the rinsing of one rinsing liquid elder generation, then directly to wash, make troubles to production after stripping.
Common stripper is made up of organic solvent, alkali (organic base or inorganic base), adjuvant.In this system, organic solvent has important effect, not only can be used for dissolving the residual photoresist of substrate, also plays the vital role preventing stripper component from failing.Usually organic solvent used is DMSO, NMP, PGMEA, BDG etc., and solvent polarity is stronger, and the ability of dissolving photoresist is also larger.But simultaneously due to strong polarity, the alkali amalgamation easily and in system is deteriorated, and causes the life-span of stripper not long.This product adopts 1,3-dimethyl-2-imidazolone (DMI), because this product has higher lightning, character is gentle, particularly can there is good binding ability with hexamethyl phosphoramide, alkyl alcoholamine, not easily separated in water system, greatly improve stripper serviceable life at high temperature.The method that the present invention adopts many methyl phosphamide, organic primary amine and water to mix, makes primary amine all ionize in water, greatly improves boiling point and the stability of organic amine, and effectively reduce the viscosity of product, and do not need rinsing after a procedure.
1. in addition, because in the present invention, organic amine ionizes completely in water, make product have alkalescence, serious hidden danger is existed to semiconductor alloy substrate, need to add effective antiseptic.Patent WO 04059700 utilizes 2-mercaptobenzimidazole for corrosion inhibiter, but under the long-time condition of water system high temperature, is difficult to control to aluminium base corrosion.The anticolodal that the present invention uses is HEDP; stable complex compound can be formed in the metal surface such as copper, aluminium in water; through test; in 250 DEG C of situations, still there is corrosion inhibition; fine dissolubility and stability is had especially in water; inhibition can be played to the corrosivity of organic amine in the basic conditions simultaneously, compare gallic acid, alkynol class, catechol etc. and better protective effect is played to aluminium lamination.Patent CN1444103, described stripper, be made up of organic solvent, organic base, antiseptic, due under high temperature, organic solvent and organic base are in easy volatilization, but the speed difference owing to volatilizing, in use for some time, product component changes, and the stripper ability of removing photoresist is failed.Compare conventional stripper, surfactant tetrabutyl ammonium bromide is with the addition of in the present invention, in Chemical Manufacture, tetrabutyl ammonium bromide can as phase transfer catalyst, effectively can increase the amalgamation of each component, organic solvent, organic amine better can be merged in aqueous systems, azeotropic is respond well, effectively delays the die-away time of stripper.Meanwhile, tetrabutyl ammonium bromide, except the amalgamation with heterogeneous system, also has the effect of surfactant, can better immersion lithography glue in stripper, can make it easier and peel off from substrate, play the effect of peeling off promoter.
Summary of the invention:
The technical problem to be solved in the present invention is, for the deficiency of the existence of prior art, provide a kind of photoresist water system stripper, it has the premium properties of stripping photoresist from glass, common metal base material.Its amount of removing photoresist is large, cost is low, do not corrode aluminium and the metal substrate route containing aluminium, not swelling to PI counterdie.And the advantage such as this stripper component safety and stability, cheap, use safety, easily process.
For achieving the above object, the present invention comprises following content:
(A) content is the polar solvent of 20 ~ 70% (mass content)
(B) content is the organic amine compound of 5 ~ 50% (mass content)
(C) content is the surfactant of 0.01 ~ 5% (mass content)
(D) content is the corrosion inhibitor of 0.01 ~ 5% (mass content)
(E) content is the deionized water of 10 ~ 60% (mass content)
In the present invention, contained polar solvent is 1,3-dimethyl-2-imidazolone (DMI), dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE (NMP), DMF (DMF), N; N-dimethyl acetamide (DMAc), diethylene glycol monobutyl ether (BDG), Methoxypropylacetate (PGMEA), methyl cellosolve, ethylene glycol monoethyl ether, sulfolane one or more mixtures wherein form.And, when described polar solvent mass content below 20% or more than 70% time, contained organicly effectively can not remove the residual photoresist of substrate.
In the present invention, contained organic amine compound is HMPA, 3 methoxypropyl amine (MOPA), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine, isopropanolamine, 2-(2-aminoethylamino)-ethanol, N-methylethanolamine one or more mixtures wherein form.And, when described organic amine mass content is below 5%, because contained organic amine is very few, the photoresist that substrate is residual effectively can not be removed; But when organic amine mass content is more than 50%, because contained organic amine is too much, strengthening the corrosion of semiconductor alloy substrate, is also unaccommodated.
In the present invention, contained surfactant is tetrabutyl ammonium bromide.And, when described phase transfer catalyst mass content below 0.01% or more than 5% time, effectively can not play and delay stripper attenuation.
In the present invention, contained corrosion inhibitor is HEDP (HEDP).And, when described corrosion inhibitor mass content below 0.01% or more than 5% time, can not effectively suppress this invention product to the corrosion of semiconductor underlayer metal substrate.
In the present invention, contained deionized water is resistance >=16M Ω. deionized water.And, when described deionized water quality content below 10% or more than 60% time, can not effectively remove substrate and remain photoresist, lower than less than 10% time to PI produce swelling.
Embodiment
Preparation of samples:
Utilize CVD machine to be coated with PI layer on 4 inch silicon wafer, after oven dry, surface gasification-precipitation obtains
aluminium lamination.Positive light anti-etching agent (Suzhou Ruihong Electronic Chemical Product Co., Ltd. produces, and model is RZJ-304) is adopted to utilize spin coating mode to obtain thickness for 1.2um.By above-mentioned painting film prebake 30 minutes in the baking oven of 110 DEG C.Then utilize previously selected mask pattern to be placed on figure film to expose.Be placed in developer solution (Suzhou Ruihong Electronic Chemical Product Co., Ltd. produces, and model is RZX-3038) in leaching subsequently, develop in 60 seconds at 23 DEG C, through pure water rinsing.Finally by above-mentioned painting film in baking oven, shaping in 125 DEG C, 30 minutes.Like this, required sample has just been made.
Specific embodiment:
Mode below by embodiment further illustrates the present invention, not therefore by the present invention be limited among described scope of embodiments.
Stripper is tested:
1.. stripper attenuation test
The stripper of required configuration is adjusted according to quality ratio, filters in the filtrator of 0.2um.The content of the stripper gas chromatographic detection configured wherein organic base, then keeps this stripper 48 hours, finally checks the content of wherein organic base with high resolution gas chromatography, check the change of wherein organic base component at the temperature of 80 DEG C.
DMSO dimethyl sulfoxide (DMSO)
DMI 1,3-dimethyl-2-imidazolone
DMF DMF
BDG diethylene glycol monobutyl ether
HMPT hexamethyl phosphoramide
MEA monoethanolamine
HEDP HEDP
From upper table: in conventional stripper, organic base mass content in use prolongation in time can diminish to some extent, and this just drastically influence the performance of stripper.And after with the addition of surfactant tetrabutyl ammonium bromide, the content fluctuation of organic base is little, the aging of stripper has been delayed greatly.In above-mentioned chart, preferred organic amine is hexamethyl phosphoramide, because it has higher boiling point, not easily decomposes, and especially follows the compatibility of organic solvent and organic base, can maintain stripper at high temperature long stability.The stripper that simultaneously with the addition of surfactant there has also been more selection in the proportioning of organic solvent, and multi-solvents can be selected composite.
2. the configuration of stripper:
DMSO dimethyl sulfoxide (DMSO)
DMI 1,3-dimethyl-2-imidazolone
DMF DMF
BDG diethylene glycol monobutyl ether
HMPT hexamethyl phosphoramide
MEA monoethanolamine
HEDP HEDP
3. the aptitude tests of stripper;
Ready-made sample was soaked in joining in stripper of temperature 60 C, then clean and dry with deionized water rinsing.Then at SEM basis of microscopic observation lower-layer wiring corrosion condition, stripping clean level.Its result is as described in table one:
☆ peels off clean, and substrate noresidue photoresist, PI is without Swelling
Substrate is corrosion-free
★ peels off unclean, and have photoresist remaining, PI has swelling
■ substrate has corrosion, and PI floats glue
From the above mentioned, a kind of washing stripper removing residual photoresist in semiconductor technology of the present invention can be easy to and remove the residual solidification photoresist layer of dry method etch technology fast, after stripping, does not need to enter rinsing process, can directly wash.And when realizing removing photoresist, this stripper is to metal membrane material, and particularly aluminium and the wiring material containing aluminium have good protective effect, and do not affect basic unit PI, and application prospect is very good.
The present invention still has multiple concrete embodiment, and all employings are equal to replacement or equivalent transformation and all technical schemes of being formed, all drop within the scope of protection of present invention.
Claims (6)
1. the composition of the water system stripper of the removal photoresist of claim 1, comprises the polar solvent of 20 ~ 70 quality %.Wherein said polar solvent is that one or more are selected from the compound in following group: 1,3-dimethyl-2-imidazolone (DMI), dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE (NMP), DMF (DMF), N; N-dimethyl acetamide (DMAc), diethylene glycol monobutyl ether (BDG), Methoxypropylacetate (PGMEA), methyl cellosolve, ethylene glycol monoethyl ether, sulfolane.
2. the composition of the water system stripper of the removal photoresist of claim 1, comprises the organic amine compound of 5 ~ 50 quality %.Wherein said organic amine is that one or more are selected from the compound in following group: HMPA, 3 methoxypropyl amine (MOPA), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine, isopropanolamine, 2-(2-aminoethylamino)-ethanol, N-methylethanolamine.
3. the composition of the water system stripper of the removal photoresist of claim 1, comprises 0.01 ~ 5 quality % surfactant.Wherein said surfactant is tetrabutyl ammonium bromide.
4. the composition of the water system stripper of the removal photoresist of claim 1, comprises the corrosion inhibitor of 0.01 ~ 5 quality %.Wherein said corrosion inhibitor is HEDP (HEDP).
5. the composition of the water system stripper of the removal photoresist of claim 1, comprises the deionized water of 10 ~ 60 quality %.Described deionized water requires: resistance >=16M Ω.
6. the composition of the water system stripper of the removal photoresist of claim 1, described semiconductor device substrates comprises: aluminium and the metal line containing aluminium, PI counterdie.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105759573A (en) * | 2015-12-23 | 2016-07-13 | 苏州瑞红电子化学品有限公司 | Stripping liquid combination for removing residual photoresist after titanium nickel silver surface etching |
| CN107193187A (en) * | 2016-03-15 | 2017-09-22 | 东友精细化工有限公司 | Anticorrosive additive stripping liquid controlling composition |
| CN108919617A (en) * | 2018-07-31 | 2018-11-30 | 赵文应 | A kind of TFT-LCD negativity developer solution |
| CN109097201A (en) * | 2018-08-22 | 2018-12-28 | 江西宝盛半导体能源科技有限公司 | One kind removing glue and the preparation method and application thereof |
| CN109634071A (en) * | 2019-01-23 | 2019-04-16 | 福建省佑达环保材料有限公司 | A kind of aqua type photoresist lift off liquid for display panel and semiconductor field |
| CN110003996A (en) * | 2019-05-21 | 2019-07-12 | 广东剑鑫科技股份有限公司 | A kind of soak and preparation method thereof and application method |
| CN110441997A (en) * | 2019-08-19 | 2019-11-12 | 江阴江化微电子材料股份有限公司 | A kind of improved environmentally friendly water system photoresist lift off liquid |
| CN112680287A (en) * | 2020-12-22 | 2021-04-20 | 青岛科金电子材料有限公司 | Glue-removing and softening integrated low-temperature deburring liquid for surface-mounted diodes |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105759573A (en) * | 2015-12-23 | 2016-07-13 | 苏州瑞红电子化学品有限公司 | Stripping liquid combination for removing residual photoresist after titanium nickel silver surface etching |
| CN107193187A (en) * | 2016-03-15 | 2017-09-22 | 东友精细化工有限公司 | Anticorrosive additive stripping liquid controlling composition |
| CN107193187B (en) * | 2016-03-15 | 2020-08-07 | 东友精细化工有限公司 | Resist stripping liquid composition |
| CN108919617A (en) * | 2018-07-31 | 2018-11-30 | 赵文应 | A kind of TFT-LCD negativity developer solution |
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| CN109634071A (en) * | 2019-01-23 | 2019-04-16 | 福建省佑达环保材料有限公司 | A kind of aqua type photoresist lift off liquid for display panel and semiconductor field |
| CN109634071B (en) * | 2019-01-23 | 2022-04-12 | 福建省佑达环保材料有限公司 | Water-based photoresist stripping liquid for display panel and semiconductor field |
| CN110003996A (en) * | 2019-05-21 | 2019-07-12 | 广东剑鑫科技股份有限公司 | A kind of soak and preparation method thereof and application method |
| CN110441997A (en) * | 2019-08-19 | 2019-11-12 | 江阴江化微电子材料股份有限公司 | A kind of improved environmentally friendly water system photoresist lift off liquid |
| CN112680287A (en) * | 2020-12-22 | 2021-04-20 | 青岛科金电子材料有限公司 | Glue-removing and softening integrated low-temperature deburring liquid for surface-mounted diodes |
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Application publication date: 20150513 |