KR100640107B1 - Cleaning composition for removing resists and manufacturing method of semiconductor device - Google Patents

Abstract

The resist removal cleaning liquid according to the present invention comprises at least one acid (component C) selected from the group consisting of a hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (component B1), an organic acid and an inorganic acid. ), And water (component D), and have a hydrogen ion concentration (pH) of 4 to 8. Moreover, it is also preferable to add ammonium salt (component E1) to the said component. Thereby, in the semiconductor device manufacturing method process, such as a copper wiring process, removal property, such as a resist residue, when removing the resist residue 6 and other etching residue 8 after an etching or ashing, Corrosion resistance of copper and an insulator film becomes high.

Ashing, Residue, Cleaning Liquid, Corrosion Resistance, Removability

Description

CLEANING COMPOSITION FOR REMOVING RESISTS AND MANUFACTURING METHOD OF SEMICONDUCTOR DEVICE}

1A-1K are cross-sectional views of each process of one embodiment of a copper wiring process using a cleaning liquid in accordance with the present invention.

2A to 2I are cross-sectional views of respective processes of another embodiment of a copper wiring process using a cleaning liquid according to the present invention.

3A to 3K are cross-sectional views of each step of a typical copper wiring process using a conventional cleaning liquid.

<Explanation of symbols for main parts of drawing>

1: copper wiring

2: insulating film

3: silicon nitride film

4: Low-k film

5: resist layer

6: resist residue

7: altered layer

21: Via Hole

The present invention provides a method for peeling and removing a reaction residue (etch residue) with a resist film, a resist residue, and other etching gas remaining after dry etching in the process of forming a metal wiring mainly composed of copper on a semiconductor substrate. The cleaning liquid for resist removal and the manufacturing method of the semiconductor using this are related.

In the highly integrated semiconductor device manufacturing process, a resist film is usually applied on a wiring material such as a metal film serving as a conductive wiring material or an interlayer insulating film material for the purpose of insulating the wiring, and a desired resist pattern is formed by a photolithography process. After molding, the process of performing dry etching using this resist film as a mask and removing the remaining resist film is employed. As a process of removing this resist film, the wet process which peels and removes the resist residue which remains on a wiring material or an interlayer insulation material after plasma ashing is common is used.

Conventionally, an Al-based wiring material is generally used as the wiring material, and a cleaning liquid based on a fluorine-based compound (Japanese Patent Application Laid-Open No. 7-201794, Japanese Patent Application Laid-Open No. 8-202052, Japan) Japanese Unexamined Patent Application Publication No. 11-271985), a hydroxylamine-containing cleaning liquid (US Pat. No. 5,332,332), a quaternary ammonium hydroxide-containing cleaning liquid (JP-A-7-247498), and the like.

However, in recent years, miniaturization and speed-up of semiconductor elements have progressed, and the drastic change of the manufacturing process of a semiconductor device is progressing. For example, due to the demand for higher speed of semiconductor devices, wiring materials are converted to Cu or Cu alloys having lower electrical resistance as compared to conventional Al or Al alloys, and the interlayer insulating film is a conventional p-TEOS. (Tetra Ethyl Ortho Silicate) A conversion to a so-called Low-k film having a lower dielectric constant than that of a film or the like is being advanced. Examples of low-k films currently promising include films made of inorganic materials such as porous silica, films made of organic materials such as polyimide and polyallylene, and films made of a mixture of the above inorganic materials and organic materials. Can be.

In addition, with the miniaturization, chemically amplified excimer resists such as KrF excimer laser resists and ArF excimer laser resists are also used as resists used in the photolithography process, and high performance cleaning liquids are desired.

The problem of the conventional washing | cleaning liquid and the manufacturing method of the semiconductor device using the same is demonstrated below.

On the semiconductor substrate on which elements such as transistors (not shown) are formed, a buried first copper wiring 1 is formed between the first insulating films 2 using a known damascene process. 3A, a silicon nitride film 3, which is a protective film for copper wiring, and a Low-k film 4, which is a low dielectric constant interlayer insulating film, are sequentially formed thereon, and a resist film 5 patterned thereon in a predetermined shape. ). As the resist material, for example, a chemically amplified excimer resist corresponding to KrF excimer laser exposure or ArF excimer laser exposure is used.

Next, referring to FIG. 3B, the via-hole 21 is formed by dry etching the Low-k film 4 until the silicon nitride film 3 is exposed using the resist film 5 as a mask. At this time, the reaction product of the gas used for dry etching, the Low-k film, and the resist film is left, and the resist residue 6 is deposited in the via hole 21.

Next, referring to FIGS. 3B and 3C, the resist film 5 is removed by plasma ashing. At this time, the altered layer 7 is formed on the low-k film surface 4 by the reaction of heat and plasma by ashing.

Next, referring to FIGS. 3C and 3D, a treatment with a cleaning liquid based on a conventional fluorine-based compound is performed to remove the resist residue 6. If this resist residue remains, it will cause a poor electrical connection with the subsequent upper wiring. Therefore, in order to ensure the removal of resist residues, since the cleaning liquid having an etching action has also been used for the insulating film, the deteriorated layer 7 or the Low-k film 4 itself on the low-k film surface It etched and caused the internal diameter of the via hole 21 to expand.

Subsequently, with reference to FIG. 3E, a patterned resist film 5 for forming trenches is formed over the Low-k film 4 in order to form wiring to be connected to the via hole 21.

Next, referring to FIG. 3F, using the resist film 5 as a mask, the low-k film is dry-etched to an intermediate position of the low-k film 4 to form the trench 22. At this time, the resist residue 6 which is a reaction product of the gas used for the dry etching, the Low-k film and the resist is deposited in the via hole 21 and the trench 22.

Next, referring to FIGS. 3F and 3G, the resist film 5 is removed by plasma ashing. At this time, the deterioration layer 7 is formed on the surface of the low-k film 4 by the reaction of heat and plasma by ashing.

Next, referring to Figs. 3G and 3H, a treatment with a cleaning liquid based on a conventional fluorine-based compound is performed to remove the resist residues 6. At this time, the deterioration layer 7 on the surface of the low-k film is etched with the removal of the resist residue, and the enlargement of the inner diameter of the via hole 21 and the width of the trench 22 occur.

Next, referring to FIG. 3I, the silicon nitride film 3 is removed by dry etching to expose the first copper wiring 1. At this time, the etching residues 8 are deposited in the via holes 21.

Next, referring to FIG. 3J, a treatment with a cleaning liquid is performed to clean the copper wiring surface. In the cleaning liquid based on the conventional fluorine-type compound, when the removal effect of a resist, a resist residue, and other etching residues was improved, the 1st copper wiring 1 had a problem which corroded. Therefore, in order to prevent corrosion of a 1st copper wiring, copper corrosion inhibitors, such as benzotriazole (BTA), were added (JP-A-2001-83712). However, even in such a cleaning agent, in order to further enhance the removal effect of the resist residue, there was a problem that the corrosion protection effect of copper is lowered.

Next, referring to FIG. 3K, copper is embedded in the via hole 21 and the trench 22 by plating or the like, and the second copper wiring 10 is formed by CMP (Chemical Mechanical Polishing). However, in the case where the first copper wiring 1 is corroded by the conventional cleaning liquid, since the second copper wiring 10 cannot be completely embedded in the via hole 21, the first copper wiring 1 and the first copper wiring 1 and the first copper wiring 1 are not completely embedded. The bonding resistance with the 2 copper wirings 10 became high, or the disconnection caused the problem.

In accordance with the miniaturization of the device, the gap 11 between the wiring and the wiring is designed to be narrow. When the conventional cleaning liquid is used in the above process, the deteriorated layer 7 and the Low-k film 4 on the low-k film surface are used. ) Itself is etched, so that the gap 11 between the wiring and the wiring is further narrowed. For this reason, there has been a problem of deterioration in characteristics such as a decrease in the driving speed of the semiconductor element due to an increase in the capacitance between wirings or a defect such as a short circuit between the wirings and the wirings. Moreover, in the conventional cleaning liquid, the performance which satisfies all the removal of a resist residue, the corrosion prevention of copper, and the corrosion prevention of a Low-k film was not obtained.

In the copper wiring process, the present invention has an excellent removal effect when removing the resist film and the etching residue after ashing, the resist residue and the etching residue after ashing, and the corrosion resistance to copper and the interlayer insulating film. It is an object of the present invention to provide a cleaning liquid for removing a resist that can be used in safer and milder conditions and a semiconductor manufacturing method using the same.

In order to achieve the above object, the cleaning solution for removing a resist according to the present invention is selected from the group consisting of a hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (B1 component), an organic acid and an inorganic acid. It contains at least one acid (component C) and water (component D), characterized in that the hydrogen ion concentration pH is 4 to 8. In addition, the resist removal cleaning liquid according to the present invention may contain an ammonia salt (component E1) in addition to the components A, B1, C and D.

In addition, the other resist removal cleaning liquid according to the present invention includes a salt of hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (component B2), phosphonic acid (component C1), and water (component D). And a base (component E) containing no metal, and having a hydrogen ion concentration pH of 2 to 8. Moreover, the resist removal cleaning liquid which concerns on this invention can contain Cu anticorrosive agent (component f) other than the said A component, B2 component, C1 component, D component, and E component.

Moreover, the manufacturing method of the semiconductor device which concerns on this invention includes the process of forming a metal film which has copper as a main component, the process of forming an insulating film on it, and the process of forming a resist film on it, The etching gas and the resist film at the time of dry etching after the step of forming holes or trenches in the insulating film by performing dry etching using the resist film as a mask and the step of removing the resist by plasma treatment or heat treatment with gas. And a resist residue generated by the reaction with an insulating film such as a low-k film is removed using the above-mentioned resist removal cleaning liquid. In addition, the etching gas according to the present invention contains fluorocarbon as a main component, and the resist residues generated by the reaction of the etching gas with an insulating film such as a resist film and a low-k film include resist residues, carbon residues, and the like. Complex is included.

In addition, another method for manufacturing a semiconductor device according to the present invention includes a step of forming a metal film containing copper as a main component, a step of forming an insulating film thereon, and a step of forming a resist film thereon, Dry etching is performed using the resist film as a mask to form holes or trenches in the insulating film, and then the remaining resist film and the reaction of the etching gas with an insulating film such as a low-k film during dry etching. The resist residue which generate | occur | produces by is remove | eliminated using the said resist removal cleaning liquid.

That is, the resist removal cleaning liquid according to the present invention has high removal resistance of the resist residue and high corrosion resistance to the copper wiring film and the insulating film, so that the gap between the copper wirings is not narrowed in the manufacture of the semiconductor. In this way, the semiconductor manufacturing apparatus can be manufactured without deterioration in characteristics such as a decrease in the driving speed of the semiconductor element or a defect such as short circuit between the wiring and the wiring.

Moreover, another manufacturing method of the semiconductor device which concerns on this invention is the process of forming a metal film which has copper as a main component on a semiconductor substrate, the process of forming an insulating film on it, and the said metal in the said insulating film by dry etching. After the step of forming a hole reaching the film, the etching residue generated by the reaction between the etching gas and the insulating film during dry etching is removed using the cleaning liquid for removing the resist.

The etching gas used in the present invention is a gas containing fluorocarbon as a main component, and the main component of the etching residue produced by the reaction between the dry etching gas and the insulating film or the metal film containing copper as the main component is a carbon residue. The removal cleaning liquid can remove not only resists and resist residues, but also etching residues that do not include resists and their residues.

Here, the metal which has copper as a main component says that content of copper is 90 mass% or more, for example in this metal.

The above and other objects, features, aspects and advantages of the present invention will become apparent from the following detailed description of the invention which is understood in conjunction with the accompanying drawings.

<First Embodiment>

One resist removal cleaning liquid according to the present application is at least one acid (C) selected from the group consisting of a hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (component B1), an organic acid and an inorganic acid. Component) and water (component D), and the hydrogen ion concentration pH is 4-8.

A component in this invention is a salt of hydrofluoric acid and the base which does not contain a metal. Examples of the base containing no metal include organic amine compounds such as hydroxyamines, primary, secondary or tertiary aliphatic amines, alicyclic amines, heterocyclic amines and aromatic amines, ammonia and lower quaternary ammonium bases. Etc. are preferably used.

Examples of the hydroxyamines include hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, and N-diethylhydroxylamine.

Examples of the primary aliphatic amine include methylamine, ethylamine, propylamine, butylamine, monoethanolamine, monoisopropanolamine, 2- (2-aminoethylamino) ethanol, and the like. Examples of secondary aliphatic amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diethanolamine, N-methylethanolamine, and N-ethylethanolamine. Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine, and N-ethyldi Ethanolamine, triethanolamine, and the like.

Cyclohexylamine, dicyclohexylamine, etc. are mentioned as alicyclic amine. Examples of the heterocyclic amine include pyrrole, pyrrolidine, pyridine, morpholine, pyradine, piperidine, oxazole, thiazole, and the like. Examples of the aromatic amines include benzylamine, dibenzylamine, N-methylbenzylamine and N-ethylbenzylamine. Tetramethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide, etc. are mentioned as a lower quaternary ammonium base.

In the base mentioned above, Preferably, ammonia, monoethanolamine, tetramethylammonium hydroxide, etc. are mentioned. Especially, ammonia is especially preferable.

The component A improves the removability by reacting with the agent for generating acid with light contained in the chemically amplified excimer resist with respect to the removal of the chemically amplified excimer resist after dry etching, and the resist residue after ashing. With respect to, the removal properties are significantly improved by promoting cleavage of chemical bonds in the resist residues.

Moreover, content of A component is 0.01 mass%-1 mass%, Preferably it is 0.05 mass%-0.5 mass%. If it is less than 0.01 mass%, the peelability of a resist film, a resist residue, and other etching residue falls, and when it exceeds 1 mass%, corrosion to interlayer insulation films, such as a copper wiring and a Low-k film, will become severe and it is unpreferable.

B1 component in this invention is a water-soluble organic solvent. Although it will not specifically limit, if it is a water-soluble organic solvent, Amides, polyhydric alcohol, its derivatives, etc. are used preferably. As amides, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethyl Acetamide, N-ethylacetamide, N, N-diethylacetamide, etc. are mentioned.

As polyhydric alcohol or its derivatives, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, propylene glycol, propylene glycol mono Methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, di Propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether And diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether and the like.

Moreover, it is preferable to use the mixture of the said amide, polyhydric alcohol, or its derivative (s) as B1 component of this invention. The mixed mass ratio of the amides and the polyhydric alcohols or derivatives thereof is not particularly limited, but from the viewpoint of chemically amplified excimer resist removal after dry etching, the KrF resist (the KrF excimer laser resist) is used. In the case of removal, since the main skeleton is polyhydroxy styrene of a phenol skeleton, it is preferable that the ratio of soluble amides having a high solubility is higher, and the ArF resist (the ArF excimer laser resist) is preferably used. In the case of removal, since the main skeleton is acryl-based, the higher the solubility of polyhydric alcohols or derivatives thereof is preferable. Also, the same tendency as above for the resist residues after dry etching and ashing. That is, what is necessary is just to determine the mixed mass ratio of amides, polyhydric alcohol, or its derivatives according to the kind of resist used before dry etching.

In particular, in the manufacture of one semiconductor device, it is useful to use a mixture of amides, polyhydric alcohols or derivatives thereof as the B1 component when an ArF resist and a KrF resist are used in combination. In this case, it is particularly preferable that the mixed mass ratio of the amides in the B1 component is 0.3 to 0.5 from the viewpoint of solubility of both resists.

50 mass%-98 mass% are preferable, and, as for content of the said B1 component, More preferably, they are 60 mass%-95 mass%. If it is less than 50 mass%, the removability of a resist film and a resist residue will fall, and corrosion to a copper wiring will become severe, and even if it exceeds 98 mass%, the removability of a resist film and a resist residue will fall, and it is unpreferable.

As the C component in the present invention, at least one acid selected from the group consisting of organic and inorganic acids is used. Examples of the organic acid include aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, glycolic acid, tartaric acid and citric acid, aromatic acids such as benzoic acid, toluic acid, and phthalic acid. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. Such C component is used for adjustment of pH (hydrogen ion concentration) of the resist removal washing | cleaning liquid, and addition amount is not specifically limited.

PH of the washing | cleaning liquid for resist removal which concerns on this invention is 4-8, Preferably it is 5.5-7.5, More preferably, it is 6.5-7.5. In the present invention, the pH of the cleaning liquid has a very important influence. If the pH is less than 4, the corrosion of the copper-based metal film is severe. If the pH is above 8, the removability of the resist film, the resist residue, and other etching residues is reduced, and the corrosion of the copper-based metal film and the Low-k film is reduced. It gets worse and is not desirable.

As D component in this invention, water is used. Water ionizes salts of hydrofluoric acid, which is a component A, with a base that does not contain a metal to enhance the removal performance of resist residues and other etching residues, and increases the flash point of the cleaning liquid to facilitate handling. do.

<2nd Example>

Another resist removal cleaning liquid according to the present invention is at least one acid selected from the group consisting of a hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (component B1), an organic acid and an inorganic acid (C). Component), water (component D) and ammonium salt (component E1), and the hydrogen ion concentration pH is 4-8. That is, in this embodiment, the E1 component is added to the A component, the B1 component, the C component, and the D component of the cleaning liquid for removing the resist in the first embodiment so as to have a pH of 4 to 8.

Here, the ammonium salt (component E1) has a function of suppressing corrosion of the insulating film, and the content thereof is preferably from 0.01% by mass to 5% by mass, more preferably from 0.05% by mass to 3% by mass. This is because when the amount is less than 0.01% by mass, corrosion of insulating films such as TEOS, SiN, SiON, and SiO ₂ is severe, and when it exceeds 5% by mass, the removability of resist films, resist residues, and the like decreases.

As an E1 component in this invention, if it is an ammonium salt, it will use without a restriction | limiting in particular. For example, aliphatic monocarboxylic acid ammonium salts, such as ammonium formate, ammonium acetate, ammonium propionate, and ammonium butyrate, ammonium glycolate, ammonium oxalate, ammonium malonate, ammonium succinate, ammonium maleate, ammonium glutarate, and ammonium adipic acid Aliphatic polycarboxylic acid ammonium salts such as ammonium lactate, ammonium gluconate, ammonium tartrate, ammonium oxycarboxylic acid salts such as ammonium citrate, and ammonium phosphonic acid salts such as ammonium sulfamate.

<Third Embodiment>

Another resist removal cleaning liquid according to the present invention includes a salt of hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (component B2), phosphonic acid (component C1), water (component D), and The base (component E) which does not contain a metal is contained and hydrogen ion concentration pH is 2-8. By adding phosphonic acid (component C1) and base not containing metal (component E), copper-based metal film anticorrosiveness is improved, so that a wide pH range (pH of 2 to 8) can be used as a cleaning liquid for removing a resist. have.

Component A in the present invention is a salt of hydrofluoric acid and a base containing no metal, the details of which are as described in the first embodiment.

B2 component in this invention is a water-soluble organic solvent. Examples of the water-soluble organic solvent include, but are not particularly limited to, amides, pyrrolidones, alkylureas, sulfoxides, sulfones, imidazolidinones, polyhydric alcohols or derivatives thereof, lactones, and carboxylic acid derivatives. It is preferably used.

As the amides, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide Amide, N-ethylacetamide, N, N-diethylacetamide, and the like. Examples of the pyrrolidones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, and the like. have. Examples of the alkyl urea include tetramethyl urea and tetraethyl urea. Examples of the sulfoxides include dimethyl sulfoxide, diethyl sulfoxide and the like. Examples of the sulfones include dimethyl sulfone, diethyl sulfone, beads (2-hydroxyethyl) sulfone, tetramethylene sulfone and the like. Examples of the imidazolidinones include 1, 3-dimethyl-2-imidazolidinone, 1, 3-diethyl-2-imidazolidinone and the like.

As a polyhydric alcohol or its derivative (s), ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol Monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether Acetate, diethylene glycol monoether ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, propylene glycol, propylene glycol monome Butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, di Propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Propyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether and the like.

Examples of the lactones include γ-butyrolactone and σ-valerolactone. Methyl acetate, ethyl acetate, methyl lactate, ethyl lactate etc. are mentioned as a carboxylic acid derivative.

As the B2 component of the present invention, it is preferable to use a mixture of a sulfur-containing compound such as sulfoxides or sulfones and a polyhydric alcohol or a derivative thereof. The mixing mass ratio of the sulfur-containing compound and the polyhydric alcohol or its derivatives is not particularly limited. However, from the viewpoint of chemically amplified excimer resist removal after dry etching, when the KrF resist is removed, the main skeleton is a phenol skeleton. Since it is polyhydroxy styrene, the higher the solubility of the sulfur-containing compound is preferable, and when the resist for ArF is removed, the main skeleton is acryl-based, so that the ratio of the high solubility polyhydric alcohol or its derivative is This higher one is preferable. Also, the same tendency as above for the resist residues after dry etching and ashing. That is, what is necessary is just to determine the mixed mass ratio of a sulfur containing compound, a polyhydric alcohol, or its derivative corresponding to the kind of resist used before dry etching.

50 mass%-95 mass% are preferable, and, as for content of the said B2 component, More preferably, they are 55 mass%-90 mass%. If it is less than 50 mass%, the removal property of a resist film and a resist residue will fall, and corrosion to a copper wiring will become severe, and even if it exceeds 95 mass%, the removal property of a resist film and a resist residue will fall, and it is unpreferable.

The C1 component in the present invention is phosphonic acid. Examples of the phosphonic acid used in the present invention include diethylenetriamine penta (methylenephosphonic acid), phenylphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid, 1-hydroxyethylene-1, 1-diphosphonic acid, and 1-hydric acid. Oxypropyldene-1, 1-diphosphonic acid, 1-hydroxybutylidene-1, 1-diphosphonic acid, ethylamino beads (methylenephosphonic acid), dodecylamino beads (methylenephosphonic acid), ethylenediamine beads (Methylenephosphonic acid), ethylenediamine tetrakis (methylenephosphonic acid), hexamethylenediaminetetrakis (methylenephosphonic acid), isopropylenediamine beads (methylenephosphonic acid), isopropylenediaminetetra (methylenephosphonic acid), nitrilotris (Methylene phosphonic acid) etc. are mentioned.

The phosphonic acid (component C1) used in the present invention functions as an anticorrosive agent for an insulating film such as a copper-based metal film or a low-k film as a wiring material by using together with a base (component E) containing no metal. In addition, it has a function as a regulator of pH. Here, as for content of a C1 component, 0.1 mass%-20 mass% are preferable, More preferably, they are 0.5 mass%-15 mass%. If the content of the C1 component is less than 0.1% by mass, the corrosion resistance to the copper-based metal film or the Low-k film is lowered. If the content of the C1 component is higher than 20% by mass, the removability of the resist film, the resist residue or the etching residue is lowered. Not.

As D component in this invention, water is used and the detail is as having demonstrated in 1st Example.

E component in this invention is a base which does not contain a metal. There is no restriction | limiting in particular as a base which does not contain the metal used for this invention, A hydroxyamine, primary, secondary, or tertiary aliphatic amine, alicyclic amine, heterocyclic amine, aromatic amine, etc. Organic amine compounds, ammonia, lower quaternary ammonium bases and the like are preferably used.

Examples of the hydroxyamines include hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, and N-diethylhydroxylamine.

Examples of the primary aliphatic amines include methylamine, ethylamine, propylamine, butylamine, monoethanolamine, monoisopropanolamine, 2- (2-aminoethylamino) ethanol, and the like. Examples of secondary aliphatic amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diethanolamine, N-methylethanolamine, and N-ethylethanolamine. Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyl diethanolamine, and N-ethyl diethanol Amine, triethanolamine, and the like.

Cyclohexylamine, dicyclohexylamine, etc. are mentioned as alicyclic amine. Examples of the heterocyclic amine include pyrrole, pyrrolidine, pyridine, morpholine, pyradine, piperidine, oxazole, thiazole, and the like. Examples of the aromatic amines include benzylamine, dibenzylamine, N-methylbenzylamine, and N-ethylbenzylamine. Tetramethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide, etc. are mentioned as a lower quaternary ammonium base.

The base (E component) which does not contain the metal used for this invention functions together with phosphonic acid (C1 component), and functions as an anticorrosive agent with respect to insulating films, such as a copper-type metal film as a wiring material, or a Low-k film. It has a function as a regulator of pH. Here, as for content of E component, 0.1 mass%-20 mass% are preferable, More preferably, they are 0.5 mass%-15 mass%. If the content of the E component is less than 0.1% by mass, the corrosion of the copper-based metal film and the Low-k film increases, and if it exceeds 20% by mass, the removability of the resist film, the resist residue, and other etching residues is deteriorated, which is not preferable. .

PH of the washing | cleaning liquid for resist removal in a present Example is 2-8, Preferably it is 2.5-7.5. If the pH is less than 2, the corrosion of the copper-based metal film is increased. If the pH is higher than 8, the removability of the resist film, the resist residue, and other etching residues is reduced, and the corrosion of the copper-based metal film and the Low-k film is reduced. As it becomes large, it is not preferable. In this embodiment, the addition of phosphonic acid (C1 component) and a base (component E) containing no metal improves the metal film anticorrosive property, so that the cleaning liquid for removing a resist in the first and second embodiments is used. Compared to the pH range (pH 4 to 8), a wider pH range (pH 2 to 8) can be used as the cleaning liquid for removing a resist.

<Fourth Example>

Another resist removal cleaning liquid according to the present invention comprises a salt of hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (component B2), phosphonic acid (component C1), water (component D), The base (E component) and Cu anticorrosive agent (F component) which do not contain a metal are contained, and hydrogen ion concentration pH is 2-8. That is, in this embodiment, the F component is further added to the A component, the B2 component, the C1 component, the D component, and the E component of the resist removal cleaning liquid in the third embodiment, so that the pH is 2 to 8.

Here, Cu anticorrosive agent (F component) has the effect | action which suppresses corrosion of a copper-type metal film, The content is preferably 0.01 mass%-5 mass%, More preferably, it is 0.05 mass%-3 mass%. If the amount is less than 0.01% by mass, the corrosion of the copper-based metal film is severe, and if it exceeds 5% by mass, the removability of the resist film, the resist residue and the like is lowered.

As the F component in the present invention, triazoles, aliphatic carboxylic acids, aromatic carboxylic acids or aminocarboxylic acids are preferably used. Moreover, two or more types of these F components can also be used together. As the triazoles, benzotriazole, o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole and dihydroxypropylbenzotriazole Etc. can be mentioned. Examples of the aliphatic carboxylic acids include oxalic acid, malonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, itaconic acid, glutanoic acid, adipic acid, lactic acid, malic acid, citric acid, tartaric acid, and the like. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, 5-sulfosalicylic acid, 2,4-dihydroxybenzoic acid, and the like. Examples of aminocarboxylic acids include glycine, dihydroxyethylglycine, alanine, varine, leucine, asparagine, glutamine, aspartic acid, glutanoic acid, lidine, arginine, iminodiacetic acid, nitriloacetic acid, ethylenediaminetetraacetic acid, 1, 2 -Cyclohexadiamine tetraacetic acid, diethylenetriamine pentaacetic acid, etc. are mentioned.

Next, an embodiment of a method for manufacturing a semiconductor device comprising removing a resist film, a resist residue, and other etching residues using a resist removal solution removal cleaning liquid according to the present invention is described. For example, it demonstrates below.

<Fifth Embodiment>

One embodiment of the copper wiring process using the cleaning liquid according to the present invention will be described with reference to FIGS. 1A to 1K. 1A-1C are the same as the case of FIGS. 3A-3C in a conventional process. Here, referring to FIGS. 1C and 1D, the resist residue 6 generated when the via hole 21 is formed is removed using the cleaning liquid according to the present invention. In the cleaning liquid according to the present invention, since the etching amount of the low-k film 4 and its altered film 7 is very small, the inner diameter of the via hole 21 does not increase.

1E-1G are the same as FIG.3E-3G in a prior process. Next, referring to Figs. 1G and 1H, the resist residue generated during the formation of the trench 22 is removed using the cleaning liquid according to the present invention. Since the cleaning liquid according to the present invention has a very small etching amount with respect to the Low-k film 4 and its altered film 7, the enlargement of the via hole inner diameter and the trench width does not occur.

Subsequently, referring to FIG. 1I, the silicon nitride film 3 is removed by dry etching to expose the first copper wiring 1. At this time, the etching residue 8 which arises by reaction of an etching gas and silicon nitride is deposited on the surface of the 1st copper wiring 1. Next, with reference to FIGS. 1I and 1J, the surface of the first copper wiring 1 is cleaned using the cleaning liquid according to the present invention. At this time, the cleaning liquid according to the present invention does not corrode the surface of the first copper wiring 1 unlike the conventional cleaning liquid. Next, referring to FIGS. 1J and 1K, the via holes 21 and the trenches may be formed by an electroplating method, a reflow sputtering method, or a metal organic chemical vapor deposition (MOCVD) method, which is a chemical vapor deposition (CVD) using an organic metal compound. The copper is embedded in 22), and unnecessary portions are removed by CMP to form the second copper wiring 10. Since the washing | cleaning liquid which concerns on this invention does not corrode the surface of the 1st copper wiring 1, the joining of the 1st copper wiring 1 and the 2nd copper wiring 10 is favorable, and a joining resistance becomes high or a disconnection is carried out. There is no problem such as becoming. In addition, the cleaning liquid according to the present invention has very low etching on the low-k film 4 and its altered layer 7, and the gap 11 between the copper wiring and the copper wiring is not narrowed, so that the characteristics of the semiconductor element are deteriorated. Or a problem such as a short between wirings does not occur.

<Sixth Example>

Another embodiment of the copper wiring process using the cleaning liquid according to the present invention will be described with reference to FIGS. 2A to 2I. 2A and 2B are similar to FIGS. 3A and 3B in the conventional process. 2B and 2C, after dry etching of the via hole 21, the plasma ashing treatment is not performed or is insufficiently performed, and the resist film 5 is used using the cleaning solution according to the present invention in a state in which the resist film 5 is left. ) And resist residue (6). This embodiment is preferable because the altered layer is not formed on the low-k film 4 surface.

2D and 2E are the same as FIG. 3E and 3F in a conventional process. After the dry etching of the trench, the plasma ashing process is not performed or is insufficiently performed, leaving the resist film 5, and referring to FIGS. 2E and 2F, the resist film 5 and the cleaning liquid according to the present invention are used. The resist residue 6 is removed. This embodiment is preferable because no strained layer is formed on the surface of the Low-k film 4.

Subsequently, referring to FIG. 2G, the silicon nitride film 3 is removed by dry etching to expose the first copper wiring 1. At this time, the etching residue 8 which arises by reaction of an etching gas and silicon nitride is deposited on the surface of the 1st copper wiring 1. Next, with reference to FIG. 2G and FIG. 2H, the surface of the 1st copper wiring 1 is wash | cleaned using the washing | cleaning liquid which concerns on this invention. The cleaning liquid according to the present invention does not corrode the surface of the first copper wiring 1 unlike the conventional cleaning liquid. Next, with reference to FIGS. 2H and 2I as described above, copper is embedded in the via holes 21 and the trenches 22, and unnecessary portions are removed to form the second copper wiring 10. Since the washing | cleaning liquid which concerns on this invention does not corrode the surface of the 1st copper wiring 1, the joining of the 1st copper wiring 1 and the 2nd copper wiring 10 is favorable, and a joining resistance becomes high or a disconnection is carried out. There is no problem such as becoming. In addition, the cleaning liquid of the present invention has very small etching to the low-k film 4, and the gap 11 between the copper wiring and the copper wiring is not narrowed. Therefore, problems such as deterioration in characteristics of the semiconductor element or short circuit between the wirings are caused. Does not occur.

Hereinafter, the present invention will be described in more detail. Removability of the resist residue by dry etching of the resist removal cleaning liquid according to the present invention, the etching residue caused by the reaction of the etching gas and the inorganic film, and the corrosion resistance to the copper film or the Low-k film are as follows. Evaluation was performed as described above.

(1) Preparation of cleaning liquid for removing resist

As an example of the resist removal cleaning liquid of the first embodiment, the resist removal cleaning liquid of the first embodiment to the twenty-first embodiment is used as the embodiment of the resist removal cleaning liquid of the second embodiment to Examples 22 to 25 The resist removal cleaning liquid of the Example was used as the resist removal cleaning liquid in the 3rd Example, the resist removal cleaning liquid of Examples 26-56, and 57th of the resist removal cleaning liquid in 4th Example The cleaning liquid for removing a resist of Examples-61 was prepared.

The resist removal cleaning liquid in Example 1 mixes 95 mass% of all the required component D (water) amounts with A component, B1 component of predetermined mass% shown in Tables 1-3, and is nitric acid which is C component. And small amount of propionic acid was added, it adjusted to predetermined | prescribed pH, and it prepared by adding D component and setting it as 100 mass%. In addition, the resist removal washing liquid in Example 2 mixes predetermined mass% A component, B1 component, and E1 component with 95 mass% of the whole required D component amount shown in Table 4, and is nitric acid which is C component, and A small amount of propionic acid was added to adjust the pH to a predetermined pH, and D was added to prepare 100 mass%. The amount of C component which should be added changed according to pH to adjust, and was 0.3 mass%-3 mass%.

The resist removal washing liquid in Example 3 confirms pH by adding D component to 100 mass% of A component, B2 component, C1 component, and E component of predetermined mass% shown to Tables 5-8. While preparing. In addition, the resist removal washing liquid in Example 4 adds D component to 100 mass% of A component, B2 component, C1 component, E component, and F component of predetermined mass% shown in Table 9, and sets pH as it is. It prepared while confirming.

(2) resist residue removal property

Referring to Fig. 1A, a buried type first copper wiring 1 is formed between a silicon oxide film, which is the first insulating film 2, using a conventional damascene process, and thereon a thickness of 60 nm as a protective film of the first copper wiring. A silicon nitride film 3 and a low-k film having a thickness of 600 nm and a CVD-SiON film (dielectric constant of 2.8) (4) were sequentially formed, and a patterned positive resist layer 5 having a thickness of 400 nm was formed thereon. . Here, PAR-101 (manufactured by Sumitomo Chemical Co., Ltd.), which is a chemically amplified ArF excimer resist containing an acrylic resin, was used as the ArF resist, and SEPR, a chemically amplified KrF excimer resist containing a phenol resin, was used as the KrF resist. -430 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

Next, with reference to FIG. 1B, the CVD-SiON film which is the Low-k film 4 is dry-etched with the mixed pressure of 10 kPa, RF power 300W, the mixed gas of fluorocarbon and Ar using a parallel plate RIE, Via holes 21 were formed to expose silicon nitride film 3. At this time, resist residues 6 were found in the via holes.

Next, referring to FIG. 1C, the resist pattern after dry etching was subjected to ashing for 90 seconds at room temperature by plasma using oxygen gas. At this time, the deterioration layer 7 was formed on the low-k film surface, and the resist residue 6 was observed in the surface and the via hole 21.

Subsequently, the above-mentioned resist residue chip (size 20 mm x 20 mm) was subjected to the cleaning liquid for removing resist 200 having the composition shown in Table 1, Table 2, Table 4, Table 5, Table 6, Table 8 or Table 9. It was immersed in 3 cm <3> at 24 degreeC for 30 minutes, and it washed with water, and dried. The resist for ArF and its resist residue removal property when using the resist removal cleaning liquid in Example 1 are shown in Table 1, and the resist for KrF and its resist residue removal property are shown in Table 2. In addition, the resist for ArF and the resist residue removal property when the resist removal cleaning liquid in Example 2 was used are shown in Table 4. In addition, the ArF resist and its resist residue removal property when using the resist removal cleaning liquid in Example 3 are shown in Table 5 and Table 8, and the KrF resist and its resist residue removal property are shown in Table 6 And Table 8. In addition, the ArF resist and its resist residue removal property and the KrF resist and its resist residue removal property when using the resist removal cleaning liquid in Example 4 are shown in Table 9. In each of the above tables, ○○ and ○ indicate that no resist residues were deposited (○○ has a better surface state than ○), and × indicates that resist residues were confirmed.

Subsequently, with reference to Figs. 1E to 1G, the trench portion 22 is formed in the portion of the Low-k film 4 in the same manner as described above, and the remaining resist remains with reference to Figs. 1G and 1H. Water was removed in the same manner as above. The removal property of the resist at this time was the same as Table 1, Table 2, Table 4, Table 5, Table 6, Table 8, or Table 9.

(3) Removability of Reaction Residue of Etching Gas and Inorganic Film

Subsequently, referring to FIG. 1I, the silicon nitride film 3 is dry-etched using a parallel plate RIE with a processing pressure of 10 kPa, RF power of 300 W, and a mixed gas of fluorocarbon and Ar to form first copper wiring. (1) was exposed. At this time, the etching residue 8 was deposited on the first copper wiring surface by the reaction between the etching gas generated by the above-described dry etching and the silicon nitride film.

Next, referring to FIGS. 1I and 1J, the etching residue 8 is removed in the same manner as in (2) by the resist removal cleaning liquid having the composition of Table 3, Table 7, Table 8 or Table 9. It was. The results are shown in the corresponding tables. (Circle), (circle), (x) in Table 3, Table 7, Table 8, or Table 9 is shown on the same criteria as Table 1 or the like.

Subsequently, referring to FIG. 1K, copper is embedded in the via hole 21 and the trench 22 by the electroplating method, and the second copper wiring 10 is formed by chemical mechanical polishing (CMP). It was.

(4) corrosion resistance of copper wiring

Corrosion resistance of copper wiring was obtained by immersing a copper chip (thickness 500 nm, 20 mm x 20 mm) in a cleaning liquid having a composition shown in Tables 1 to 9 at 24 ° C. for 30 minutes and then washing with water to dry the copper plate. The etching amount (decrease in thickness) was measured by 4Probe (manufactured by Podition), which is a film thickness measuring device using fluorescent X-rays. The etching amount was less than 1 nm, and the thing of (circle) and less than 2 nm was shown to Table 1-Table 9 by making (circle) and 2 or more things into x.

(5) Corrosion Resistance of Low-k Film

The corrosion resistance of the Low-k film was washed with water after immersing the CVD-SiON film chip (thickness 500 nm, 20 mm x 20 mm) in a resist removal cleaning liquid having a composition shown in Tables 1 to 9 for 30 minutes at 24 ° C. The etching amount (reduction in thickness) of the CVD-SiON film chip when dried was measured by NanoSpec (manufactured by Nanometrics), which is an optical interference film thickness measuring apparatus. The etching amount was less than 1 nm, and the thing of (circle) and less than 2 nm was shown to Table 1-Table 9 by making (circle) and 2 or more things into x.

In Tables 1 to 9, NH ₄ F is ammonium fluoride, DMAC is N, N-dimethylacetamide, DGBE is diethylene glycol monobutyl ether, DMSO is dimethyl sulfoxide, DGME is diethylene glycol monomethyl ether, MDP is methylenediphosphonic acid, DEEA is N, N-diethylethanolamine, DMAC is N, N-dimethylacetamide, PGME is propylene glycol monomethyl ether, PGBE is propylene glycol monobutyl ether, MEA is monoethanolamine, BTA means benzotriazole.

The resist removal cleaning liquid in Examples 1 to 8 includes all components of A component, B1 component, C component, and D component, and the pH is within the range of 4 to 8. It is high in corrosion resistance, Cu film corrosion resistance and Low-k film corrosion resistance. In contrast, in Comparative Example 1, since the A component was not contained, resist removal for ArF was reduced. Since pH of the comparative example 2 is less than 4, the resist removal property and Ar film corrosion resistance for ArF fell. Since pH of the comparative example 3 is larger than 8, Cu film corrosion resistance and Low-k film corrosion resistance fell.

Also, from the third and fifth to eighth embodiments, the higher the content of diethylene glycol monobutyl ether in the B1 component, the more the acrylic resin-containing ArF resist and its residue can be removed. It can be seen.

The resist removal cleaning liquid in the ninth to sixteenth examples includes all components of the A component, the B1 component, the C component, and the D component, and the pH thereof is within the range of 4 to 8, so that the resist removal for KrF It is high in corrosion resistance, Cu film corrosion resistance and Low-k film corrosion resistance. In contrast, in Comparative Example 4, since the A component was not contained, the resist removal property for KrF was reduced. Since pH of the comparative example 5 is less than 4, Cu film corrosion resistance fell. Since the pH of Comparative Example 6 is larger than 8, the resist removal property for KrF, Cu film corrosion resistance, and Low-k film corrosion resistance were all reduced.

In addition, from the tenth and thirteenth to sixteenth examples, the higher the content of N and N-dimethylacetamide in the B1 component, the higher the removal of KrF resists and residues containing phenolic resin. Able to know.

The resist removal cleaning liquid in Examples 17-21 includes all components of A component, B1 component, C component and D component, and the pH is within the range of 4 to 8, so that the etching residue is removed. It is high in corrosion resistance, Cu film corrosion resistance and Low-k film corrosion resistance. Although the said resist residue does not contain the said resist and the resist residue, since the carbon residue derived from the etching gas contains many, the cleaning liquid for removing a resist which concerns on this invention can be applied.

In contrast, in Comparative Example 7, since the A component was not included, the etching residue removal property was reduced. Since pH of the comparative example 8 is less than 4, Cu film corrosion resistance fell. Since pH of the comparative example 9 is larger than 8, Cu film corrosion resistance and Low-k film corrosion resistance fell.

The resist removal cleaning liquid in Examples 22 to 25 contains all components of A component, B1 component, C component and D component, and the pH is within the range of 4 to 8, so that the resist removal for ArF is removed. It is high in corrosion resistance, Cu film corrosion resistance and Low-k film corrosion resistance. In contrast to the third and sixth examples in which the E1 component is not included, the symbols in the table are the same ○, but the low-k film corrosion resistance tended to be further improved. This tendency was confirmed not only for the ArF resist and its resist residue removal property, but also for the KrF resist and its resist residue removal property.

The resist removal cleaning liquids of Examples 26 to 35 contain all components of A component, B2 component, C1 component, D component and E component, and their pH is in the range of 2 to 8, and thus ArF The solvent resist removal property, Cu film corrosion resistance, and Low-k film corrosion resistance are all large. In contrast, in Comparative Example 10, since the A component was not contained, the resist removal property for ArF was reduced. Since pH of the comparative example 11 is smaller than 2, Cu film corrosion resistance fell. Since pH of the comparative example 12 is larger than 8, Cu film corrosion resistance and Low-k film corrosion resistance fell.

Further, from Examples 27 and 30 to 33, the higher the content of diethylene glycol monomethyl ether in the B2 component, the more the acrylic resin-containing ArF resist and its residue can be removed. It can be seen.

The cleaning liquid for removing a resist in Examples 36 to 45 includes all components of A component, B2 component, C1 component, D component and E component, and the pH thereof is in the range of 2 to 8, so that KrF The solvent resist removal property, Cu film corrosion resistance, and Low-k film corrosion resistance are all large. In contrast, in Comparative Example 13, since the A component was not contained, the KrF resist removal property was reduced. Since pH of the comparative example 14 is smaller than 2, Cu film corrosion resistance fell. Since the pH of Comparative Example 15 is larger than 8, the resist removal property for KrF, Cu film corrosion resistance, and Low-k film corrosion resistance were all reduced.

Further, from Examples 37 and 40 to 43, it can be seen that the higher the dimethyl sulfoxide content in the B2 component, the more the KrF resist and the residue containing phenolic resin can be removed. have.

The cleaning liquid for removing a resist in Examples 46 to 50 includes all components of A component, B2 component, C1 component, D component, and E component, and the pH thereof is within the range of 2 to 8, so that etching liquid Residue removal, Cu film corrosion resistance and Low-k film corrosion resistance are all great. The present etching residue does not contain the resist and the resist residue, but since the carbon residue derived from the etching gas is large, the cleaning liquid for removing the resist according to the present invention can be applied.

In contrast, in Comparative Example 16, since the A component was not contained, the etching residue removal property was reduced. Since the pH of Comparative Example 17 was less than 2, the etching residue removal property and the Cu film corrosion resistance were lowered. Since pH of the comparative example 18 is larger than 8, Cu film corrosion resistance and Low-k film corrosion resistance fell.

The resist removal cleaning liquid in Examples 51-56 contains all components of A component, B2 component, C1 component, D component, and E component, and since the pH is in the range of 2-8, ArF The resist removal property for resist, resist removal property for KrF, etching residue removal property, Cu film corrosion resistance and Low-k film corrosion resistance are all great. In the above embodiment, the B2 component is a sulfur-containing compound (for example, dimethyl sulfoxide) or an amine (for example, N, N-dimethylacetamide) and a polyhydric alcohol or a derivative thereof (for example, diethylene glycol). Monomethyl ether, diethylene glycol monobutyl ether, etc.) shows that the mixture is preferable.

The resist removal cleaning liquid in Examples 57-61 contains all the components of A component, B2 component, C1 component, D component, E component, and F component, and the pH is in the range of 2-8. Therefore, resist removal for ArF, resist removal for KrF, etching residue removal, Cu film corrosion resistance and Low-k film corrosion resistance are all great. The present etching residue does not contain the resist and the resist residue, but since the carbon residue derived from the etching gas contains a large amount, the cleaning liquid for removing a resist according to the present invention can be applied.

On the other hand, in Comparative Example 21, since the A component was not contained, the resist removal property for ArF, the resist removal property for KrF, and the etching residue removal property became small. Since the comparative example 22 had a pH less than 2, etching residue removal property and Cu film corrosion resistance fell. Since the pH of Comparative Example 23 was larger than 8, the resist removal property for KrF, Cu film corrosion resistance, and Low-k film corrosion resistance were lowered.

While the invention has been described in detail, it is for the purpose of illustration and not of limitation, and it will be clearly understood that the spirit and scope of the invention is limited only by the appended claims.

As described above, the cleaning liquid of the present invention has high removability of resist residues caused by resist and dry etching, and long-term etching residues by reaction between dry etching gas and inorganic film, and corrosion resistance of copper wiring and Low-k film. Since it is high, there is no enlargement of via hole diameter and trench width, the space | interval between wirings can be maintained, and manufacture of a highly integrated semiconductor device is possible without degrading the characteristic of a semiconductor element.

Claims (6)

In the cleaning liquid for removing a resist, Contains at least one acid (component C) and water (component D) selected from the group consisting of a hydrofluoric acid and a base containing no metal (component A), a water-soluble organic solvent (component B1), an organic acid and an inorganic acid And the content of at least one acid (component C) selected from the group containing the organic acid and the inorganic acid is 0.3% by mass to 3% by mass, and the hydrogen ion concentration pH is 4-8. . In the cleaning liquid for removing a resist, Contains a salt of hydrofluoric acid with a base that does not contain a metal (component A), a water-soluble organic solvent (component B2), phosphonic acid (component C1), water (component D), and a metal-free base (component E) The content of the phosphonic acid (C1 component) is 0.1% by mass to 20% by mass, the content of the base (component E) not containing the metal is 0.1% by mass to 20% by mass, and the hydrogen ion concentration pH is 2 It is -8, The cleaning liquid for resist removal characterized by the above-mentioned. In the manufacturing method of a semiconductor device, Forming a metal film containing copper as a main component on a semiconductor substrate; Forming an insulating film thereon; Forming a hole reaching the metal film in the insulating film by dry etching; Process of removing the etching residue which arises at the time of dry etching using the resist removal washing | cleaning liquid of Claim 1 or 2. Method for manufacturing a semiconductor device comprising a. The method of claim 1, A cleaning liquid for removing a resist, further comprising an ammonium salt (component E1). In the manufacturing method of a semiconductor device, Forming a metal film containing copper as a main component on a semiconductor substrate; Forming an insulating film thereon; Furthermore, the process of forming a resist film thereon, Forming a hole or a trench in the insulating film by performing dry etching using the resist film as a mask; After the step of removing the resist by plasma treatment or heat treatment with a gas, a step of removing the remaining resist residues using the cleaning solution for removing a resist according to claim 1 or 2. Method for manufacturing a semiconductor device comprising a. In the manufacturing method of a semiconductor device, Forming a metal film containing copper as a main component on a semiconductor substrate; Forming an insulating film thereon; Furthermore, the process of forming a resist film thereon, After the process of forming a hole or a trench in the said insulating film by performing dry etching using the said resist film as a mask, the resist film which remain | survives at the time of dry etching and the resist film which remain | survives is made into the resist of Claim 1 or 2. Removal process using removal cleaning solution Method for manufacturing a semiconductor device comprising a.

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