CN100338530C - Method for releasing resist - Google Patents

Method for releasing resist Download PDF

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Publication number
CN100338530C
CN100338530C CNB028216881A CN02821688A CN100338530C CN 100338530 C CN100338530 C CN 100338530C CN B028216881 A CNB028216881 A CN B028216881A CN 02821688 A CN02821688 A CN 02821688A CN 100338530 C CN100338530 C CN 100338530C
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Prior art keywords
resist stripping
resist
stripping composition
amino
copper
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CN1578932A (en
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清水英贵
松永裕嗣
大户秀
池本一人
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority claimed from JP2001338436A external-priority patent/JP2003140364A/en
Priority claimed from JP2001338438A external-priority patent/JP2003140365A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H01L21/31138—Etching organic layers by chemical means by dry-etching

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

In the resist stripping method of the present invention, a wiring substrate having a remaining resist layer is brought into contact with a resist stripping composition in an atmosphere containing oxygen in a proportion of 2% by volume or less. Preferably, the resist is removed after pretreating the remaining resist layer with hydrogen peroxide. A resist stripping composition comprising an amine compound, a solvent, a strong alkali, and water is preferably used in the resist stripping method of the present invention.

Description

Peel off the method for resist
Technical field
The present invention relates to the composition of removing resist and the method in the manufacturing of SIC (semiconductor integrated circuit), liquid crystal board, organic EL plate, printed circuit board (PCB) etc., used.
Background technology
In producing, the lithography of integrated circuit such as IC and LSI, display device such as LCD and El element, printed circuit board (PCB), micromachine, DNA chip and micro device is extensive use of photoresist.
The solution that contains organic base and water-soluble solvent is conventionally used as the resist stripping composition.Especially, amines is commonly used for organic base and as the resist stripping composition, has used the non-aqueous solution that for example contains alkanolamine and dimethyl sulfoxide; The aqueous solution that contains alkanolamine, water-soluble solvent and sugar alcohol; The aqueous solution that contains alkanolamine, azanol and catechol.These alkaline resist stripping compositions are quite effective removing aspect the resist that comprises the phenolic hydroxy group compound and contain the ester bond compound.
These resist stripping compositions have been used for mainly removing the resist on non-copper matrix such as aluminium and aluminium alloy under room temperature-100 ℃.
Recently, low resistance copper begins as wiring material, and being used as with LSI day by day especially is the semiconductor wiring material of representative.Simultaneously, low dielectric layer begins as insulating material.In conventional method, form resist, carry out dry corrosion and ashing, remove then.Yet cineration technics is easy to change the surface nature of low dielectric layer, diminishes the function of circuit.Therefore, require not carry out the method for cineration technics.Because its character marked change of dry corrosion resist is so can not adopt known amine-containing compound fully to remove resist as the resist stripping composition of effective constituent.In addition, because the resist stripping composition of amine-containing compound produces copper-amine complex, therefore corrode copper cash easily.
Disclosure of the Invention
The purpose of this invention is to provide and do not corroding copper, especially under the copper cash situation, by using the resist stripping composition of amine-containing compound, the method for removing resist.Another purpose of the present invention provides the resist stripping composition of the amine-containing compound that uses in removing the method for resist.
The present inventor found that furtheing investigate at the resist of removing on the copper cash matrix, and the composition of amine-containing compound, solvent, highly basic and water under the situation of not corroding copper or aldary, can be removed resist.
In addition, the present inventor has furtherd investigate under the situation of not corroding copper, removes the top condition of resist.The result, opposite with the general knowledge of amines corrosion copper, the present inventor finds, be dissolved in the dioxygen oxidation copper in the resist stripping composition, be converted to soluble copper-amine complex with the copper of oxidation, promote the corrosion of copper, that is to say, find that the oxygen that is dissolved in the resist stripping composition is the main cause of corrosion copper.
Therefore, the invention provides a kind of resist stripping means, it may further comprise the steps: in containing the atmosphere that ratio is 2% volume or lower oxygen, the wiring matrix that has residual resist after etching is contacted with the resist stripping composition.In preferred embodiments, after with the residual resist layer of hydrogen peroxide pre-service, carry out and the contacting of resist stripping composition.
In addition, the invention provides a kind of resist stripping composition, it comprises amines, solvent, highly basic and water, and it can use in above resist stripping means.
Implement optimal mode of the present invention
The resist stripping composition comprises amines, solvent, highly basic (optional components) and water.
The example of amines comprises ammonia, single alkanamine, two alkanamines, three alkanamines, alkanolamine, polyamines, hydroxylamine compound and cyclammonium.
Single alkanamine can comprise methylamine, ethamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutyl amine, tert-butylamine, amylamine, the 2-aminopentane, the 3-aminopentane, 1-amino methyl butane, 2-amino-2-methyl butane, 3-amino-2-methyl butane, 4-amino-2-methyl butane, hexylamine, 5-amino-2-methyl pentane, heptyl amice, octylame, nonyl amine, decyl amine, heptadecyl-amine, dodecyl amine, tridecyl amine, tetradecylamine, pentadecyl amine, cetylamine, heptadecylamine (HDA) and octadecane amine; Two alkanamines can comprise dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-sec-butylamine, two tert-butylamines, diamylamine, dihexylamine, two heptyl amices, dioctylamine, nonyl amine, didecylamine, methyl ethyl-amine, the methyl propylamine, methyl isopropyl amine, the methyl n-butylamine, the methyl isobutyl amine, the methyl sec-butylamine, the methyl-tert butylamine, dimethylpentylamine, the methyl isoamyl amine, the ethyl propylamine, the ethyl isopropylamine, the ethyl n-butylamine, the ethyl isobutyl amine, the ethyl sec-butylamine, the ethyl tert-butylamine, ethyl iso penlyl amine, propyl group n-butylamine and propyl group isobutyl amine; Can comprise trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, triamylamine, dimethyl amine, methyl-diethyl-amine and methyl-di-n-propylamine with three alkanamines.
Alkanolamine can comprise monoethanolamine, 1-amino-2-propyl alcohol, N-(amino-ethyl) monoethanolamine, the N-methylethanolamine, the N-ehtylethanolamine, N-propyl group monoethanolamine, the N-butylethanolamine, diethanolamine, isopropanolamine, N-methyl isopropyl hydramine, N-ethyl isopropanolamine, N-propyl group isopropanolamine, 2-aminopropane-1-alcohol, N-methyl-2-aminopropane-1-alcohol, N-ethyl-2-aminopropane-1-alcohol, 1-aminopropane-3-alcohol, N-methyl isophthalic acid-aminopropane-3-alcohol, N-ethyl-1-aminopropane-3-alcohol, 1-butylamine-2-alcohol, N-methyl isophthalic acid-butylamine-2-alcohol, N-ethyl-1-butylamine-2-alcohol, 2-butylamine-1-alcohol, N-methyl-2-butylamine-1-alcohol, N-ethyl-2-butylamine-1-alcohol, 3-butylamine-1-alcohol, N-methyl-3-butylamine-1-alcohol, N-ethyl-3-butylamine-1-alcohol, 1-butylamine-4-alcohol, N-methyl isophthalic acid-butylamine-4-alcohol, N-ethyl-1-butylamine-4-alcohol, 1-amino-2-methyl propane-2-alcohol, 2-amino-2-methyl propane-1-alcohol, 1-aminopentane-4-alcohol, 2-amino-4-methylpentane-1-alcohol, 2-aminohexane-1-alcohol, the amino heptane of 3--4-alcohol, 2-amino-octane-2-alcohol, 5-amino-octane-4-alcohol, 1-aminopropane-2, the 3-glycol, 2-aminopropane-1, the 3-glycol, three (oxygen methyl) aminomethane, 1,2-diaminopropanes-3-alcohol, 1, the pure and mild 2-of 3-diaminopropanes-2-(2-amino ethoxy) ethanol.
Polyamines can comprise ethylenediamine, propane diamine, the trimethylene diamines, tetra-methylenedimine, 1, the 3-diaminobutane, 2, the 3-diaminobutane, five methylene diamine, 2,4-diamido pentane, hexamethylene diamine, the heptamethylene diamines, eight methylene diamine, nine methylene diamine, the N-methyl ethylenediamine, N, the N-dimethyl-ethylenediamine, the trimethyl ethylenediamine, the N-ethylethylenediamine, N, the N-diethyl ethylenediamine, the triethyl ethylenediamine, 1,2,3-triamido propane, hydrazine, three (2-amino-ethyl) amine, four (amino methyl) methane, diethylene triamine, trien, tetren, seven ethylidene, eight amine, nine ethylidene, ten amine, the diazabicyclo undecylene, hydrazine, dimethylhydrazine, methyl hydrazine and hydroxyethylhydrazine.
Hydroxylamine compound can comprise azanol, N-methyl hydroxylamine, N-ethyl azanol and N, N-diethyl hydroxylamine.
Cyclammonium can comprise the pyrroles, the 2-methylpyrrole, the 3-methylpyrrole, the 2-N-ethyl pyrrole N-, the 3-N-ethyl pyrrole N-, 2, the 3-dimethyl pyrrole, 2, the 4-dimethyl pyrrole, 3, the 4-dimethyl pyrrole, 2,3,4-trimethyl pyrroles, 2,3,5-trimethyl pyrroles, the 2-pyrrolin, pyrrolidine, the 2-crassitude, the 3-crassitude, pyrazoles, imidazoles, 1,2,3-triazoles, 1,2,3, the 4-tetrazolium, piperidines, pipecoline, the 3-methyl piperidine, the 4-methyl piperidine, 2, the 4-lupetidine, 2, the 6-lupetidine, 3, the 5-lupetidine, piperazine, the 2-methyl piperazine, 2, the 5-lupetazin, 2,6-lupetazin and morpholine.
In the middle of above-described amines, the preferred at least a following compound that is selected from: monoethanolamine, 1-amino-2-propyl alcohol, N-(amino-ethyl) monoethanolamine, N-methylethanolamine, N-ehtylethanolamine, diethanolamine, isopropanolamine, 2-(2-amino ethoxy) ethanol, ethylenediamine, propane diamine, butanediamine, diethylene triamine, piperazine, morpholine, trien, tetren and penten.
The preferred at least a compound that is selected from the following substances of highly basic: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, bursine and hydroxide acetylcholine, wherein more preferably Tetramethylammonium hydroxide and bursine.
Solvent preferably can be with amines the miscible and example comprise ether solvents such as ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether; Amide solvent such as formamide, monomethyl formamide, dimethyl formamide, single ethyl-formamide, diethylformamide, acetamide, monomethyl acetamide, dimethyl acetamide, single ethyl acetamide, diethyl acetamide, N-Methyl pyrrolidone and N-ethyl pyrrolidone; Alcoholic solvent such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol and propylene glycol; Sulfoxide solvent such as dimethyl sulfoxide; Sulfoxide solvent such as dimethyl sulfone, diethyl sulfone, two (2-hydroxy sulfones) and tetramethylene sulfone; The imidazolidinone solvent is as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone and 1,3-diisopropyl-2-imidazolidinone; With interior ester solvent such as gamma-butyrolacton and δ-Wu Neizhi.
In the middle of above-mentioned solvent, preferred dimethyl sulfoxide, N, dinethylformamide, N, N-dimethyl acetamide, N-Methyl pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether and propylene glycol, this is because of their easy acquisitions and owing to higher boiling causes due to the easy to handle character.In addition, above-mentioned amines can be used as solvent.
In order to remove resist under the situation of not corroding copper cash, the resist stripping composition preferably contains the amines of 5-95wt%, the solvent of 3-85wt%, the highly basic of 0.01-5wt% and the water of 1-25wt%; The amines that more preferably contains 10-40wt%, the solvent of 50-80wt%, the highly basic of 0.1-3wt% and the water of 5-20wt%.Resist stripping composition of the present invention can contain the conventional additives of not negative effect of consumption effect of the present invention, as surfactant and the corrosion inhibitor that comprises sorbierite and catechol.
Can have no concrete restrictedly by conventional known method production resist stripping composition.
In the present invention, by under 20-60 ℃, make after etching and preferred residual resist before ashing, contact 1-30 minute with the resist stripping composition, wherein said resist stripping composition comprises amines, solvent, highly basic (optional component) and water.Usually in the resist stripping composition, carry out operating of contacts by the matrix impregnation that will have residual resist.
For example, the resist of widely used phenolic hydroxy group changes its surface nature because of dry corrosion technology.Known resist stripping composition is by utilizing the salt that forms between amines and phenolic hydroxyl group, with the addition reaction of amines with the carbonyl that forms by oxidation, thereby remove resist, yet, so ineffective to removing of the resist of its character marked change.In this case, using the resist contain highly basic to peel off combination can improve and form the ability of salt with phenolic hydroxyl group and remove the ability of the halogen that generates and also increase hydrolysis function in dry corrosion technology.
As mentioned above, the oxygen that is dissolved in the resist stripping composition is the main cause of copper and corrosion of copper alloy.3% or higher alkali content (amines+highly basic) and remove under the high oxygen concentration of atmosphere in the operation at resist, it is remarkable that corrosive attack becomes.Therefore, in the present invention,, under preferred 1% volume or the littler oxygen concentration, remove resist, so that effectively prevent the corrosion of copper and aldary at 2% volume or littler.By using nitrogen, argon gas or hydrogen, preferably use nitrogen, realize the hypoxemia atmosphere.More preferably, in order effectively to prevent the corrosion of copper and aldary, under 2% volume or littler oxygen concentration, by to keep the oxygen content that has dissolved in the resist stripping composition be under 3ppm or the littler situation to wherein being blown into such as nitrogen, argon gas and hydrogen gas, remove resist simultaneously.Can before using, remove the air in the resist stripping composition.As mentioned above, resist stripping composition of the present invention can be removed resist residual on the matrix with copper layer or copper alloy layer most effectively.
In addition, the present inventor finds, can remove the resist of its performance marked change effectively by the hydrogen peroxide pre-service.With the resist surface of its performance marked change of hydrogen peroxide pre-service meeting oxidation, reduce molecular weight, thereby promote the formation of carbonyl.As mentioned above, this quickens removing of resist.
Before after etching and with the resist stripping composition, handling, for example under 20-60 ℃, matrix impregnation is containing 0.5wt% or higher by connecting up, in the solution of preferred 1-10wt% hydrogen peroxide 1-30 hour, wiring matrix is contacted with hydrogen peroxide, thereby use the pre-service of hydrogen peroxide.Superoxol can be an aqueous solution.Adjuvant such as sequestrant and surfactant can join in the superoxol.Directly or after washing with water, remove operation to carrying out resist with the pretreated wiring matrix of hydrogen peroxide.
By with reference to following embodiment, explain the present invention in more detail, wherein the embodiment scope that should not be construed as limiting the invention.
Embodiment 1-6 and comparative example 1 and 2
Have according to the following stated order dry corrosion on 6 inches wafers of lamination copper layer, silicon nitride layer, silicon dioxide interlayer insulation course and resist layer on the silicon matrix, forming via structure.This via structure arrives the copper layer.Under 70 ℃, with matrix impregnation in having the resist stripping composition of prescription shown below 30 minutes.After with water rinse, the degree of removing of check resist and the corrosion of copper layer under scanning electron microscope.The results are shown in Table 2.
In nitrogen atmosphere, use digital oxygen analyser (the DO-5509 model is limited to 0.5ppm under detecting) available from N.T.Corporation, measure the oxygen content of dissolving in the resist stripping composition.
Table 1
The resist stripping composition
Amines Solvent Highly basic Water
Kind wt％ Kind wt％ Kind wt％
Embodiment
1 EA 30 DMSO 60 TMAH 0.2 Aequum
2 EA 25 NMP 65 TMAH 1 Aequum
3 1A2P 32 PG 61 TMAH 0.5 Aequum
4 TETA 18 DGME 72 CH 1 Aequum
5 PEHA 30 DGBE 60 TMAH 2 Aequum
6 AEEA 10 MEA 80 CH 0.1 Aequum
The comparative example
1 EA 30 DMSO 60 - - Aequum
2 EA 30 DMSO 60 TMAH 0.2 Aequum
EA: monoethanolamine
1A2P:1-amino-2-propyl alcohol
TETA: trien
PEHA: penten
AEEA: amino ethyl ethanolamine
TMAH: Tetramethylammonium hydroxide
CH: bursine
DMSO: dimethyl sulfoxide
The NMP:N-methyl pyrrolidone
PG: propylene glycol
DGME: diethylene glycol monomethyl ether
DGBE: diethylene glycol monobutyl ether
The MEA:N-methylethanolamine
Table 2
Oxygen concentration in the atmosphere (ppm) Removing of resist The corrosion of copper The oxygen concentration (ppm) of dissolving
Embodiment
1 500 Well Do not have 0.5 it is or lower
2 200 Well Do not have 0.6
3 400 Well Do not have 1.3
4 800 Well Do not have 0.5 it is or lower
5 200 Well Do not have 1.5
6 400 Well Do not have 0.5 it is or lower
The comparative example
1 500 Do not remove Do not have 0.5 it is or lower
2 200000 Well Significantly 5.8
Embodiment 7-12 and comparative example 3 and 4
Have according to the following stated order dry corrosion on 12 inches wafers of lamination copper layer, silicon nitride layer, silicon dioxide interlayer insulation course and resist layer on the silicon matrix, forming via structure.This via structure arrives the copper layer.Under 60 ℃, with matrix impregnation in having the solution shown in the following table 3 15 minutes, matrix is carried out pre-service, then, under 70 ℃, with matrix impregnation in resist stripping composition 30 minutes with prescription shown in the following table 3.After with water rinse, the degree of removing of check resist and the corrosion of copper layer under scanning electron microscope.The results are shown in Table 4.
Table 3
Pre-service The resist stripping composition
Hydrogen peroxide Amines Solvent Highly basic Water
Dense change (wt%) Adjuvant (wt%) Kind wt％ Kind wt％ Kind wt％
Embodiment
7 6 EA 30 DMSO 60 TMAH 0.2 Aequum
8 5 EDTA(0.001) TETA 25 NMP PG 25 40 TMAH 1 Aequum
9 3 - 1A2P 25 DMSO 65 TMAH 15 Aequum
10 4 NH4F(0.001) EA 18 DGM E 72 CH 1 Aequum
11 4 - PEHA 30 DGBE 60 TMAH 2 Aequum
12 4 - AEEA 10 MEA 80 CH 0.1 Aequum
The comparative example
3 - - EA 30 DMSO 60 TMAH 0.2 Aequum
4 - - EA 30 NMP 65 TMAH 1 Aequum
EA: monoethanolamine
1A2P:1-amino-2-propyl alcohol
TETA: trien
PEHA: penten
AEEA: amino ethyl ethanolamine
TMAH: Tetramethylammonium hydroxide
CH: bursine
DMSO: dimethyl sulfoxide
The NMP:N-methyl pyrrolidone
PG: propylene glycol
DGME: diethylene glycol monomethyl ether
DGBE: diethylene glycol monobutyl ether
The MEA:N-methylethanolamine
EDTA: ethylenediamine tetraacetic acid
Table 4
Oxygen concentration in the atmosphere (ppm) Removing of resist The corrosion of copper The oxygen concentration (ppm) of dissolving
Embodiment
7 200 Well Do not have 0.5 it is or lower
8 200 Well Do not have 0.5 it is or lower
9 200 Well Do not have 1.0
10 200 Well Do not have 0.5 it is or lower
11 200 Well Do not have 0.5 it is or lower
12 200 Well Do not have 0.5 it is or lower
The comparative example
3 200 Do not remove Do not have 0.5 it is or lower
4 200 Do not remove Do not have 0.5 it is or lower
Find out from table 2 and 4, adopt resist stripping means of the present invention, can remove the resist on the wiring matrix under the situation that does not have to corrode at the copper layer.In addition, by using the hydrogen peroxide pre-service, even when only being difficult to remove resist, quickened removing of resist by the resist stripping composition.
Embodiment 13-15 and comparative example 5
Under 50 ℃, be that the thick silicon matrix of 400 dusts is immersed in the resist stripping composition with following prescription with the copper layer, measure the corrosion speed of copper layer.The results are shown in Table 5.
The resist stripping composition
Monoethanolamine: 45wt%
Diethylene glycol monomethyl ether: 20wt%
Water: 32wt%
Sorbierite: 3wt%
Table 5
The atmosphere condition Corrosion speed (dust/minute)
Embodiment
13 In nitrogen atmosphere 0.7
14 When being blown into the resist stripping composition, handles nitrogen 0.3
15 In the nitrogen that contains 1% oxygen 1
The comparative example
5 In air 7
Find that the corrosion speed of copper is subjected to the influence of oxygen widely.If continue the supply air, the then same corrosion that continues to promote copper.Therefore, should remove oxygen source, prevent the corrosion of copper.
Embodiment 16 and 17 and comparative example 6
Under 50 ℃, be that the thick silicon matrix of 400 dusts is immersed in the resist stripping composition with following prescription with the copper layer, measure the corrosion speed of copper layer.In being furnished with the spherical box of aerial oxygen analyser, measure.The results are shown in Table 6.
The resist stripping composition
Monoethanolamine: 40wt%
Diethylene glycol monobutyl ether: 38wt%
Water: 20wt%
Catechol: 2wt%
Table 6
The atmosphere condition Corrosion speed (dust/minute)
Embodiment
16 In nitrogen atmosphere 1.3
17 After removing air, the resist stripping composition contains in the nitrogen atmosphere of 200ppm oxygen 0.5
The comparative example
6 In air 2.0
Embodiment 18 and comparative example 7
Under 50 ℃, be that the thick silicon matrix of 400 dusts is immersed in the resist stripping composition with following prescription with the copper layer, measure the corrosion speed of copper layer.In being furnished with the spherical box of aerial oxygen analyser, measure.The resist stripping composition
Monoethanolamine: 30wt%
N-Methyl pyrrolidone: 55wt%
Water: 10wt%
Catechol: 5wt%
After applying photoresist, composition and dry corrosion, under 50 ℃, silicon matrix is immersed in the resist stripping composition.Residual resist required time is removed in measurement, and observes under optical microscope simultaneously.The results are shown in Table 7.
Table 7
The atmosphere condition Corrosion speed (dust/minute) Remove resist time (minute)
Embodiment
18 In nitrogen atmosphere 0.8 15
The comparative example
7 In air 4.5 15
By in nitrogen, carrying out remove (in the hypoxemia atmosphere) of resist, can remove the corrosion that prevents copper under the situation of ability not influencing resist.
Industrial applicibility
According to the present invention, the resist after can in the situation of not corroding copper, removing dry corrosion. Therefore, the invention enables and to adopt conventional resist stripping composition, and the resist stripping composition of described routine impairs the processing of the matrix with image. In addition, can by using the hydrogen peroxide preliminary treatment, easily remove the resist that is difficult to remove.

Claims (8)

1. resist stripping means, it comprises the steps:
In containing the atmosphere that ratio is 2% volume or lower oxygen, the wiring matrix that has residual resist layer after etching is contacted with the resist stripping composition,
Wherein before making wiring matrix and the resist stripping composition contact, by contacting residual resist layer is carried out pre-service with hydrogen peroxide, and this resist stripping composition comprises the amines of 5-95wt%, the solvent of 3-85wt%, the highly basic of 0.01-5wt% and the water of 1-25wt%, wherein said highly basic are at least a compounds that is selected from Tetramethylammonium hydroxide, bursine, tetraethyl ammonium hydroxide and the TBAH.
2. the resist stripping means of claim 1, wherein when from the resist stripping composition, expelling dissolved gas, the step that wiring matrix is contacted with the resist stripping composition.
3. the resist stripping means of claim 1, wherein after making the degassing of resist stripping composition, the step that wiring matrix is contacted with the resist stripping composition.
4. any one resist stripping means of claim 1-3 is that 0.5wt% or higher solution contact by making residual resist layer and concentration of hydrogen peroxide wherein, carries out pre-service.
5. any one resist stripping means of claim 1-3, wherein in the resist stripping composition, the concentration of oxygen of having dissolved is 3ppm or lower.
6. claim 1 or 3 resist stripping means, wherein amines is at least a compound that is selected from following compounds: monoethanolamine, 1-amino-2-propyl alcohol, N-(amino-ethyl) monoethanolamine, N-methylethanolamine, N-ehtylethanolamine, diethanolamine, isopropanolamine, 2-(2-amino ethoxy) ethanol, ethylenediamine, propane diamine, butanediamine, diethylene triamine, piperazine, morpholine, trien, tetren and penten.
7. any one resist stripping means of claim 1-3, wherein solvent is at least a compound that is selected from following compounds: dimethyl sulfoxide, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether and propylene glycol.
8. any one resist stripping means of claim 1-3, the matrix that wherein connects up has copper layer or copper alloy layer.
CNB028216881A 2001-11-02 2002-10-31 Method for releasing resist Expired - Lifetime CN100338530C (en)

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JP2001338436A JP2003140364A (en) 2001-11-02 2001-11-02 Resist removing solution for copper wiring board
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JP2001338438A JP2003140365A (en) 2001-11-02 2001-11-02 Method for using resist removing solution
PCT/JP2002/011358 WO2003038529A1 (en) 2001-11-02 2002-10-31 Method for releasing resist

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CN1578932A (en) 2005-02-09
TWI311694B (en) 2009-07-01

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