KR101366904B1 - Stripper composition for removing dry etching residue and stripping method - Google Patents

Abstract

The present invention provides a release agent composition for peeling a resist film on a semiconductor or FPD substrate and a peeling method using the same. More specifically, the present invention provides a release agent composition for removing a photoresist film remaining after pattern formation and a modified polymer etching residue after dry etching, and a peeling method using the same.

Photoresist film, dry etching, release agent composition.

Description

Stripping solution composition for removing dry etching residues and stripping method using the same {STRIPPER COMPOSITION FOR REMOVING DRY ETCHING RESIDUE AND STRIPPING METHOD}

The present invention relates to a release agent composition and a peeling method for peeling a resist film and a dry etching residue on a semiconductor or a substrate for a flat panel display (hereinafter referred to as "FPD"). Lithographic techniques using resists are employed in semiconductor device and FPD manufacturing processes. Specifically, a resist is formed on the substrate, the resist is patterned by an exposure technique, and then the lower substrate is etched using the resist as a mask to form wiring and elements. Especially in the manufacture of semiconductor devices, wiring and element formation by dry etching employing a special gas are common for the purpose of forming a finer structure. In addition, the resist after forming a wiring or an element is generally removed by a release agent. For example, Japanese Patent Application Laid-open No. Hei 9-319098 discloses a method of depositing and removing a substrate by about 70 ° C. for 10 minutes using a release agent composition composed of ammonium hydroxide, alkanol amine, sugar alcohol, chelating agent, and organic solvent. have.

In the manufacture of FPD, on the other hand, the formation of wiring and the like by wet etching employing chemicals has been mainstream until now, but in this field, a dry etching process is introduced in order to cope with the miniaturization and low cost of wiring.

In resist stripping by dry etching, there are modified etching residues generated by dry etching in addition to the resist component as objects to be removed. The residue cannot be removed by the release agent used in the conventional wet etching process.

Moreover, since the board | substrate for FPD is large in board | substrate size compared with the board | substrate for semiconductor devices like a liquid crystal display glass substrate, for example, processing methods, such as deposition in the peeling process after etching, cannot be used, and a spray method etc. Therefore, it is required to peel off the substrate for one to three minutes in a short time. Therefore, when the release agent for semiconductor devices, such as Unexamined-Japanese-Patent No. 9-319098, is used as it is, there exists a problem of the nonuniformity of the peeling performance in which resist peeling and dry etching residue removal are inadequate, or a part of resist on a wide board | substrate cannot be removed. Occurs. In addition, after peeling process, water rinse is performed in order to remove the peeling liquid adhering to a board | substrate, but in that case, the problem that the wiring on a board | substrate may corrode by the remaining peeling liquid component may generate | occur | produce, and more efficient dry etching Later release agents for FPD substrates have been requested.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a resist releasing agent composition capable of uniformly peeling a resist on a large large substrate and a dry etching residue in a short time and not causing corrosion of metal wiring.

In order to achieve the above technical problem, the resist release agent composition of the present invention, (A) urea compounds, (B) alkanolamines or hydroxides, (C) metal corrosion inhibitors, (D) organic solvents and (E) water It provides a resist release agent composition comprising a.

The resist releasing agent composition can uniformly peel off the resist on the large substrate and the dry etching residue in a short time, and does not cause corrosion or damage to the metal film on the substrate.

As the urea compounds of the component (A) used in the present invention, for example, urea, urea acetate, phosphate urea, thiourea, urea peroxide, hydroxyurea, N-methylurea, 1,1-dimethylurea, 1, Monomers such as 3-dimethyl urea, N, N-dimethyl urea, tetramethyl urea, ethyl urea, 1,3-diethyl urea, phenyl urea, 1,3-diphenyl urea, allyl urea, ethylene urea and cyclohexyl urea Compounds are preferred, among which urea, urea acetate, urea phosphate, thiourea, urea peroxide, hydroxyurea and the like are more preferred, and urea and thiourea are even more preferred.

The urea compounds may be used alone in the release agent and may be used in a mixture. 0.01-15 weight% is preferable, as for the density | concentration of the urea compound in a peeling agent, 0.1-10 weight% is more preferable, and 0.1-5 weight% is still more preferable. When the concentration of the urea compound is less than 0.01% by weight, the performance as a resist release agent, in particular, the removability of the dry etching residue is lowered. When the concentration of the urea compound is higher than 15% by weight, the solubility of the release agent is reduced or the peeling treatment is performed depending on the compound used. There is a possibility of remaining on the substrate later.

The said concentration is the density | concentration of the one compound, when urea compounds are used independently, and the density | concentration of the sum total when two or more types are mixed and used.

As hydroxides of (B) component used by this invention, an inorganic hydroxide, organic hydroxide, etc. are mentioned. Specific examples of the inorganic hydroxide include ammonium hydroxide, potassium hydroxide and sodium hydroxide, and specific examples of the organic hydroxide include tetramethylammonium hydroxide and choline.

As the alkanolamines of the component (B), monoethanolamine, diethanolamine, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, diethylamino Ethanol, nitrilotriethanol, 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine, dibutanolamine and the like.

Among these hydroxides or alkanolamines, preferred are tetramethylammonium hydroxide, choline, 2- (ethylamino) ethanol, 2- (methylamino) ethanol and 1-amino-2-propanol which are organic hydroxides. Among these, 1-amino-2-propanol is more preferable.

In the release agent of this invention, these hydroxides or alkanol amines are 10 to 60 weight% normally, Preferably it is 10 to 50 weight%, More preferably, 10 to 40.0 weight% is contained. In the release agent of the present invention, when the hydroxides or alkanolamines are less than 10% by weight, the resist stripping performance tends to deteriorate. When the release agent is more than 60% by weight, the solubility of other components decreases and manufacturing becomes difficult. There is a case.

As a metal corrosion inhibitor of (C) component used by this invention, the organic compound or sugar which contains at least 1 of the elements of nitrogen, oxygen, phosphorus, and sulfur in a molecule | numerator is preferable.

In the case of an organic compound comprising at least one of the elements of nitrogen, oxygen, phosphorus and sulfur in the molecule, for example a compound possessing at least one mercapto group in the molecule, a compound comprising at least one azole in the molecule, a molecule A benzene derivative compound having two or more hydroxy groups in the compound, a compound containing at least one hydroxy group and a carboxyl group in the molecule, a compound containing at least one mercapto group in the molecule and having 2 or more carbon atoms constituting the compound The aliphatic alcohol compound etc. which couple | bonded adjacent to the carbon couple | bonded with the carbon couple | bonded with and the hydroxyl group couple | bonded are mentioned.

Specifically, examples of the compound possessing at least one mercapto group in the molecule include thioacetic acid, thiobenzoic acid, thioglycolic acid, thioglycerol, cysteine and the like, and the compound containing at least one azole in the molecule is benzotriazole. , Tortoliazole, 4-methylimidazole, 1-hydroxybenzotriazole, 5-hydroxymethyl-4-methylimidazole, 3-aminotriazole and the like, and two or more hydroxy groups in the molecule Examples of the benzene derivatives possessing the benzene derivatives include catechol, resorcinol, hydroquinone, pyrogarol, and the like. Examples of the compound containing at least one hydroxy group and carboxyl group in the molecule include a succinic asset, tannic acid, and the like. A compound containing at least one mercapto group and having at least 2 carbon atoms constituting the compound and having a mercapto group bonded thereto The aliphatic alcohol-based compounds bonded with adjacent bonded carbon can be given thioglycolate, thioglycerol and the like.

As a saccharide which can be used as a corrosion inhibitor of the metal of (C) component in this invention, monosaccharides, such as aldose and ketose, a sugar alcohol, etc. are mentioned, for example.

Specific examples of the aldose include glyceraldehyde, threose, erythrose, arabinose, xylose, ribose, altorose, glucose, mannose, galactose, and the like. , Tagatose, fructose and the like. Moreover, as a sugar alcohol, adonitol, arabitol, xylitol, sorbitol, mannitol, igitol, etc. are mentioned.

The release agent of this invention may contain two or more types of such metal corrosion inhibitors.

Among the metal corrosion inhibitors, catechol, resorcinol, hydroquinone, pyrogarol, and sugar alcohols, which are benzene derivative compounds having two or more hydroxy groups in the molecule, are preferable, and catechol and sorbitol are more preferable. Do.

In the peeling agent of this invention, the corrosion inhibitor of these metals is 0.01 to 20 weight% normally, Preferably it is 0.1 to 15 weight%, More preferably, 0.1 to 10 weight% is contained. When the corrosion inhibitor of the metal in the release agent of the present invention is less than 0.01% by weight, there is a tendency that the corrosion inhibitory effect on the metal is less likely to be exhibited, and when it is more than 20% by weight, the solubility in the release agent is deteriorated or the peeling treatment is performed. There is a possibility of remaining on the later FPD substrate.

As an organic solvent of (D) component used for this invention, it is preferable that solubility parameter (delta) is the range of 9-16.

As the solubility parameter δ of the compound, for example, it is described in a handbook such as Hansen Solubility Parameters (Charles M. Hansen, CRC Press, 2000) and the like, and specific compounds include alkylene glycol monoalkyl ether and alkylene glycol monoalkyl ether. Ester derivatives, pyrrolidone compounds, imidazolidinone compounds, γ-butylollactone and dimethyl sulfoxide. Specifically, ethylene glycol monomethyl ether, ethylene glycol mono ethyl ether, ethylene glycol mono isopropyl ether, ethylene glycol mono butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono ethyl ether, diethylene glycol mono isopropyl Ether, diethylene glycol mono butyl ether, dipropylene glycol mono methyl ether, 3-methoxy-3-methyl butanol, propylene glycol mono butyl ether, dipropylene glycol mono propyl ether, ethylene glycol phenyl ether, propylene glycol monomethyl ether acetate , N-methyl pyrrolidone, N-ethyl pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, 1,3-dipropyl- 2-imidazolidinone, gamma -butyl olactone, dimethyl sulfoxide Seed, sulfolane, etc. are mentioned.

Among them, the solubility parameter δ is preferably in the range of kV to 12, and specific examples thereof include ethylene glycol mono butyl ether, diethylene glycol mono butyl ether, N-methyl pyrrolidone, γ-butyl olactone, dimethyl sulfoxide, Sulfolane and the like. There may be only one type of such an organic solvent and may be a mixed solvent of two or more types of solvents.

When an organic solvent having a solubility parameter δ of less than ８ is used, there may be a problem in affinity with other components, and if it is mixed, it may not be a uniform composition solution, and the solubility parameter δ is an organic solvent having a value higher than 16. When using, the resist peeling performance may fall.

Moreover, as a density | concentration in the total peeling agent of the organic solvent in which the value of such a solubility parameter (delta) exists in the range of 8-16, 20 to 80 weight% is preferable, and 30 to 80 weight% is especially preferable, and 40 to 70 weight% It is more preferable that is.

When the concentration of the organic solvent is lower than 20% by weight, the peeling performance of the resist may decrease, and when higher than 80% by weight, the removal performance of the dry etching residue may decrease.

In the present invention, a residual amount of deionized water is used.

In the present invention, a surfactant may be additionally used as necessary. Anionic surfactants, cationic surfactants, and nonionic surfactants can be used, but nonionic surfactants are preferred among them.

As a nonionic surfactant, a polyoxy ethylene alkyl ether type, polyoxy ethylene alkyl phenyl ether type, polyoxy ethylene polyoxy propylene alkyl ethyl type, polyoxyethylene polyoxybutylene alkyl ethyl type, polyoxyethylene alkyl amino ether type, Surfactants, such as a polyoxyethylene alkylamide ether type, a polyethylene glycol fatty acid ester type, a sorbitan fatty acid ester type, a glycerin fatty acid ester type, an alkrolamide form, and a glycerin ester type, are mentioned, Among them, General formula (I) below, Nonionic surfactants of the polyoxyethylene polyoxypropylene alkyl ether type and the polyoxyethylene polyoxybutylene alkyl ether type described in (II), (III) and (IV) are preferable.

H-((EO) x- (PO) y) z-H (I)

H-((EO) x- (BO) y) z-H (II)

R-[((EO) a- (PO) b) c-H] m (III)

R-[((EO) a- (BO) b) c-H] m (IV)

(EO means oxyethylene group, PO means oxypropylene, PO means oxybutylene group. X and y are 0.05 to 0.5 in x / (x + y), and a and b are a / (a + b). ) Means an integer that satisfies 0.05 to 0.5. Z and c mean an integer.

Monovalent groups represented by

Divalent groups represented by

A trivalent group represented by

Means a tetravalent group represented by

R1 means a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group and / or an alkyl group, and m means an integer of 1 or more and 4 or less corresponding to the value of R.)

In the formulas (I) to (IV), the oxyethylene group is -CH ₂ -CH ₂ -O-, and the oxypropylene group is -CH (CH ₃ ) -CH ₂ -O- or -CH ₂ -CH (CH ₃ )- O-, oxybutylene group is -CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-, -CH (CH ₃ ) -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -CH ₂ -O- or -CH ₂ -CH ₂ -CH (CH ₃ ) ₂ -O-.

In formulas (I) to (IV), x and y, a and b mean an integer where x / (x + y) and a / (a + b) satisfy 0.05 to 0.7, and z and c Means an integer.

When the values of x / (x + y) and a / (a + b) are less than 0.05, respectively, the solubility at the time of preparing the peeling solution is insufficient, while when the value is larger than 0.7, the bubble removing ability of the liquid is insufficient.

The peeling liquid of this invention may contain two or more types of compounds from which the value in x / (x + y) and a / (a + b) differs.

Here, ((EO) x- (PO) y) z, ((EO) a- (PO) b) c, ((EO) x- (BO) y in the formulas (I) to (IV) The polymerized part of the oxy ethylene group, oxy propylene group, and oxybutylene group represented by) z, ((E) a- (BO) b) c may be a block polypolymer, a random polypolymer, or a random polypolymer having block properties. .

R is represented by a monovalent, divalent, trivalent or tetravalent group, and R1 means a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group and / or an alkyl group.

As a hydrocarbon group, specifically, alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, alkylene groups, such as a methylene group, ethylene group, trimethylene group, and a propylene group, alkenyl groups, such as a vinyl group and an allyl group, and a phenyl group Etc. can be mentioned.

As R represented by monovalent to tetravalent group, the residue remove | excluding hydrogen atom from the hydroxyl group of an alcohol or an amine more specifically is mentioned.

Examples of the alcohol or amine include 2-ethylhexyl alcohol, lauryl alcohol, sicyl alcohol, oleyl alcohol, tridecyl alcohol, tallow alcohol and palm oil alcohol, monoethanolamine, and the like. As the compound represented by a valent group, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2-methyl-1,2 -Furopanediol, 2-methyl-1,3-propanediol, diethanolamine, etc. are mentioned, As a compound represented by a trivalent group, glycerin, a trimetholethane, a trimetholpropane, etc. are mentioned, 4 Pentaerythritol, sorbitol, triethanolamine, ethylenediamine, propylenediamine, etc. are mentioned as a compound represented by an additional group.

In Formula (II), m represents the integer of 1 or more and 4 or less corresponding to the value of R.

In the nonionic surfactants represented by formulas (I) and (III), the average molecular weight of the total amount of the oxypropylene groups is usually 500 to 5000, preferably 900 to 3,500, and more preferably 1500 to 3500. desirable. When the average molecular weight is less than 500, the peeling performance tends to be insufficient, and when the average molecular weight exceeds 5000, the solubility at the time of manufacture tends to be deteriorated.

In the nonionic surfactant represented by Formula (II) and (IV), the average molecular weight of the whole is 300-10000, Preferably it is 500-8000, More preferably, it is 800-5000. When the average molecular weight is less than 300, the peeling performance tends to be insufficient, and when the average molecular weight exceeds 10000, the solubility at the time of manufacture tends to be poor.

As a specific example of the nonionic surfactant represented by Formula (I), a polyoxyethylene polyoxypropylene condensate is mentioned, As a specific example of the nonionic surfactant represented by Formula (II), polyoxyethylene polyoxy Butylene condensates.

These condensates may be block copolymerization or random copolymerization.

As a specific example of the nonionic surfactant represented by Formula (III), polyoxyethylene polyoxypropylene 2-ethylhexyl ether, polyoxyethylene polyoxypropylene lauryl ethyl, polyoxyethylene polyoxypropylene stearyl ether, a glycerin addition type Polyoxyethylene polyoxypropylene condensate, ethylene diamine addition type polyoxyethylene polyoxypropylene condensate, etc., The specific example of the nonionic surfactant represented by Formula (IV) is polyoxyethylene polyoxybutylene 2-ethyl. Hexyl ether, polyoxyethylene polyoxybutylene lauryl ethyl, polyoxyethylene polyoxybutylene stearyl ethyl, glycerin addition polyoxyethylene polyoxybutylene condensate, ethylene diamine addition polyoxyethylene polyoxybutylene condensate, etc. are mentioned. have.

Two or more types of nonionic surfactant may be contained in the peeling agent of this invention, Surfactant represented by Formula (I)-(IV) may be contained individually, respectively, and each may contain in multiple numbers.

In the release agent of the present invention, the surfactants of these formulas (I) to (IV) are usually 0.0001 to 10% by weight, preferably 0.001 to 1.0% by weight, more preferably 0.01 to 0.5% by weight. When the nonionic surfactant is lower than 0.0001% by weight, the resist on the glass substrate may not be evenly removed. When the nonionic surfactant is higher than 10% by weight, the foaming property of the release agent is severe and the handling tends to be difficult. .

As the anionic surfactant, alkyldiphenyl ether disulfonic acid, alkylene disulfonic acid, alkylbenzene sulfonic acid, dialkyl succinate sulfonic acid, monoalkyl succinate sulfonic acid, alkylphenoxyethoxyethylsulfonic acid, naputarensulfonic acid Formic acid formalin condensate, phenolsulfonic acid formalin condensate, phenylphenolsulfonic acid formalin condensate, polyoxyalkyrene alkylphenyl ether sulfate ester, polyoxyalkyrene alkyl ether sulfate ester, polyoxyalkyrenda ring phenyl ether sulfate ester, poly Oxyalkyrene arylethersulfuric acid ester, alkylmethyltaurine, acylmethyltaurine, fatty acid methyltaurine, polyoxyalkyrenealkyletherinic acid, pulleyoxyalkyrenealkylphenyletherphosphoric acid, acylsalcosine, fatty acid sarcosine, alkylsulfovacic acid, poly And oxyalkyrenealkylsulfovacic acid.

Examples of the cationic surfactants include alkyltrimethylammonium salts, alkylamidoamines, and alkyldimethylbenzyl ammonium salts.

In addition, inorganic acids, organic acids, and the like may be additionally used as necessary.

Examples of inorganic acids include eosinic acid, oxo acid, phosphoric acid, diphosphoric acid, tripulic acid, sulfuric acid, hypochlorous acid, chlorous acid, perchloric acid, acetic acid, acetic acid, next hypophosphorous acid, phosphorous acid, sulfurous acid, hydrobromic acid, hydrochloric acid, hydrofluoric acid, hydrofluoric acid, Hydrogen sulfide, acetic acid peroxide, phosphoric acid peroxide, diphosphate peroxide, sulfuric acid peroxide, bisulfate peroxide, etc. are mentioned.

Examples of organic acids include formic acid, acetic acid, propionic acid, glyoxylic acid, birvinic acid, gluconic acid, 2-ketogulic acid, 1,3-acetonedicarboxylic acid, oxalic acid, melon acid, succinic acid, gultanic acid, aziping acid, and pimeric acid. , Maleic acid, formic acid, futal acid, hydroxybutyric acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, aspartic acid, glutamic acid and the like.

The release agent of this invention can be obtained by mixing each component. The mixing order and the method of mixing are not particularly limited, and a known method can be applied.

As temperature at the time of use of the peeling agent of this invention, it is 10-80 degreeC normally, Preferably it is 30-80 degreeC, More preferably, it is the range of 40-70 degreeC.

As a method of peeling and removing the resist and dry etching residue on a FPD board | substrate using the peeling agent of this invention, the method of adjusting the peeling agent of this invention to the above-mentioned temperature range, for example, depositing a FDP board in it, or the above-mentioned The method of spraying the peeling agent of this invention heated to the temperature range to the said board | substrate is mentioned. In that case, it is also possible to remove | eliminate more effectively by rotating a board | substrate or moving under the blowing-up peeling liquid at a constant speed. In that case, you may use together a physical process, such as making the ultrasonic wave irradiate, rotate, or contacting the brush which rocked left and right.

After the peeling agent treatment, the peeling liquid remaining on the substrate surface can be removed by subsequent rinse treatment. In a rinse process, it is the same as that of the peeling agent except having adopted water or isopropyl alcohol instead of a peeling agent. In general, when water is used in the rinse step, the remaining release agent is dispersed in the rinse liquid, and the dispersed release agent component may cause corrosion of the metal wiring on the substrate, and the like, and isopropyl alcohol or the like before rinsing with water. The rinse may cause rinsing of the FDF, which causes an increase in the number of steps of manufacturing the FPD. However, the releasing agent of the present invention does not need to be rinsed with isopropyl alcohol because the corrosion of the metal wiring does not occur not only in the peeling step but also in the water rinsing step. Therefore, the number of manufacturing processes does not increase.

The release agent of this invention can be used in order to remove the resist and the dry etching residue after the dry etching process in FPD manufacture.

More specifically, (I) a step of providing a resist layer on the inorganic film formed on the substrate, (II) a step of selectively exposing the resist layer, and (III) developing a resist layer after exposure to prepare a resist pattern. The resist peeling method which consists of a process and (IV) dry-etching this inorganic film using the said resist pattern as a mask, (V) the process of peeling off the resist pattern after etching and the etching residue which arose by dry etching from a board | substrate. It is characterized by peeling the resist pattern and dry etching residue after etching using the peeling agent composition of this.

As a board | substrate employ | adopted by FDP manufacture here, not only a glass substrate but also bendable and bend | foldable plastic, paper, a nonwoven fabric, and also a rigid metal or ceramic may be sufficient as it.

As a display system for functioning as a display, not only a liquid crystal display but also an organic EL display, an inorganic EL display, a plasma display, an electric field discharge type display, an electronic paper display, an electrophoretic display, an electrolytic precipitation dissolving display, and light writing. A type electronic paper system etc. are mentioned.

The peeling agent of this invention can be employ | adopted by removal of the resist and dry etching residue after the dry etching process at the time of manufacturing this kind of FPD.

Hereinafter, the present invention will be described in more detail with reference to the following experimental examples, but the present invention is not limited to these experimental examples.

Experimental Example 1

After etching a metal film by immersing a test piece in which a wiring pattern was formed of Al-Nd / Mo and photoresist using a thin film sputtering method on a glass substrate in a conventional etching solution according to a conventional method, the compounds described in Table 1 The test piece was deposited in a peeling solution prepared from the above under the treatment conditions as specified in Table 2, washed with deionized water, and then observed with a scanning electron microscope (SEM, HITACHI S-4700) to observe the result. And the anti-corrosion ability for the bottom layer was evaluated and the results are shown in Table 2. Evaluation criteria by SEM are as follows.

[Peeling ability] ◎: Good, △: Normal, ×: Poor

[Corrosion prevention ability] ◎: Good, △: Normal, ×: Poor

TMAH: tetramethylammonium hydroxide

  MEA: Monoethanolamine

  MIPA: isopropanolamine

  BDG: diethylene glycol monobutyl ether

  EGB: Ethylene Glycol Monobutyl Ether

 TEGB: triethylene glycol monobutyl ether

  EG: ethylene glycol

    PG: Propylene Glycol

    TEG: triethylene glycol

Experimental Example 2

On the basis of the content mentioned in Experimental Example 1, the addition effect of the urea compound was observed. A specimen (Sample 1) and a specimen in which a metal film is etched by immersing a test piece in which a wiring pattern is formed of an Al-Nd / Mo double layer and a photoresist using a thin film sputtering method on a glass substrate in a conventional etching solution according to a conventional method. According to the phosphorus method, the test piece in which the wiring pattern was formed by SiN and photoresist using the thin film sputtering method using the thin film sputtering method was prepared with the normal dry etching method, and the test piece (Sample 2) which formed the pattern after each was prepared, respectively. The stripping solutions prepared from the compounds listed in Table 3 were then deposited onto specimens 1 and 2, respectively, under treatment conditions as specified in Table 4, washed with deionized water and then with a scanning electron microscope (SEM, HITACHI S-4700). The results were observed. Specimen 1 evaluated the peeling ability of the photoresist film and the corrosion protection of the metal layer and the lower layer. In specimen 2, the degree of removal of the dry etching residue was evaluated and the results are shown in Table 4.

TMAH: Tetramethylammonium Hydroxide

MEA: Monoethanolamine

MIPA: isopropanolamine

NMP: N-methyl-2-pyrrolidone

DMSO: Dimethyl Sulfoxide

THFA: Tetrahydrofuryl Alcohol

BDG: diethylene glycol monobutyl ether

EGB: Ethylene Glycol Monobutyl Ether

TEGB: triethylene glycol monobutyl ether

EG: ethylene glycol

PG: Propylene glycol

TEG: Triethylene Glycol

As shown in Table 4, when the urea-based compound was added, it was confirmed that the solubility of the dry etching residue in the release agent was excellent without affecting the peeling ability and the corrosion preventing ability of the release agent. The results are not limited to urea among urea compounds.

The resist release agent composition of the present invention can uniformly remove the resist and the dry etching residue after the dry etching step in FPD production in a short time, and also has the effect of not corroding the metal wiring even in the water rinse after the peeling step. .

Claims (10)

(A) urea compounds, (B) alkanolamines or hydroxides, (C) a metal corrosion inhibitor which is a sugar alcohol, (D) an organic solvent, and (E) containing aluminum or an aluminum alloy A resist stripper composition for peeling a single film or a multilayer film. The resist release agent according to claim 1, wherein the urea compounds of component (A) are at least one compound selected from the group consisting of urea, urea acetate, urea phosphate, thiourea, urea peroxide, and hydroxyurea. Composition. The alkanolamine of the component (B) is at least one compound selected from the group consisting of 2- (ethyl amino) ethanol, 2- (methylamino) ethanol, and 1-amino-2-propanol. Resist release agent composition, characterized in that. The resist release agent composition according to claim 1, wherein the hydroxides of component (B) are at least one compound selected from the group consisting of ammonium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, and choline. delete delete The resist release agent composition according to claim 1, further comprising catechol as the metal corrosion inhibitor. The resist release agent composition according to claim 1, wherein the organic solvent of component (D) is a compound having a solubility parameter δ in a range of 8-16. The metal according to claim 1, wherein the content of the urea compounds as the component (A) is 0.01 to 15% by weight, the content of the alkanolamines or hydroxides as the component (B) is 10 to 60% by weight and the component (C). The content of the corrosion inhibitor is 0.01-20 wt%, the content of the organic solvent of (D) component is 30-80 wt%, and the content of the water is a residual amount. (i) providing a resist layer over the inorganic film formed on the substrate, (ii) selectively exposing the resist layer, (iii) developing the resist layer after exposure to provide a resist pattern; (iv) dry etching the inorganic film using the resist pattern as a mask, (v) A resist peeling method according to any one of claims 1 to 4 and 7 to 9, comprising a step of peeling a resist pattern after etching and an etching residue generated by dry etching from a substrate. A resist stripping method, wherein the resist pattern after etching and the etching residue generated by dry etching are peeled off from the substrate.