CN104122763A

CN104122763A - Composition for stripping photoresist and method of use thereof

Info

Publication number: CN104122763A
Application number: CN201410157681.2A
Authority: CN
Inventors: 刘骐铭; 施俊安
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2013-04-25
Filing date: 2014-04-18
Publication date: 2014-10-29
Also published as: TWI566058B; TW201441774A

Abstract

The invention relates to a composition for stripping photoresist and a using method thereof. A composition for stripping a photoresist comprises an amine compound, an alcohol compound, a quaternary ammonium salt compound, an organic solvent and water. The amine-based compound includes at least one tertiary amine-based compound consisting of the following group: a nitrogen heterocyclic compound represented by the formula and a chain polyamine compound having at least two tertiary amines. The alcohol-based compound includes at least one first alcohol-based compound consisting of the following group: sugar-based compounds and alkynyl-containing alcohol-based compounds.

Description

Peel off constituent and using method thereof for photoresistance

Technical field

The present invention relates to a kind of photoresistance constituent of peeling off, particularly relate to a kind of comprise amine compound and alcohol based compound peel off photoresistance constituent, wherein, this alcohol based compound comprises the first alcohol based compound that at least one is comprised of following group: sugared based compound and containing the alcohol based compound of alkynyl.

Background technology

In manufacture of semiconductor, be on wafer, to form integrated circuit, and this integrated circuit is consisted of many metallic circuits, wherein, described metallic circuit is mainly to form by lithographic process.This lithographic process comprises processing substrate, light blockage coating, exposure, development, etching and photoresistance and the step such as peels off.Microminiaturization along with integrated circuit size, to the more requirement of the quality of formed metallic circuit, except the improvement by photoresistance composition reaches the quality demand of metallic circuit, also more and more pay attention to the technology of optical resistance stripping steps, wherein, exploitation one constituent of effectively photoresistance being peeled off from metallic circuit is the problem of this technical field person skilled active research.

Japanese patent application publication No. 2005070230 discloses a kind of photoresistance constituent of peeling off.This is peeled off photoresistance and comprises 2,3-dihydroxy naphthlene (A), organic amine compound (B), polar organic solvent (C) and carbohydrate (D) with constituent, and wherein, organic amine compound (B) is selected from monoethanolamine, isopropanolamine or diglycol.This is peeled off photoresistance and can be avoided metallic circuit to be corroded and photoresistance can be peeled off from metallic circuit with constituent.Although this is peeled off photoresistance and photoresistance can be peeled off with constituent, but the photoresistance that can occur to have peeled off returns the phenomenon of being stained with on metallic circuit, and per unit volume to peel off the efficiency that photoresistance peels off photoresistance with constituent not good so that clean capacity (capacity for cleaning) deficiency.

In view of above-mentioned, thus improvement peel off photoresistance and return and be stained with to metal level or insulation course with the photoresistance that constituent is avoided having peeled off, meanwhile, improve the clean capacity of peeling off photoresistance use constituent, be the problem that this technical field person skilled can break through again.

Summary of the invention

The first object of the present invention be to provide a kind of photoresistance of avoiding having peeled off to return to be stained with to metal level or insulation course and have large clean capacity peel off photoresistance constituent.

The present invention peels off photoresistance constituent, comprises:

Amine compound, comprises the tertiary amine based compound that at least one is comprised of following group: the nitrogen heterocyclic shown in formula (I) and have the chain polyamine compounds of at least two tertiary amines;

In formula (I), A and B represent respectively or condition is at least one expression in A and B wherein, this R represents the C being unsubstituted ₁to C ₄alkyl, or the C being substituted ₁to C ₄alkyl;

Alcohol based compound, comprises the first alcohol based compound that at least one is comprised of following group: sugared based compound and containing the alcohol based compound of alkynyl;

Quarternary ammonium salt compound;

Organic solvent; And

Water.

The present invention peels off photoresistance constituent, the C that this is substituted ₁to C ₄alkyl be selected from the C replacing through hydroxyl ₁to C ₄alkyl, the C replacing through amino ₁to C ₄alkyl, or the C replacing through cyano group ₁to C ₄alkyl.

The present invention peels off photoresistance constituent, and this chain polyamine compounds with at least two tertiary amines is selected from N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-4-methyl-diaminopropane, two [2-(N, N-dimethylamino) ethyl] ether, N, N, N', N'', N''-five methyl diethylentriamine, N, N, N', N'-4-methyl hexamethylene diamine, or their combination.

The present invention peels off photoresistance constituent, total amount based on this amine compound is 100 weight portions, the use amount scope of this alcohol based compound is that the use amount scope of 10 to 100 weight portions, this quarternary ammonium salt compound is that the use amount scope of 5 to 100 weight portions, this organic solvent is 500 to 4,000 weight portion, and the use amount scope of this water is 100 to 1,000 weight portions.

The present invention peels off photoresistance constituent, and this organic solvent comprises the first solvent; This first solvent is selected from glycol based compound, alcohol ether based compound, or their combination.

The present invention peels off photoresistance constituent, and this sugar based compound is selected from glucose, mannose, galactose, D-sorbite, mannitol, xylitol, or their combination.

The present invention peels off photoresistance constituent, should be selected from 3-methyl isophthalic acid-butynyl-3-alcohol, 3-methyl-1-pentene alkynyl-3-alcohol, 3 containing the alcohol based compound of alkynyl, 6-dimethyl-4-octyne base-3,6-glycol, 2,4,7,9-tetramethyl-5-decynyl-4,7-glycol, 3,5-dimethyl-1-hexin base-3-alcohol, 2-butynyl-1,4-glycol, or their combination.

The second object of the present invention is to provide a kind of use to peel off the method for constituent for photoresistance.

The present invention uses and peels off the method for constituent for photoresistance, comprises following steps:

Laminate is provided, comprises substrate, be formed on metal level or insulation course on this substrate, and be formed on the photoresist layer on this metal level or insulation course;

The photoresist layer of this laminate is contacted with constituent with the above-mentioned photoresistance of peeling off, until this photoresist layer is peeled off from this laminate;

Bestow cleaning treatment.

The present invention uses and peels off the method for constituent for photoresistance, is also contained in after cleaning treatment, bestows dry processing.

Beneficial effect of the present invention is: this peel off photoresistance with constituent by the cooperative effect of described composition, making this peel off photoresistance can prevent with constituent that the photoresistance of having peeled off from returning and be stained with to metal level or insulation course, then promote the yield of successive process, and this is peeled off photoresistance and has the large capacity of cleaning with constituent, can make the photoresistance of peeling off of per unit volume increase by the amount that constituent is peeled off photoresistance, then can promote production capacity and utilization benefit.

Embodiment

The present invention peels off photoresistance constituent, comprises:

Quarternary ammonium salt compound;

Organic solvent; And

Water.

By one by one this being peeled off to photoresistance, with each composition in constituent, be elaborated below:

< amine compound >

This amine compound comprises the tertiary amine based compound that at least one is comprised of following group: the nitrogen heterocyclic shown in formula (I) and have the chain polyamine compounds of at least two tertiary amines.This peels off the chain polyamine compounds that does not use the nitrogen heterocyclic shown in formula (I) in constituent or have at least two tertiary amines for photoresistance, can produce the photoresistance of having peeled off and return the problem of being stained with to metal level or insulation course, and this clean capacity of peeling off photoresistance use constituent is not good.

<< tertiary amine based compound >>

[nitrogen heterocyclic shown in formula (I)]

Nitrogen heterocyclic shown in this formula (I):

In formula (I), A and B represent respectively or condition is at least one expression in A and B wherein, this R represents the C being unsubstituted ₁to C ₄alkyl, or the C being substituted ₁to C ₄alkyl.

The C that this is substituted ₁to C ₄alkyl be selected from the C replacing through hydroxyl ₁to C ₄alkyl, the C replacing through amino ₁to C ₄alkyl, or the C replacing through cyano group ₁to C ₄alkyl.

Nitrogen heterocyclic shown in this formula (I) can be used alone or as a mixture, and the nitrogen heterocyclic shown in this formula (I) is such as but not limited to morpholine (morpholine), N-methylmorpholine (N-methylmorpholine), N-ethylmorpholine (N-ethyl morpholine), N-propyl group morpholine (N-propyl morpholine), N-butyl morpholine (N-butyl morpholine), N-(2-hydroxyethyl) morpholine [N-(2-hydroxyethyl) morpholine], N-(3-aminopropyl) morpholine [N-(3-aminopropyl) morpholine], N-(2-cyano ethyl) morpholine [N-(2-cyanoethyl) morpholine], N-(2-amino-ethyl) piperazine [N-(2-aminoethyl) piperazine], N-(2-hydroxyethyl) piperazine [N-(2-hydroxyethyl) piperazine], or N-methyl-N'-(2-hydroxyethyl) piperazine [N-methyl-N'-(2-hydroxyethyl) piperazine] etc.

Preferably, the nitrogen heterocyclic shown in this formula (I) is selected from N-(2-amino-ethyl) piperazine, N-(2-hydroxyethyl) piperazine, N-(3-aminopropyl) morpholine, or their combination.

[the chain polyamine compounds with at least two tertiary amines]

This chain polyamine compounds with at least two tertiary amines is selected from N, N, N', N'-tetramethylethylenediamine (N, N, N', N'-tetramethylethylenediamine), N, N, N', N'-4-methyl-diaminopropane (N, N, N', N'-tetramethylpropylene diamine), two [2-(N, N-dimethylamino) ethyl] ether { bis[2-(N, N-dimethylamino) ethyl] ether}, N, N, N', N'', N''-five methyl diethylentriamine (N, N, N', N'', N''-pentamethyldiethylenetriamine), N, N, N', N'-4-methyl hexamethylene diamine (N, N, N', N'-tetramethyl hexamethylene diamine), or their combination.

Preferably, this chain polyamine compounds with at least two tertiary amines is selected from N, N, N', N'-tetramethylethylenediamine, two [2-(N, N-dimethylamino) ethyl] ether, N, N, N', N'', N''-five methyl diethylentriamine, or their combination.

This amine compound also comprises other amine compounds that at least one is comprised of following group: monoethanolamine (monoethanolamine), diethanolamine (diethanolamine), triethanolamine (triethanolamine), 2-(2-amino ethoxy) ethanol [2-(2-aminoethoxy) ethanol], N-(2-amino-ethyl) monoethanolamine [N-(2-aminoethyl) ethanolamine], N, N-dimethylethanolamine (N, N-dimethyl ethanolamine), N, N-diethyl ethanolamine (N, N-diethyl ethanolamine), N, N-dibutyl diethanolamine (N, N-dibutyl ethanolamine), N-methylethanolamine (N-methyl ethanolamine), N-ehtylethanolamine (N-ethyl ethanolamine), N-butylethanolamine (N-butyl ethanolamine), N methyldiethanol amine (N-methyl diethanolamine), N-ethyldiethanolamine (N-ethyl diethanolamine), monoisopropanolamine (monoisopropanolamine), diisopropanolamine (diisopropanolamine), triisopropanolamine (triisopropanolamine), ethylenediamine (ethylenediamine), diethylene triamine (diethylene triamine), trien (triethylenetetramine), tetren (tetraethylenepentamine), penten (pentaethylenehexamine), triethylenediamine (triethylenediamine), propane diamine (propane diamine), butanediamine (butane diamine), hexane diamine (hexamethylene diamine), imidazoles (imidazole), 1-methylimidazole (1-methyl imidazole), glyoxal ethyline (2-methyl imidazole), 1,2-methylimidazole (1,2-dimethyl imidazole), 1,2,4,5-tetramethyl-imidazoles (1,2,4,5-tetramethyl-imidazole), 2-ethyl-4-methylimidazole (2-ethyl-4-methyl imidazole), cyclohexylamine (cyclohexylamine), 2-DEHA (2-ethyl hexyl amine), Benzyl amine (benzylamine), aniline (aniline), triethylamine (triethylamine), tripropyl amine (TPA) (tripropylamine) and tri-n-butylamine (tributylamine).

< alcohol based compound >

This alcohol based compound comprises the first alcohol based compound that at least one is comprised of following group: sugared based compound and containing the alcohol based compound of alkynyl.This peels off photoresistance with not using this alcohol based compound in constituent, can produce the photoresistance of having peeled off and return the problem of being stained with to metal level or insulation course.

<< the first alcohol based compound >>

[sugared based compound]

This sugar based compound is selected from glucose (glucose), mannose (mannose), galactose (galactose), D-sorbite (sorbitol), mannitol (mannitol), xylitol (xylitol), or their combination.

[containing the alcohol based compound of alkynyl]

Should be selected from 3-methyl isophthalic acid-butynyl-3-alcohol (3-methyl-1-butyne-3-ol) containing the alcohol based compound of alkynyl, 3-methyl-1-pentene alkynyl-3-alcohol (3-methyl-1-pentyne-3-ol), 3, 6-dimethyl-4-octyne base-3, 6-glycol (3, 6-dimethyl-4-octyne-3, 6-diol), 2, 4, 7, 9-tetramethyl-5-decynyl-4, 7-glycol (2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol), 3, 5-dimethyl-1-hexin base-3-alcohol (3, 5-dimethyl-1-hexyne-3-ol), 2-butynyl-1, 4-glycol (2-butyne-1, 4-diol), or their combination.

Preferably, this first alcohol based compound is selected from mannitol, D-sorbite, 3-methyl isophthalic acid-butynyl-3-alcohol, 3,6-dimethyl-4-octyne base-3,6-glycol, or their combination.

This alcohol based compound also comprises the second alcohol based compound.

<< the second alcohol based compound >>

The second alcohol based compound can be used alone or as a mixture, and this second alcohol based compound is such as but not limited to phenol (phenol), cresols (cresol), catechol (catechol), resorcinol (resorcin), 2,3-dihydroxy naphthlene (2,3-dihydroxynaphthalene), 2,3-pyridine glycol (2,3-pyridine diol), 1,2,3,-thrihydroxy-benzene (pyrogallol), salicylic acid (salicylic acid), or 3,4,5-trihydroxybenzoic acid (gallic acid) etc.

< quarternary ammonium salt compound >

This peels off photoresistance with not using quarternary ammonium salt compound in constituent, and this clean capacity of peeling off photoresistance use constituent is not good.This quarternary ammonium salt compound is selected from has four (C ₁to C ₆alkyl) ammonium hydroxide (ammonium hydroxide), there are four (C ₁to C ₆alkyl) hartshorn salt (ammonium carbonate), there are four (C ₁to C ₆alkyl) ammonium acetate (ammonium acetate), there are four (C ₁to C ₆alkyl) ammonium citrate (ammonium citrate), there are four (C ₁to C ₆alkyl) ammonium silicate (ammonium silicate), trialkyl-2-hydroxy alkyl ammonium hydroxide (trialkyl-2-hydroxy-alkyl ammonium hydroxide), trialkyl-2-hydroxyl-alkoxy ammonium hydroxide (trialkyl-2-hydroxy-alkoxy ammonium hydroxide), or their combination.

<< has the ammonium hydroxide >> of four (C1 to C6 alkyl)

This has four (C ₁to C ₆alkyl) ammonium hydroxide can be used alone or as a mixture, and this has four (C ₁to C ₆alkyl) ammonium hydroxide is such as but not limited to Tetramethylammonium hydroxide (tetramethylammonium hydroxide) or TBAH (tetrabutylammonium hydroxide) etc.

<< has the hartshorn salt >> of four (C1 to C6 alkyl)

This hartshorn salt with four (C1 to C6 alkyl) can be used alone or as a mixture, and this has four (C ₁to C ₆alkyl) hartshorn salt is such as but not limited to tetramethyl hartshorn salt (tetramethyl ammonium carbonate).

<< has four (C ₁to C ₆alkyl) ammonium acetate >>

This has four (C ₁to C ₆alkyl) ammonium acetate can be used alone or as a mixture, and this has four (C ₁to C ₆alkyl) ammonium acetate is such as but not limited to tetramethyl ammonium acetate (tetramethyl ammonium acetate).

<< has four (C ₁to C ₆alkyl) ammonium citrate >>

This has four (C ₁to C ₆alkyl) ammonium citrate can be used alone or as a mixture, and this has four (C ₁to C ₆alkyl) ammonium citrate is such as but not limited to tetramethylammonium citrate (tetramethyl ammonium citrate).

<< has four (C ₁to C ₆alkyl) ammonium silicate >>

This has four (C ₁to C ₆alkyl) ammonium silicate can be used alone or as a mixture, and this has four (C ₁to C ₆alkyl) ammonium silicate is such as but not limited to tetramethyl silicic acid ammonium (tetramethylammonium silicate).

<< trialkyl-2-hydroxy alkyl ammonium hydroxide >>

This trialkyl-2-hydroxy alkyl ammonium hydroxide can be used alone or as a mixture, and this trialkyl-2-hydroxy alkyl ammonium hydroxide is such as but not limited to trimethyl-2-hydroxyethyl ammonium hydroxide [trimethyl-2-hydroxyethyl ammonium hydroxide is commonly called as choline (choline)] etc.

<< trialkyl-2-hydroxyl-alkoxy ammonium hydroxide >>

This trialkyl-2-hydroxyl-alkoxy ammonium hydroxide can be used alone or as a mixture, and this trialkyl-2-hydroxyl-alkoxy ammonium hydroxide is such as but not limited to trimethyl-2-hydroxyl-oxethyl ammonium hydroxide (trimethyl-2-hydroxyethoxy ammonium hydroxide), or trimethyl-2-(2-hydroxyl-oxethyl) ethoxy ammonium hydroxide [trimethyl-2-(2-hydroxyethoxy) ethoxy ammonium hydroxide] etc.

Preferably, this quarternary ammonium salt compound is selected from Tetramethylammonium hydroxide, TBAH, trimethyl-2-hydroxyethyl ammonium hydroxide, or their combination.

< organic solvent >

This organic solvent can be used alone or as a mixture, and this organic solvent is such as but not limited to acid amides based compound or the first solvent, and wherein, this first solvent is selected from glycol based compound, alcohol ether based compound, or their combination.

<< acid amides based compound >>

This acid amides based compound can be used alone or as a mixture, and this acid amides based compound is such as but not limited to formamide, acetamide, N-METHYLFORMAMIDE, N-methylacetamide, N-ethyl-formamide, N-ethyl acetamide, N, dinethylformamide, N, N-dimethyl acetamide, N, N-diethylformamide, N, N-diethyl acetamide, N, N-methylimidazole, METHYLPYRROLIDONE (N-methyl-2-pyrrolidone, be called for short NMP), or N-ethyl-2-pyrrolidone etc.

<< the first solvent >>

[glycol based compound]

This glycol based compound can be used alone or as a mixture, and this glycol based compound is such as but not limited to ethylene glycol, diethylene glycol, propylene glycol or 1,3-BDO etc.Preferably, this glycol based compound is selected from ethylene glycol, propylene glycol, or their combination.

[alcohol ether based compound]

This alcohol ether based compound can be used alone or as a mixture, and this alcohol ether based compound is such as but not limited to glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, glycol methyl ether acetate, ethylene glycol ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol list ethylether, triethylene glycol butyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol monomethyl ether, DPE etc., dipropylene glycol list propyl ether, dipropylene glycol single-butyl ether, or Tripropylene glycol monomethyl Ether etc.Preferably, this alcohol ether based compound is selected from diethylene glycol monobutyl ether, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, or their combination.

For making this peel off photoresistance, with constituent, have and preferably clean capacity effect, preferably, this organic solvent comprises the first solvent.

This peels off photoresistance is that amine compound, alcohol based compound, quarternary ammonium salt compound, organic solvent and water are positioned in stirrer and are stirred by the method for making of constituent, and it is evenly mixed.

Total amount based on this amine compound is 100 weight portions, the use amount scope of this alcohol based compound is that the use amount scope of 10 to 100 weight portions, this quarternary ammonium salt compound is that the use amount scope of 5 to 100 weight portions, this organic solvent is 500 to 4,000 weight portion, and the use amount scope of this water is 100 to 1,000 weight portions.

Preferably, total amount based on this amine compound is 100 weight portions, the use amount scope of this alcohol based compound is that the use amount scope of 15 to 95 weight portions, this quarternary ammonium salt compound is that the use amount scope of 10 to 95 weight portions, this organic solvent is 600 to 3,800 weight portions, and the use amount scope of this water is 150 to 900 weight portions.

More preferably, total amount based on this amine compound is 100 weight portions, the use amount scope of this alcohol based compound is that the use amount scope of 20 to 90 weight portions, this quarternary ammonium salt compound is that the use amount scope of 15 to 90 weight portions, this organic solvent is 700 to 3,500 weight portions, and the use amount scope of this water is 200 to 800 weight portions.

Bestow cleaning treatment.

Preferably, the present invention's use is peeled off photoresistance and is also contained in after cleaning treatment by the method for constituent, bestows dry processing.

The preparation method of this laminate is not particularly limited, can adopt the mode in the past used, for example, the preparation method of this laminate comprises following steps: the mode by photosensitive resin composition with rotary coating, is coated on the substrate with metal level or insulation course.Then, this photosensitive resin composition is carried out to lithographic process, then, with pure water, clean.After cleaning, be placed in baking oven and be dried, on this metal level or insulation course, form the photoresist layer with specific pattern.Then; be soaked in etchant; metal level or insulation course are carried out to etch processes; with by not removed by metal level or the insulation course of photoresist layer protection, form metal level or the insulation course with specific pattern, wherein; this has the metal level of specific pattern or the specific pattern in insulation course is corresponding with this specific pattern having in the photoresist layer of specific pattern; then, carry out cleaning treatment and dry processing, can obtain laminate.

At this, have in the substrate of metal level, the material of this substrate is not particularly limited, such as but not limited to alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass, in the above-mentioned substrate that adheres to nesa coating on glass, or for photo-electric conversion device substrate of solid-state image sensor etc. etc.

At this, have in the substrate of metal level, the material of this metal level is not particularly limited, and can adopt used, such as but not limited to copper, aluminium, aluminium alloy, titanium or titanium nitride etc. in the past.The mode that this metal level is formed at substrate is not particularly limited, and can adopt mode in the past, such as but not limited to chemical vapour deposition technique or sputtering method etc.

At this, have in the substrate of insulation course, the material of this insulation course is not particularly limited, and can adopt used, such as but not limited to amorphous silicon (a-Si), polysilicon (p-Si), acrylic acid series polymeric compounds or polysiloxane based polymer etc. in the past.The mode that this insulation course is formed at substrate is not particularly limited, can adopt mode in the past, for example, material be amorphous silicon (a-Si) or polysilicon (p-Si) with formation such as chemical vapour deposition technique or sputtering methods, and material is that acrylic acid series polymeric compounds or polysiloxane based polymer are with formation such as rotary coating or curtain coating coatings.

This photoresist layer is formed through lithographic process by photosensitive resin composition.This lithographic process can adopt the mode in the past used, so repeat no more.There is no particular restriction for this photosensitive resin composition, can adopt used, such as but not limited to photosensitive resin composition that comprises novolac resin etc. in the past.

This etchant is not particularly limited, as long as metal level or the insulation course that this can be had on the substrate of metal level or insulation course remove, such as but not limited to phosphoric acid etch agent or hydrofluoric acid etch agent etc.

The photoresist layer of this laminate is peeled off the mode that photoresistance contacts with constituent and is not particularly limited with above-mentioned, can adopt mode in the past, such as but not limited to laminate is dipped to, peels off photoresistance with in constituent.Preferably, at the temperature of 24 ℃ to 100 ℃, contact 30 seconds to 30 minutes, more preferably, contact 1 minute to 20 minutes.

As long as this cleaning treatment can allow peel off photoresistance can be not residual with constituent, and can adopt mode in the past, so repeat no more.

As long as this dry laminate that can allow after stripping resistance layer of processing is dried, and can adopt mode in the past, for example, the laminate after stripping resistance layer is placed in to vacuum drying chamber and is dried.

The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are only for illustrating use, and should not be interpreted as restriction of the invention process.

<< embodiment >>

<< embodiment 1>>

By the N-of 100 weight portions (2-amino-ethyl) piperazine, the mannitol of 10 weight portions, the Tetramethylammonium hydroxide, 1 of 20 weight portions, the water of the propylene glycol of the diethylene glycol monobutyl ether of 000 weight portion, 500 weight portions and 500 weight portions is uniformly mixed under room temperature, can obtain the present invention and peel off photoresistance constituent.

The photoresistance of peeling off of embodiment 1 uses the using method of constituent as follows:

Provide a laminate, and the preparation method of this laminate comprises following steps: by the positive-type photosensitive resin composition (label: Qimei Industry Co., Ltd.'s system of novolac resin system; Model: TR305) in the mode of rotary coating, be coated on the glass substrate with copper metal film of 100mm * 100mm * 0.7mm.Then, with 100mmHg, carry out drying under reduced pressure, last after 5 seconds, in baking oven with 90 ℃ pre-baked 2 minutes to 3 minutes, form thickness 6 the pre-baked of μ m and film.By this pre-baked mask of filming with specific pattern (exposure machine label: M & R Nano Technology that exposes; Model: AG500-4N), its exposure energy is 100mJ/cm ², then, the potassium hydroxide aqueous solution by it with 0.05wt% is developed 1 minute at 45 ℃, through pre-baked the filming of exposure, removes, and then, with pure water, cleans.After cleaning, be placed in baking oven, and carry out latter roasting 30 minutes with 235 ℃, on this copper metal film, form photoresist layer.Be soaked in the etchant that contains phosphoric acid and carried out etch processes, not removed by the copper metal film of photoresist layer protection, then, with washed with de-ionized water dry, can be obtained laminate.The photoresistance of peeling off that above-mentioned laminate is soaked in to the embodiment 1 of 50 ℃ is used in constituent, and soaks 20 minutes, then, also dry with washed with de-ionized water after taking-up.

<< embodiment 2 to 9 and comparative example 1 are to 9>>

Embodiment 2 to 9 and comparative example 1 to 9 are with the step identical with embodiment 1, to prepare this to peel off photoresistance constituent, and different places are: the kind of feed change and use amount thereof, and as shown in table 1 and table 2.

Embodiment 2 to 9 and comparative example 1 to 9 peel off photoresistance with the using method of constituent and embodiment 1 to peel off photoresistance identical by the step of the using method of constituent, so repeat no more.

<< test item >>

Photoresistance returns is stained with detection: the photoresistance of peeling off of the embodiment of 100 weight portions 1 to 9 and comparative example 1 to 9 is used in constituent, added respectively the positive-type photosensitive resin composition that the contains novolac resin (label: Qimei Industry Co., Ltd.'s system of 2 weight portions; Model: TR305), form 18 mixed liquors, then, by 18 glass substrates with copper metal film, at 60 ℃, impregnated in respectively in described mixed liquor 2 minutes, then, whether take out respectively this 18 glass substrates with copper metal film, and use scanning electron-microscopic observation copper metal film to have photoresistance to stick, decision procedure is as follows:

Zero: copper metal film sticks without photoresistance;

*: copper metal film has photoresistance to stick.

Clean capacity check: by the embodiment of 100 weight portions 1 to 9 and comparative example 1 to 9 peel off photoresistance constituent, add respectively the positive-type photosensitive resin composition that the contains novolac resin (label: Qimei Industry Co., Ltd.'s system of XT weight portion; Model: TR305), form 18 mixed liquors.By the laminate described in embodiment 1, at 60 ℃, impregnated in respectively in described mixed liquor 2 minutes, then, whether take out and use the photoresist layer on this laminate of scanning electron-microscopic observation to divest totally, and with the number of XT consumption, judging the quality of the capacity of cleaning, decision procedure is as follows:

◎: X _t>3 weight portion, can divest the photoresist layer on this laminate totally;

Zero: 2.5 weight portion <X _t≤ 3 weight portions, can divest the photoresist layer on this laminate totally;

*: 2.5 weight portions>=X _t, the photoresist layer on this laminate can be divested totally, maybe cannot divest clean.

Table 1

Table 2

Experimental result from above-mentioned table 1, the photoresistance of peeling off of embodiment 1 to 3 and embodiment 7 comprises the nitrogen heterocyclic shown in formula (I), alcohol based compound, quarternary ammonium salt compound, organic solvent and water with constituent, can effectively prevent that the photoresistance of having peeled off from returning is stained with to metal level or insulation course, and has large clean capacity.

The photoresistance of peeling off of embodiment 4 to 6 and embodiment 9 comprises chain polyamine compounds, alcohol based compound, quarternary ammonium salt compound, organic solvent and the water with at least two tertiary amines with constituent, can effectively prevent that the photoresistance of having peeled off from returning is stained with to metal level or insulation course, and has large clean capacity.

The photoresistance of peeling off of embodiment 8 comprises the nitrogen heterocyclic shown in formula (I), has chain polyamine compounds, alcohol based compound, quarternary ammonium salt compound, organic solvent and the water of at least two tertiary amines with constituent, can effectively prevent that the photoresistance of having peeled off from returning is stained with to metal level or insulation course, and has large clean capacity.

Comparative example 1 and 2 the photoresistance of peeling off are not used quarternary ammonium salt compound with constituent, and clean capacity is not good.

Comparative example 3,6,7 and 9 peel off the chain polyamine compounds that photoresistance is not used the nitrogen heterocyclic shown in formula (I) with constituent or has at least two tertiary amines, have the photoresistance of having peeled off and return the problem of being stained with on metal level or insulation course, and clean capacity is not good.

Comparative example 4,5 and 8 the photoresistance of peeling off are not used the application's alcohol based compound with constituent, have the photoresistance of having peeled off and return the problem of being stained with on metal level or insulation course.

In sum, this peel off photoresistance with constituent by the cooperative effect of described composition, making this peel off photoresistance can prevent with constituent that the photoresistance of having peeled off from returning and be stained with to metal level or insulation course, then promote the yield of successive process, and this is peeled off photoresistance and has the large capacity of cleaning with constituent, can make the photoresistance of peeling off of per unit volume increase by the amount that constituent is peeled off photoresistance, then can promote production capacity and utilization benefit, so really can reach object of the present invention.

Claims

1. A composition for stripping photoresist, characterized in that it comprises:

Amine compounds, including at least one tertiary amine compound consisting of the following groups: nitrogen heterocyclic compounds represented by formula (I) and chain polyamine compounds with at least two tertiary amines;

In formula (I), A and B represent respectively or The condition is that at least one of A and B represents Wherein, the R represents an unsubstituted C ₁ to C ₄ alkyl group, or a substituted C ₁ to C ₄ alkyl group;

Alcohol-based compounds, including at least one first alcohol-based compound composed of the following groups: sugar-based compounds and alkyne-containing alcohol-based compounds;

Quaternary ammonium compounds;

organic solvents; and

water.

2. The composition for stripping photoresist according to claim 1, wherein the substituted _C1 to _C4 alkyl is selected from the group consisting of _C1 to _C4 alkyl substituted by hydroxyl, amino substituted A C ₁ to C ₄ alkyl group, or a C ₁ to C ₄ alkyl group substituted by a cyano group.

3. The composition for stripping photoresist according to claim 1, wherein the chain polyamine compound having at least two tertiary amines is selected from the group consisting of N,N,N',N'-tetramethylethylenedi Amine, N,N,N',N'-tetramethylpropylenediamine, bis[2-(N,N-dimethylamino)ethyl]ether, N,N,N',N'', N''-pentamethyldiethylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, or combinations thereof.

4. The composition for stripping photoresist according to claim 1, characterized in that, based on 100 parts by weight of the total amount of the amine compound, the amount of the alcohol compound used ranges from 10 to 100 parts by weight. The ammonium salt compound is used in an amount ranging from 5 to 100 parts by weight, the organic solvent is used in an amount ranging from 500 to 4,000 parts by weight, and the water is used in an amount ranging from 100 to 1,000 parts by weight.

5 . The photoresist stripping composition according to claim 1 , wherein the organic solvent comprises a first solvent; the first solvent is selected from glycol compounds, alcohol ether compounds, or combinations thereof.

6. The composition for stripping photoresist according to claim 1, wherein the sugar compound is selected from glucose, mannose, galactose, sorbitol, mannitol, xylitol, or combinations thereof .

7. The photoresist stripping composition according to claim 1, wherein the alkynyl-containing alcohol compound is selected from 3-methyl-1-butynyl-3-alcohol, 3-methyl- 1-pentynyl-3-ol, 3,6-dimethyl-4-octynyl-3,6-diol, 2,4,7,9-tetramethyl-5-decynyl-4 ,7-diol, 3,5-dimethyl-1-hexynyl-3-ol, 2-butynyl-1,4-diol, or combinations thereof.

8. A method for using a composition for stripping photoresist, characterized in that it comprises the following steps:

Provide a laminate, including a substrate, a metal layer or insulating layer formed on the substrate, and a photoresist layer formed on the metal layer or insulating layer;

contacting the photoresist layer of the laminate with the composition for stripping photoresist according to any one of claims 1 to 7, until the photoresist layer is peeled from the laminate;

Give cleaning treatment.

9 . The method of using the composition for stripping photoresist according to claim 8 , further comprising performing drying treatment after the cleaning treatment. 10 .