DE10331033A1 - Cleaning composition, used for removing resist or residues of resist or from dry etching in semiconductor device production, contains fluoride of non-metal base, water-soluble organic solvent, acid and water - Google Patents

Abstract

Cleaning composition for removing resists contains (A) a salt of hydrofluoric acid (HF) and a base containing a non-metal, (B1) a water-soluble organic solvent, (C) an (in)organic acid and (D) water and has a pH of 4-8. Independent claims are also included for the following: (1) cleaning composition, pH 4-8, containing components (A), (B1), (C) and (D) as above and (E1) ammonium salt; (2) cleaning composition, pH 2-8, containing components (A) salt as above, (B) water-soluble organic solvent, (C1) phosphonic acid, (D) water and (E) a base containing a non-metal; cleaning composition, pH 2-8, containing components (A), (B2), (C2), (D) and (E) as above and (F) a copper-corrosion inhibitor; (3) 3 methods of producing a semiconductor device, in which the residues of the resist film or from dry etching are removed with the cleaning composition.

Description

The present invention relates refer to a manufacturing method of a semiconductor device and a Cleaning composition therefor. In particular, the invention relates to a cleaning composition for peeling and removing a resist film, from resist residues and other reaction residues with an etching gas (i.e. etching residues), those on a semiconductor substrate after dry etching in one step of forming a metal interconnect with copper as the main component, and a method of manufacturing a semiconductor device using the same Cleaning composition used.

Generally, in a manufacturing process highly integrated semiconductor elements, a resist film first on a Intermediate connection material, such as a metal film, which is an interconnect for electrical Conduit, and an interlayer insulation film material, the insulation ensures between interconnections, applied. A desired one Resist pattern is formed by photolithography, and dry etching is performed performed using the resist film as a mask, and then the remaining resist film is removed. To remove the Resist film it is common a wet treatment after plasma ashing for stripping and removal the remains of the resist, which are on the interconnect material and Interlayer insulation material remain to be performed by a cleaning composition is used. With an interconnect material aluminum-based, which is traditional Examples of the cleaning composition included: Fluorine compound based cleaning compositions (Japanese Patent publication JP 7-201 794 A, JP 8-202 052 A, JP 11-271 985 A), a cleaning compensation containing hydroxylamine (U.S. Patent 5,334,332) and a cleaning composition, the quaternary ammonium hydroxide contains (Japanese Patent Laid-Open JP 7-247 498 A).

With the arrival of downsizing and accelerating semiconductor elements in recent years however, the manufacturing process of the semiconductor devices changed significantly. For example, to fulfill The requirement to accelerate the semiconductor elements is aluminum or aluminum alloy, conventionally used as the interconnect material have been used by Cu or Cu alloys with a lower electrical resistance as Al or Al alloy replaced, and a p-TEOS (tetraethyl orthosilicate) film or the like, which is conventional when the interlayer insulating film has been used by one so called film low k with a lower dielectric constant as the p-TEOS film has been replaced. Examples of the film base k, the present considered promising, include: a film, which is made of inorganic material such as porous silicon oxide or the like is a film made of an organic material like polyimide, Polyarylene or the like, and a film made of a mixture of the above-mentioned inorganic and organic material is formed.

Next is the arrival of the downsizing an i-line resist that is conventional has been used in the photolithographic process by chemical increased Excimer resists, such as KrF excimer resist, ArF excimer resist and the like, been replaced, and a highly effective cleaning composition accordingly, it has been requested.

Problems of the conventional cleaning composition and the manufacturing method of a semiconductor device using the same will now be described with reference to FIG 3A - 3K described.

An element such as a transistor (not shown) is formed on a semiconductor substrate. Referring to 3A becomes a first copper interconnect 1 of an embedded type in a first insulating film 2 using a known damascene process. A silicon nitride film 3 as a protective film of the copper interconnect and a low k 4 film as an interlayer insulating film of a low dielectric constant are successively formed thereon, and a resist film 5 that is patterned with a prescribed shape is formed on it. Here, a chemically amplified excimer resist corresponding to an exposure with a KrF excimer laser or an exposure with an ArF excimer laser is used as the resist material.

Next, referring to 3B the low k 4 film is dry etched by the resist film 5 is used as a mask to expose the silicon nitride film 3 so that a through hole 21 is formed. At this time, reaction products of the gas used for dry etching and the low k film and the resist film collect in the through hole 21 as remains of resists 6 ,

Next, referring to 3B and 3C the resist film 5 removed by plasma ashing. At that time, a modified film 7 formed on the surface of the film low k 4 according to the reaction of heat and plasma during ashing.

Next, referring to 3C and 3D the Resistest 6 removed by processing with a conventional fluorine compound based cleaning composition. Any remaining resist would cause a loose electrical connection with an upper interconnect chen, which is formed afterwards. Thus, to ensure removal of the resist residue, the cleaning composition that is likely to etch the insulating film itself has been used. As a result, the modified layer 7 on the surface of the film low k as well as the film low k 4 itself etched what in a through hole 21 of an enlarged internal diameter results.

Then referring to 3E a resist film 5 patterned for trenching, patterned on the low k 4 film to form an interconnect through the through hole 21 is to be connected.

Next, referring to 3F the film low k 4, the resist film 5 is used as a mask up to its middle position to form a trench 22 dry-etched. At this time, the remains of the rugs gather 6 , which are reaction products of the gas used for dry etching, and the film low k in the through hole 21 and the trench 22 ,

Next, referring to 3G and 3H the Resistest 6 removed by processing with a conventional fluorine compound-based cleaning composition. The conventional cleaning composition removes the resist residue and etches the modified layer 7 on the surface of the film low k, so the inner diameter of the through hole 21 is enlarged and the width of the trench 22 increases.

Next, referring to 3I the silicon nitride film 3 by dry etching to expose the first copper interconnect 1 away. At this time, etching residues are collecting 8th in the through hole 21 ,

Next, referring to 3J cleaned the surface of the copper interconnect with the cleaning composition. In the conventional fluorine compound based cleaning composition, the first copper interconnect would 1 corrodes if the removal activity of the resist residue and other etching residues would be increased. Thus, a copper corrosion inhibitor such as benzotriazole (BTA) is added to prevent corrosion of the first copper interconnect (Japanese Patent Laid-Open JP 2001 83 712 A ). With such a cleaning composition, however, there is a problem that if an attempt is made to further improve the residue removal activity, the copper corrosion prevention effect would be deteriorated.

Next, referring to 3K Copper in the through hole 21 and the trench 22 filled by plating or the like. A second copper interconnect 10 is then formed by CMP (chemical mechanical polishing). When the first copper interconnect 1 However, the second copper interconnect may have been corroded by the conventional cleaning composition 10 not the through hole 21 fill completely. In such a case, the contact resistance between the first copper interconnect and the second copper interconnect 10 high, or it can even be interrupted.

A distance / interval 11 between the interconnections, narrow or narrow has been designed with the progress of the miniaturization of the elements. When the conventional cleaning composition is used for the process described above, the modified layer 7 on the surface of the low k film as well as the low k 4 film itself to further narrow the distance 11 etched between interconnects. This would cause a deterioration in properties such as a decrease in the driving speed of the semiconductor element due to an increased electrical capacitance between the interconnections or a defect such as a short circuit between the interconnections. Furthermore, with the conventional cleaning composition, performance that ensures complete removal of the resist residue as well as corrosion control of the two copper films and the low k film would not be achieved.

It is therefore an object of the present Invention, a cleaning composition for removing resists To be used under safe and moderate conditions can be removed if a resist film and an etching residue are removed after dry etching and if a resist residue and an etching residue after ashing in one Copper interconnection process can be removed, and the excellent Removal effectiveness thereof and also excellent corrosion prevention effects on a copper and interlayer insulation film, and it is also object of the invention, a manufacturing method of a semiconductor device to be provided using this cleaning composition.

This task is solved by a cleaning composition according to claim 1.

The cleaning composition for removing the resists according to the present invention is characterized in that it comprises a salt of a hydrofluoric acid and a base which contains no metal (A component), a water-soluble organic solvent (B1 component), at least one acid which consists of selected from a group consisting of an organic acid and an inorganic acid (C component) and containing water (D component), the hydrogen ion concentration (pH value) 4 to 8.

This task is also solved by a cleaning composition according to claim 2.

The cleaning composition for Removal of resists of the present invention can further Ammonium salt (E1 component) additionally to the A, B1, C and D components described above.

This task is also solved by a cleaning composition according to claim 6.

This cleaning composition for removing resists according to the present invention is characterized in that it contains a salt of hydrofluoric acid and a base containing no metal (A component), a water-soluble organic solvent (B2 component), phosphonic acid (C1 component) , Water (D component) and a base which contains no metal (E component), wherein their hydrogen ion concentration (pH) is 2 to 8.

This task is also solved by a cleaning composition according to claim 8.

The cleaning composition for Removing resists of the present invention can also Cu corrosion inhibitor (F component) in addition to those described above A, B2, C1, D and E components included.

The task is also solved by a manufacturing method according to claim 10.

The manufacturing process of a semiconductor device according to the present Invention contains the step of forming a metal film, the copper as its Main component contains on a semiconductor substrate, the step of forming an insulating film, like a low k film, on the step of forming one Resist film on it, the step of providing a hole or a trench in the insulating film by means of dry etching using the resist film as a mask, the step of removing the resist by plasma processing or heat treatment and the step of removing using the cleaning composition for removing resists, as described above, of the resist residue, the while the reaction between the etching gas and the resist film is formed, and the insulating film at the time of Dry etching.

That in the present invention used etching gas can contain fluorocarbon as its main component, and that according to the reaction between the etching gas and the resist film generated from the resist film and the insulating film such as the film low k, can be a resist residue, a carbon residue and contain a composition thereof.

The task is also solved by a manufacturing method according to claim 12.

Another manufacturing method of a semiconductor device according to the present invention includes the step of forming a metal film containing copper as its main component on a semiconductor substrate, the step of forming an insulating film such as a low k film thereon, the step of forming a resist film thereon , the step of providing a hole or trench in the insulating film by performing dry etching with the resist film as a mask, and the step of removing using the cleaning composition for removing resist as described above, the remaining resist film, and Resist residues generated during the reaction between the etching gas and the resist film and the insulating film at the time of dry etching.

As such, the cleaning composition shows for removing resists according to the present Invention an excellent removal effectiveness of the resist residue and excellent corrosion resistance effects for the copper interconnection film and the insulating film. Consequently, it is possible to manufacture the semiconductor device the narrowing a distance between the copper interconnects, the deterioration characteristics such as the decrease in driver speed, the Semiconductor elements and a defect, such as a short circuit between the interconnections to prevent.

This task is also solved by a manufacturing method according to claim 13.

Another manufacturing process a semiconductor device according to the present Invention contains the step of forming a metal film, the copper as its Main component contains on a semiconductor substrate, the step of forming an insulating film the step of making a hole in the insulating film, that reaches the metal film by dry etching and the step of removing using the cleaning composition to remove Resists, as described above, the etching residue, which is due to the Reaction between the etching gas and the insulating film during of dry etching is.

That in the present invention used etching gas can contain fluorocarbon as its main component, and thus the main component of the etching residue, which during the Reaction between the dry etching gas and the insulating film or the metal film, the copper as its main component contains, a Carbon residue. The cleaning composition for removing Resists according to the present Invention can not only resist and resist but also the etching residue Remove that does not contain the resist or the resist residue.

Herein, the metal that contains copper as its main component means that the content of the copper contains within the relevant material, for example, at least 90% by mass.

Further features and advantages of the invention result from the following description of exemplary embodiments with reference to the figures. From the figures show: 1A to 1K Cross-sectional views illustrating sequential steps in one embodiment of a copper interconnect process using the cleaning composition of the present invention;

2A to 2I Cross-sectional views illustrating sequential steps in another embodiment of the copper interconnect process using the cleaning composition of the present invention; and

3A to 3K Cross-sectional views illustrating successive steps of a typical copper interconnect process using a conventional cleaning composition.

First embodiment

A cleaning composition for Removal of resists (hereinafter also referred to as "resistance removal cleaner" called) contains a salt of a hydrofluoric acid (Hydrofluoric acid) and a base that does not contain a metal (A component), a water-soluble one organic solvent (B1 component), at least one acid which is selected from a group, that from organic acid and inorganic acid (C component), and water (D component). The hydrogen ion concentration (i.e. the pH value) 4 to 8.

The A component is the salt of the Hydrofluoric acid and a base that does not contain a metal. As a base that is not a Contains metal, are organic amino compounds, such as hydroxyamines, primary, secondary or tertiary Fatty amines, alicyclic amine, heterocyclic amine and aromatic amine, Ammonia, low quaternary Ammonium base and others, preferably used.

The hydroxyamines contain hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine and other.

The primary fatty acid amine contains methylamine, Ethylamine, propylamine, butylamine, monoethanolamine, monoisopropanolamine, 2- (2-aminoethylamino) ethanol and other. The secondary fatty amine contains Dimethylamine, diethylamine, dipropylamine, dibutylamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine and others. The tertiary fatty acid amine contains Trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Triethanolamine and others.

The alicyclic amine contains cyclohexylamine, Dicyclohexylamine and others. The heterocyclic amine contains pyrrole, Pyrrolidine, pyridine, morpholine, pyrazine, piperidine, oxazole, thiazole and other. The aromatic amine contains benzylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine and others. The low quaternary ammonium base contains Tetramethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide and other.

Are preferred among those given above Bases ammonium, monoethanolamine, tetramethylammonium hydroxide and others, of which ammonium is particularly preferred.

The A component described above improves the removal effectiveness of the chemically reinforced excimer resist after dry etching by reacting with an acid generating agent Light that is chemically amplified Excimer resist is included. additionally the A component remarkably improves the removal effectiveness of the resist residue after ashing by conveying breaking the chemical bonds with the resist residue.

Furthermore, the content of the A component from 0.01% by mass to 1% by mass and preferably from 0.05% by mass up to 0.5 mass%. If it is less than 0.01 mass%, the Abstreifeffektivität of the resist film, the resist residue and the other etching residue deteriorated. If it exceeds 1 mass%, the corrosion the copper interconnect and the interlayer insulation film, like the film lower k, undesirable intensive.

The B1 component is a water soluble organic solvent. Although it is not specifically limited, amides, alcohols are used several hydroxyl groups and their derivatives and others are preferably used. The amides contain formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide and others.

The polyhydric alcohol or its derivatives contain 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 ethylene, diethylene glycol ethylene, diethylene glycol ethylene, diethylene glycol ethylene glycol monoethyl ether, Diethylenglycolmonopropylether, diethylene glycol monobutyl ether, Diethylenglycolmonomethyletheracetat, diethylene glycol monoethyl ether, Diethylenglycolmonopropyletheracetat, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylenglycolmonopropylether, dipropylene glycol monobutyl ether, Dipropylenglycolmonomethyletheracetat, Dipropylenglycolmonoethyletheracetat, Dipropylenglycolmonopropyletheracetat, Dipropylenglycolmonobutyletheracetat, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylenglycoldipropylether, diethylene glycol dibutyl ether, Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether and others.

It is further preferred to use a mixture the amides and alcohol with several hydroxyl groups or its To use derivatives described above as the B1 component are. Although the mixed mass ratio of amides and alcohol with several hydroxyl groups or its derivatives not specifically The following can be limited from the standpoint of the removal effectiveness of the chemical increased Excimer resists after dry etching be said. This means, if the KrF resist (resist for the KrF excimer laser) is removed, it is preferred since it is in the Essentially consists of hydroxystyrene of a phenolic framework / network higher relationship to have the amides that are highly soluble in it. If the ArF resist (Resist for the ArF excimer laser), the main framework / framework of which is acrylic, is removed, it is preferred to have a higher alcohol ratio with several To have polyhydroxyl groups or its derivatives that are highly soluble in it are. The same point of view is on the resist residue after dry etching and Ashing applicable. In other words, the mixed mass ratio of the Amides and alcohol with polyhydroxyl groups or its derivatives According to Art of the resist to be used before dry etching.

In particular, it is advantageous the mixture of amides and alcohol with polyhydroxyl groups or its To use derivatives as the B1 component in the case where the ArF resist and the KrF resist together in making one and the same semiconductor device can be used. In such a Case it is particularly preferred from the level of solubility of the two resists, that the mixed mass ratio of amides in the B1 component is 0.3 to 0.5.

The content of the B1 component is preferably from 50 mass% to 98 mass% and more preferably from 60 Mass% to 95 mass%. If it is less than 50 mass%, that would be Distance effectiveness the resist film and the resist residue are deteriorated, and the corrosion of the copper interconnect would become more intense. If on the other hand, it exceeds 98% by mass, would Removal effectiveness of the Remove the resist film and the resist residue again undesirably.

As the C component of the present Invention becomes at least one acid, those selected from the group is, the organic acid and inorganic acid contains. The organic acid contains aliphatic acids, like formic acid, Acetic acid, propionic acid, butyric acid, oxalic acid, glycolic acid, Tartaric acid and citric acid, and aromatic acids, like benzoic acid, Toluic acid and terephthalic acid and other. The inorganic acid contains Sulfuric acid, Hydrochloric acid, Nitric acid, phosphoric acid and other. The C component is used to adjust the pH (hydrogen ion concentration) of the resist remover, and the amount added is not particularly limited.

The pH of the resistant remover is 4 to 8, preferably 5.5 to 7.5 and more preferably 6.5 to 7.5. The pH of the cleaning composition has very important effects. If the pH is less than 4, would the metal film based on copper corrode heavily. If the pH exceeds 8, would Distance effectiveness the resist film, the resist residue and other etching residues are deteriorated, and corrosion of the copper-based metal film and the film low k would undesirable progress.

Water is used as the D component. Water is used to ionize the hydrofluoric acid and salt the base that does not contain metal, as the A component, to improve the removal effectiveness of the resist residue and other etching residues, and also to raise the flash point of the cleaning composition to facilitate handling of it.

Second embodiment

Another cleaning composition for removing resists a salt of a hydrofluoric acid and a base that does not contain metal (A component), a water-soluble one organic solvent (B1 component), at least one acid which is selected from a group, that from organic acid and inorganic acid consists (C component), water (D component) and an ammonium salt (E1-component). It has a hydrogen concentration (pH) of 4 to 8. This means the present embodiment contains the E1 component in addition to the A, B, C and D components of the cleaning composition for removing resists of the first embodiment, and the pH is set to 4 to 8.

The ammonium salt (E1 component) serves to suppress corrosion of the insulating film. The content of the E1 component is preferably 0.01 to 5 mass%, and more preferably 0.05 to 3 mass%. If it is less than 0.01 mass%, the corrosion of the insulating film such as TEOS, SiN, SiON, SiO _{2 would become} more intense. If it exceeds 5 mass%, the removal efficiency of the resist film, the resist residue and others would be deteriorated.

As the E1 component, any Unlimited ammonium salt to be used. It contains: aliphatic Monocarboxylsäureammoniumsalz, such as ammonium formate, ammonium acetate, ammonium propionate and ammonium butyrate; aliphatic polycarboxylic acid ammonium salt, such as ammonium glycolate, ammonium oxalate, ammonium malonate, ammonium succinate, Ammonium moleate, ammonium glutanate and ammonium adipinate; Oxycarboxylsäureammoniumsalz, such as ammonium acetate, ammonium gluconate, ammonium tartrate, ammonium malate and ammonium citrate; and aminophosphonic acid ammonium salt such as ammonium sulfamate.

Third embodiment

Yet another cleaning composition for removing resists contains a salt of hydrofluoric acid and a base that does not contain a metal (A component), a water-soluble organic solvent (B2 component), phosphonic acid (C1 component), water (D component ) and a Base that does not contain a metal (E component) and its hydrogen ion concentration (pH) is 2 to 8. Adding the phosphonic acid (C1 component) and the base that does not contain a metal (E component) improves the Corrosion resistance effect of the copper-based metal film and thus enables the use of the resistance removal cleaner in a wider pH range (pH: 2 to 8).

The A component of the present Invention is the salt of hydrofluoric acid and a base that is not contains a metal details of which have been described in the above first embodiment.

The B2 component of the present Invention is a water soluble organic solvent. Even though it is not particularly limited, amides, pyrrolidones, alkylureas, Sulfoxides, sulfones, imidazolydinones, alcohol with polyhydroxyl groups or its derivatives, lactones, carboxylic acid derivatives and others are preferred used.

The amides contain formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide and others. The pyrrolidones contain N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone and other. The alkylureas contain tetramethylurea, tetraethylurea and other. The sulfoxides contain dimethyl sulfoxide, diethyl sulfoxide and other. The sulfones contain dimethyl sulfone, diethyl sulfone, bis- (2-hydroxyethyl) sulfone, tetramethylene sulfone and others. The imidazolydinones contain 1,3-dimethyl-2-imidazolydinone, 1,3-diethyl-2-imidazolydinone and others.

The alcohol with multiple polyhydroxyl groups or its derivatives contain 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 monomethyl 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, dipropylene glycol monomethyl ether acetate, Dipropylene glycol monoethyl ether acetate, diproplene glycol monopropyl ether acetate, Dipropylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, Dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether and other.

The lactones contain γ-butyrolactone, σ-valerolactone and other. The carboxylic acid derivatives contain methyl acetate, ethyl acetate, methyl lactate, ethyl lactate and other.

It is preferred to use a mixture of a sulfur-containing compound such as sulfoxides or sulfones and the alcohol with multiple polyhydroxyl groups or its derivatives, which are described above as the B2 component as described above. Although the mixed mass ratio of the sulfur-containing compound and the alcohol having multiple polyhydroxyl groups or its derivatives are not particularly limited, the following can be said from the viewpoint of the removal efficiency of the chemically amplified excimer resist after dry etching. That is, when the KrF resist is removed because its backbone is polyhydroxystyrene of a phenol backbone, it is preferred to have a higher sulfur-containing compound ratio that is readily soluble therein. In comparison, when the ArF resist is removed, its main is acrylic, it is preferred to have a higher ratio of alcohol with polyhydroxyl groups or its derivatives, which are readily soluble therein. The same point of view applies to the residual residue after dry etching and ashing. In other words, the mixed mass ratio of the sulfur-containing compound and the alcohol having polyhydroxyl groups or its derivatives can be determined according to the kind of the resist to be used before the dry etching.

The content of the B2 component is preferred 50 mass% to 95 mass% and more preferably from 55 mass% to 90 mass%. If it is less than 50 mass%, that would be Removal effectiveness of the Resist film and the resist residue are deteriorated, and the Corrosion of the copper interconnect would become more intense. If on the other hand, it exceeds 95% by mass, would turn the removal effectiveness of the resist film and the resist residue undesirably deteriorated become.

The C1 component is the phosphonic acid. Examples the phosphonic acid used contain: diethylenetriaminepenta (methylenephosphonic acid), phenylphosphonic acid, methylene diphosphonic acid, ethylidene diphosphonic acid, 1-hydroxylethylidene-1,1-diphosphonic acid, 1-hydroxylpropylidene-1,1-diphosphonic acid, 1-hydroxylbutylidene-1,1-diphosphonic acid, ethylamino-bis (methylenephosphonic acid) Dodecylamino-bis (methylenephosphonic acid), ethylenediamine bis (methylenephosphonic acid), ethylenediamine tetrakis (methylenephosphonic acid), hexamethylenediamine tetrakis (methylenephosphonic acid), isopropylenediamine bis (methylenephosphonic acid), isopropylenediamine tetra (methylenephosphonic acid), tris (methylenephosphonic acid) other.

The phosphonic acid used (C1 component), when used with the base that does not contain a metal (E component), serves as a corrosion inhibitor for the copper-based metal film as the interconnect material or the insulating film such as the Film low k and also serves as a pH adjuster. Here is the salary the C1 component preferably from 0.1 mass% to 20 mass% and more preferably from 0.5 mass% to 15 mass if it is less than 0.1 Is% by mass the effect of corrosion protection on the copper-based metal film or the film low k be deteriorated. If it exceeds 20 mass%, would Distance effectiveness of the resist film, the resist residue or the etching residue undesirably deteriorate.

The water is called the D component used, the details of the first embodiment have been described.

The E component is the base that does not contain a metal. Although the non-metal base used is not particularly limited, organic amine compounds such as hydroxyamines, primary, secondary or tertiary fatty acid amine, alicyclic amine, heterocyclic amine and aromatic amine, ammonia, low quaternary ammonium base and others, preferably used.

The hydroxyamines contain hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine and other.

The primary fatty acid amine contains methylamine, Ethylamine, propylamine, butylamine, monoethanolamine, monoisopropanolamine, 2- (2-aminoethylamino) ethanol and other. The secondary fatty amine contains Dimethylamine, diethylamine, dipropylamine, dibutylamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine and others. The tertiary fatty acid amine contains Trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Triethanolamine and others.

The alicyclic amine contains cyclohexylamine, Dicyclohexylamine and others. The heterocyclic amine contains pyrrole, Pyrrolidine, pyridine, morpholine, pyrazine, piperidine, oxazole, thiazole and other. The aromatic amine contains benzylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine and others. The low quaternary ammonium base contains Tetramethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide and other.

The base that does not contain a metal (E component), which is used here, when used together with the phosphonic acid (C1 component) is used as a corrosion inhibitor for the copper-based metal film as the interconnect material or the insulating film such as the Film low k, and also serves as a pH adjuster. Here is the Content of the E component preferably from 0.1% by mass to 20% by mass and more preferably from 0.5 mass% to 15 mass%. If he's less is 0.1 mass%, the corrosion of the copper-based metal film and the film's low k very intense. If it exceeds 20 mass%, take the removal effectiveness the resist film, the resist residue and other etch residues undesirably from.

The pH of the resistant removal cleaner is 2 to 8 and preferably 2.5 to 7.5. If the pH is less than 2, the copper-based metal film would be severely corroded. If the pH exceeds 8, the removal efficiency of the resist film, the resist residue and the other etching residue would deteriorate, and the corrosion of the copper-based metal film and the low k film would undesirably proceed. In the present embodiment, the addition of the phosphonic acid (C1 component) and the non-metal base (E component) improves the corrosion resistance effect on a metal film, and thus enables the use of the resist remover in a wider pH range (pH: 2 to 8) as the pH range (pH: 4 to 8) of the resist removal cleaner of the first and second embodiments.

Fourth embodiment

Another cleaning composition for removing resists a salt of a hydrofluoric acid and a base that does not contain a metal (A component), a water-soluble one organic solvent (B2 component), phosphonic acid (C1 component), water (D component), a base that is not a Contains metal (E component) and a Cu corrosion inhibitor (F component), and its hydrogen ion concentration (pH) is 2 to 8. That is the present embodiment contains further the F component additionally to the A, B2, C1, D and E components of the resistance removal cleaner third embodiment, and the pH is adjusted to 2 to 8.

The Cu corrosion inhibitor is used here (F component) to suppress corrosion of a copper-based metal film, and its content is preferably from 0.01 mass% to 5 mass%, and more preferably from 0.05 mass% to 3 mass%. If it is less than 0.01 mass% is would the corrosion of the copper-based metal film become intense. If it exceeds 5 mass%, would Removal effectiveness of the Resist film, resist residue and others are deteriorated.

As the F component, triazoles, aliphatic carboxylic acids, aromatic carboxylic acids or aminocarboxylic acids preferably used, or two or more kinds thereof may be used together be used. The triazoles contain benzotriazole, o-tolyl-triazole, m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, Dihydroxypropylbenzotriazole and others. Contain the aliphatic carboxylic acids oxalic acid, malonic, Acrylic acid, methacrylic acid, maleic acid, Fumaric acid, succinic acid, itaconic acid, glutaric acid, adipic acid, lactic acid, maleic acid, citric acid, tartaric acid and other. The aromatic carboxylic acids contain benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, 5-sulfosalicylic acid, 2,4-dihydroxybenzoic acid and other. The aminocarboxylic acids contain glycine, dihydroxyethylglycine, alanine, valine, leucine, asparagine, Glutamine, aspartic acid, glutaric, Lysine, arginine, iminodiacetic acid, Nitrilotriacetsäure, Ethylendiamintetraacetsäure, 1,2-cyclohexadiamine tetraacetic acid, diethylenetriaminepentaacetic acid and other.

Next is an embodiment described the manufacturing method of a semiconductor device, in which a resist film, a resist residue and another etching residue are removed are made using the resistant removal cleaner according to the above described embodiments, taking a copper interconnect process as an example becomes.

Fifth embodiment

Hereinafter, an embodiment of the copper interconnection process using the cleaning composition of the present invention will be described with reference to FIG 1A to 1K described. In the 1A to 1C The steps described are the same as those described in 3A to 3C described conventional steps. After that, referring to 1C and 1D that during the formation of a viahole / vial hole / through hole 21 generated resist residue 6 removed using the cleaning composition of the present invention. Here is the expansion of the inside diameter of the through hole 21 suppresses because the cleaning composition hardly the film low k 4 and its modified film 7 etched.

In the 1E to 1G The steps shown are the same as those shown in 3E to 3G conventional steps shown. Next, referring to 1G and 1H that while forming the trench 22 generated resist residue is removed using the cleaning composition of the present invention. Here again, the inside diameter of the through hole and the width of the trench are prevented from increasing because the cleaning composition of the present invention hardly affects the low k 4 film and its modified film 7 etched.

After that, referring to 1I the silicon nitride film 3 by dry etching to expose the first copper interconnect 1 away. At this time, the etching residue collects 8th , which is generated according to the reaction of the etching gas and the silicon nitride, on the surface of the. first copper interconnect 1 , Next, referring to FIG 1I and 1y cleaned the surface of the first copper interconnect using the cleaning composition of the present invention. At this time, unlike the conventional cleaning process, the cleaning composition does not corrode the surface of the first copper interconnect 1 , Next, referring to 1y and 1K Copper in the through hole 21 and the trench 22 filled by, for example, reflux sputtering or MOCVD (organometallic chemical vapor deposition), which is a CVD (chemical vapor deposition) that uses an organic metal compound. An unnecessary part of it is removed by CMP, leaving a second copper interconnect 10 is formed. The cleaning composition of the present invention does not cause corrosion of the surface of the first copper interconnect 1 , This advantageously ensures a transition between the first copper interconnect 1 and the second copper interconnect 10 with no problem of increased contact resistance or separation. The distance / interval becomes wider 11 between copper interconnects prevented from becoming narrow / narrow since the cleaning composition of the present invention hardly affects the low k 4 film and its modified layer 7 etched. As a result, problems such as the deterioration in the properties of the semiconductor elements and the short circuit between the interconnections are avoided.

Sixth embodiment

Another embodiment of the copper interconnect process using the cleaning composition of the present invention will now be described with reference to FIG 2A to 2I described. In the 2A and 2 B The steps shown are the same as those shown in 3A and 3B conventional steps shown. Referring to 2 B and 2C are after dry etching the through hole 21 in a state in which the resist film 5 is left, whereby a plasma ashing is not carried out or is carried out only inadequately, the resist film 5 and the remains of resists 6 removed using the cleaning composition of the present invention. The present embodiment is advantageous in that a modified layer is not formed on the surface of the low k 4 film.

In the 2D and 2E The steps shown are the same as those in 3E and 3F conventional steps shown. Referring to 2E and 2F after dry etching the trench in a state in which the resist film 5 is left, whereby plasma ashing has not been carried out or has been carried out inadequately, the resist film 5 and the remains of resists 6 removed using the cleaning composition of the present invention. Here again a modified layer is not formed on the surface of the low k 4 film.

After that, referring to 2G the silicon nitride film 3 by dry etching to expose the first copper interconnect 1 away. At this time, the etching residue collects 8th , which is generated according to the reaction of the etching gas and the silicon nitride, on the surface of the first copper interconnect 1 ,

Next, referring to 2G and 2H the surface of the first interconnect 1 cleaned with the cleaning composition of the present invention. Here, unlike the conventional cleaning composition, the cleaning composition of the present invention does not corrode the surface of the first copper interconnect 1 , Next, referring to 2H and 2I Copper in the through hole 21 and the trench 22 filled, and an unnecessary part of it becomes the second copper interconnect 10 removed as described above. The cleaning composition of the present invention does not cause corrosion of the surface of the first copper interconnect, and thus becomes an advantageous transition between the first and second copper interconnects 1 and 10 ensured without problem of increasing contact resistance or separation. The distance / interval becomes wider 11 prevented from becoming narrow between the copper interconnects because the cleaning composition of the present invention hardly etches the low k 4 film. As a result, problems such as deterioration in the properties of the semiconductor elements and the short circuit between the interconnections are avoided.

The following is the present Invention in greater detail described.

The removal effectiveness of the resist residue, by dry etching is generated, the removal effectiveness of the etching residue, according to the reaction of the etching gas is produced with the inorganic film, and the corrosion prevention effects on the copper film and the low k film of the resist remover according to the present Invention were evaluated as follows.

(1) Preparation of the cleaning composition to remove resists

Different cleaning compositions for removing resists have been shown. The resistant removal cleaners of Examples 1 to 21 are examples of the resist remover the first embodiment. Correspond similarly those examples 22 to 25 of the second embodiment, those of examples 26 to 56 correspond to the third embodiment and those examples 57 to 61 correspond to the fourth embodiment.

To prepare the corresponding resist removal cleaner of the first embodiment, the A and B1 components, the prescribed mass% as shown in Tables 1 to 3 and 95 mass% of the total amount of the D component (water) were mixed together. Nitric acid and propionic acid as the C component were added to the mixture in small amounts to achieve a prescribed pH. The D component was added to achieve 100 masses of the cleaning composition. Each of the resist removal cleaners of the second embodiment was as follows shown. The A, B1 and E1 components of the prescribed mass% as shown in Table 4 and 95 mass% of the total required amount of the D component were mixed together, including nitric acid and propionic acid as the C component in FIG small amounts were added to obtain a prescribed pH, and the D component was further added to achieve 100 mass% of the cleaning composition. The amount of the C component to be added varies with the pH to be obtained from 0.3% by mass to 3% by mass.

Each of the resistant removal cleaners the third embodiment was represented by adding the D component to the A, B2, C1 and E component of the prescribed % By mass as shown in Tables 5 to 8 to obtain 100 Mass% of the cleaning composition while the pH was confirmed. Each of the resist removal cleaners of the fourth embodiment was represented by adding the D component to the A, B2, C1, E and F components of the prescribed % By mass as shown in Table 9 to achieve 100% by mass the cleaning composition while the pH confirmed has been.

(2) Removal effectiveness of resist residue

Referring to 1A became an embedded first copper interconnect 1 in the silicon oxide film as the first insulating film 2 using a known damascene process. A silicon nitride film 3 a film thickness of 60 nm as the protective film of the first copper interconnect 1 and a CVD-SiON film (dielectric constant: 2.8) having a film thickness of 600 nm as a low k 4 film were successively formed thereon. A patterned positive resist film 5 with a film thickness of 400 nm was further formed thereon. Here, a chemically amplified ArF excimer resist with an acrylic resin PAR-101 (manufactured by Sumitomo Chemical Co., Ltd.) was used as the ArF resist. As the KrF resist, the chemically amplified KrF excimer resist with phenolic resin SEPR-430 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

Next, reference was made to 1B the CVD-SiON film as a low k 4 film dry-etched using a parallel plate RIE at a machining pressure of 10 Pa with an RF power of 300 W by a mixed gas of fluorocarbon and Ar to form the through hole 21 to expose the silicon nitride film 3 subjected. At that time the resin residue was gathering 6 in the through hole 21 ,

Next, reference was made to 1C subjecting the resist pattern to ashing by plasma using an oxygen gas at room temperature for 90 seconds after dry etching. At that time the modified layer 7 formed on the surface of the film low k 4, and the resist residue 6 collected on its surface and in the through hole 21 ,

Next, a chip (20 mm × 20 mm in size) to which the above resist residue adhered was placed in 200 cm ^{3 of} the resist remover having a composition as shown in Tables 1, 2, 4, 5, 6, 8 or 9 is shown immersed at a temperature of 24 ° C for 30 minutes. It was dried with water after washing. The removal effectiveness of the ArF resist and its resist residue, and the removal effectiveness of the KrF resist and its resist residue at the time when the resist removal cleaner of the first embodiment was used are shown in Table 1 and Table 2, respectively. The removal effectiveness of the ArF resist and its resist residue at the time the resist removal cleaner of the second embodiment was used is shown in Table 4. Further, the removal effectiveness of the ArF resist and its resist residue and the removal effectiveness of the KrF resist and its resist residue at the time the resist removal cleaner of the third embodiment was used are shown in Tables 5 and 8 and Tables 6 and 8, respectively. Still further, the removal effectiveness of the ArF resist and its resist residue and the removal effectiveness of the KrF resist and its resist residue at the time the resist removal cleaner of the fourth embodiment was used are shown in Table 9. In each table, OO and O indicate that the resist residue was not found (OO with a surface condition better than that of O), and x indicates that the resist residue was found.

After that, reference was made to 1E to 1G the ditch 22 in the low k 4 film formed in the same manner as described above and referring to FIG 1G and 1H the remaining resist residue was removed in the same way as above. The resistance removal effectiveness at this time was the same as in Tables 1, 2, 4, 5, 6, 8 or 9.

(3) Removal effectiveness of the reaction residue of the etching gas and the inorganic film

After that, reference was made to 1I the silicon nitride film 3 Dry etched using the parallel plate RIE at a machining pressure of 10 Pa with an RF power of 300 W through a mixed gas of fluorocarbon and Ar to expose the first copper interconnect 1 , At that time, the etching residue was collecting 8th which during the reaction of the etching gas with the silicon nitride film during of the dry etching it was produced on the surface of the first copper interconnect.

Next, reference was made to 1I and 1y the etching residue 8th removed using the resist removal cleaner having the composition shown in Tables 7, 8 or 9 in the same manner as in (2) above. The result is shown in the corresponding table. OO, O and x in Tables 3, 7, 8 and 9 are used on the same basis as in Tables 1 and others.

After that, reference was made to 1K Copper in the through hole 21 and the trench 22 filled by electroplating, and an unnecessary part of it was removed by CMP. The second copper interconnect 10 was thus formed.

(4) corrosion resistance the copper interconnect

For evaluating the corrosion resistance the copper interconnect was an etched amount (or a decrease the thickness) of a copper plate chip (a size of 20 mm × 20 mm with a thickness of 500 nm) when it is in the resistant removal cleaner with a composition as shown in Tables 1 to 9, at 24 ° C while Immersed for 30 minutes and dried after washing with water, measured using a film thickness measuring device, wherein a fluorescent X-ray 4 sample was used (available by Four Dimension, Inc.). In Tables 1 to 9, OO indicates that the etched amount was less than 1 nm, O denotes the etched amount was less than 2 nm, and x denotes the etched amount Was 2 nm or larger.

(5) corrosion resistance of the film low k

For evaluating the corrosion resistance of the film's low k was an etched amount (or a decrease in thickness) of a CVD-SiON film chip (20 mm × 20 mm in size with a thickness of 500 nm) when the chip in the resistant removal cleaner with a composition as shown in Tables 1 to 9, at 24 ° C while Immersed for 30 minutes and dried after washing with water, using an optical film thickness measuring device Interference types, NanoSpec (available from Nanometrics, Inc.) measured. In Tables 1 through 9, OO indicates that the etched amount was less than 1 nm, O denotes the same less was 2 nm, and x denotes the same at least 2 nm scam.

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

The resist removal cleaners in Examples 1 to 8 all contain the A, B1, C and D components, and their pH range is in the range of 4 to 8. Thus, each cleaner shows excellent ArF resistance removal effectiveness and excellent corrosion prevention effects on the Cu film and the film low k. In comparison, Comparative Example 1 does not contain the A component, so that the ArF resistance removal effectiveness became poor. Comparative Example 2 has a pH less than 4, so that the ArF resistance removal effectiveness and the corrosion resistance of the Cu film were deteriorated. Comparative Example 3 has a pH exceeding 8, so that the corrosion resistance of both the Cu film and the low k film has deteriorated.

It was from Examples 3 and 5 to 8 found that the acrylic resin contained ArF resist in a large amount and its remainder were removed more effectively when the diethylene glycol monobutyl ether content is enlarged within the B1 component.

The resist removal cleaners in Examples 9 to 16 all contain the A, B1, C and D components, and their pH range is in the range of 4 to 8. Thus, each cleaner shows excellent KrF resistant removal effectiveness and excellent corrosion prevention effects on the Cu film and the film low k. In comparison, Comparative Example 4 does not contain the A component, so it shows poor KrF resistance removal effectiveness. Comparative example 5 has a pH less than 4, so that the corrosion resistance of the Cu film has deteriorated. Comparative Example 6 has a pH exceeding 8, so that its KrF-resistant removal efficiency and corrosion prevention effects on the Cu film and the low k film were all deteriorated.

It became from Examples 1 and 13 to 16 found that the phenolic resin contained a large amount of KrF resist and its remainder can be removed more effectively if the content of N, N-dimethylacetamide is within the B1 component is enlarged.

The resist removal cleaners in Examples 17 to 21 all contain the A, B1, C, and D components, and their pH is in the range of 4 to 8. Thus, each cleaner shows excellent etching residue removal efficiency and excellent corrosion prevention effects on the copper. Film and the film low k. Although the etching residue does not contain the resist or the resist residue as was above, it contains a large amount of carbon residue resulting from the etching gas, so that the resist removal cleaner according to the present invention is applicable.

Comparative example 7 does not contain the A component so that it shows poor etch residue removal effectiveness. Comparative example 8 has its pH less than 4, so that the corrosion resistance of the Cu film has deteriorated. Comparative example 9 has its pH greater than 8 so that the corrosion resistance of both the Cu film and also the film's low k was deteriorated.

The resist removal cleaners in Examples 22 to 25 all contain the A, B1, C, D and E1 components, and their pH is in the range of 4 to 8. Thus, each cleaner shows excellent ArF resistance removal effectiveness and excellent Corrosion prevention effects on the Cu film and the film low k. It was also found that the corrosion resistance of the low k film was further improved compared to Examples 3 and 6, which do not contain the E1 component, although they are identified by the same symbol O in the tables. Such tendency was found not only in the removal effectiveness of the ArF resist and the resist residue, but also in the removal effectiveness of the KrF resist and its resist residue.

The resist removal cleaners in Examples 26 to 35 all contain the A, B2, C1, D and E components, and their pH is in the range of 2 to 8. Thus, each cleaner shows excellent ArF resistance removal effectiveness and excellent Corrosion prevention effects on the Cu film and the film low k. In comparison, Comparative Example 10 does not contain the A component, so that the ArF resistance removal effectiveness became weak. Comparative example 11 has a pH less than 2, so that the corrosion resistance of the Cu film has deteriorated. Comparative Example 12 has a pH exceeding 8, so that the corrosion resistance of both the Cu film and the low k film has deteriorated.

It became examples 27 and 30 to 33 found that the acrylic resin contained ArF resist in a large amount and its remainder were removed more effectively when the diethylene glycol monomethyl ether content is enlarged within the B2 component.

The resist removal cleaners in Examples 36 to 45 all contain the A, B2, C1, D and E component, and their pH is in the range of 2 to 8. Thus, each cleaner shows excellent KrF resistance removal effectiveness and excellent Corrosion prevention effects on the Cu film and the film low k. In comparison, Comparative Example ¹³ does not contain the A component, so it shows poor KrF resistance removal effectiveness. Comparative example 14 has a pH less than 2, so that the corrosion resistance of the Cu film has deteriorated. The comparative example 15 has a pH exceeding 8, so that _s i _ne KrF resist removing efficiency and Korrosionsverhinde gseffekte ^run on the Cu film and the film of low k were all deteriorated.

It became Examples 37 and 40 to 43 found that the phenolic resin contained a large amount of KrF resist and its remainder can be removed more effectively if the content of dimethyl sulfoxide is enlarged within the B2 component.

The resist removal cleaners in Examples 46 to 50 all contain the A, B2, C1, D and E components, and their pH is in the range of 2 to 8. Thus, each cleaner exhibits excellent etching residue removal efficiency and excellent corrosion prevention effects the Cu film and the film low k. Although the etching residue does not contain the resist or the resist residue as above, it contains a large amount of. Carbon residue resulting from the etching gas, so that the resist removal cleaner according to the present invention is applicable. Comparative Example 16 does not contain the A component, so it shows poor etching residue removal effectiveness. Comparative Example 17 has a pH less than 2, so that the etching residue removal efficiency and the corrosion resistance of the Cu film were deteriorated. Comparative Example 18 has a pH exceeding 8, so that the corrosion resistance of both the Cu film and the low k film was deteriorated.

The resist removal cleaners in Examples 51 to 56 all contain the A, B2, C1, D and E components, and their pH is in the range of 2 to 8. Thus, each cleaner shows an excellent removal efficiency of the ArF resist , the KrF resist and the etching residue and it also shows excellent cor anti-corrosion effects on the Cu film and the low k film. The relevant examples show that a mixture of sulfur-containing compound (e.g. dimethyl sulfoxide) or amines (e.g. N, N-dimethylacetamide) and alcohol with several hydroxyl groups or its derivative (e.g. diethylene glycol monomethyl ether, diethylene glycol monobutyl ether) is preferred as the B2 component.

The resistant removal cleaners in Examples 57 to 61 all contain the A-, B2-, C1-, D-, E- and F component, and their pH is in the range of 2 to 8. Thus each cleaner shows an excellent removal effectiveness of the ArF resist, of the KrF resist and the etching residue and also shows excellent corrosion prevention effects the Cu film and the low k film. Although the etching residue is not the resist or resist residue, as above, contains one huge Amount of carbon residue resulting from the etching gas, so that the resist remover according to the present Invention is applicable.

Comparative example 21 does not contain the A component, making it poor removal effectiveness of the ArF resist, of the KrF resist and the etching residue shows. Comparative Example 22 has a pH less than 2, so that the etching residue removal effectiveness and the Corrosion resistance of the Cu film was deteriorated. The comparative example 23 has a pH exceeding 8, so that the KrF resistant removal effectiveness and corrosion resistance deteriorated from both the Cu film and the low k film were.

Claims (13)

Cleaning composition for removing resists, with: one Salt of hydrofluoric acid and a base that does not contain metal (A component); one water-soluble organic solvents (B1 component); an acid, the selected from a group is that from organic acid and inorganic acid exists (C component); and Water (D component); and with a hydrogen ion concentration (pH) of 4 to 8. Cleaning composition for removing resists, with: one Salt of hydrofluoric acid and a base that does not contain metal (A component); one water-soluble organic solvents (B1) component; at least one acid, from a group selected is that from organic acid and inorganic acid exists (C component); Water (D component); and ammonium salt (E1 component); and with a hydrogen ion concentration (pH) from 4 to 8. A cleaning composition according to claim 1 or 2, wherein the water-soluble organic solvents (the B1 component) a mixture of amides and alcohol with several Is hydroxyl groups or its derivative. Cleaning composition after. one of claims 1 to 3, in which the base, which does not contain metal, for forming the salt of the Hydrofluoric acid and a base that does not contain metal (the A component) at least is a base selected from a group consisting of an organic Amine compound, ammonia and a low quaternary ammonium base. Cleaning composition according to one of claims 1 to 4, in which the content of the salt of hydrofluoric acid and a base that does not contain metal (the A component) is 0.01 to 1 mass%. Cleaning composition for removing resists, with: one Salt of hydrofluoric acid and a base that does not contain metal (A component); one water-soluble organic solvents (B2 component); phosphonic (C1 component); Water (D component); and a base, that doesn't contain metal (E component); and with a hydrogen ion concentration (pH) from 2 to 8. The cleaning composition of claim 6, wherein the water-soluble organic Solvents (the B2 component) a mixture of a sulfur-containing compound and is alcohol having multiple hydroxyl groups or its derivative. Cleaning composition for removing resists, with: a salt of hydrofluoric acid and a base that does not contain metal (A component); a water-soluble organic solvent (B2 component); a phosphonic acid (C1 component); Water (D component); a base that does not contain metal (E component); and a Cu corrosion inhibitor (F component); and with a hydrogen ion concentration (pH) of 2 to 8. The cleaning composition of claim 8, wherein the Cu corrosion inhibitor (the F component) contains at least one species selected from a group, those of triazole, aliphatic carboxylic acids, aromatic carboxylic acids and aminocarboxylic acids consists. Method of manufacturing a semiconductor device, comprising the steps of: forming a metal film ( 1 ) with copper as its main component on a semiconductor substrate; Forming an insulating film ( 4 ) thereon; Forming a resist film ( 5 ) thereon; Provide a hole ( 21 ) or a trench ( 22 ) in the insulating film ( 4 ) by dry etching using the resist film ( 5 ) as a mask; Remove the resist ( 5 ) by gas plasma treatment or heat treatment; and removal of the remaining resist residue ( 6 ) using the cleaning composition according to any one of claims 1 to 9. A manufacturing method according to claim 10, wherein the resist film used as a mask in the dry etching ( 5 ) is a chemically amplified excimer resist. A semiconductor device manufacturing method comprising the steps of: forming a metal film ( 1 ) with copper as its main component on a semiconductor substrate; Forming an insulating film ( 4 ) thereon; Forming a resist film ( 5 ) thereon; Provide a hole ( 21 ) or a trench ( 22 ) in the insulating film ( 4 ) by dry etching using the resist film ( 5 ) as a mask; and removing the remaining resist film ( 5 ) and the remains of resists ( 6 ) generated during dry etching using the cleaning composition according to any one of claims 1 to 9. A semiconductor device manufacturing method comprising the steps of: forming a metal film ( 1 ) with copper as its main component on a semiconductor substrate; Forming an insulating film ( 4 ) thereon; Provide a hole ( 21 ) in the insulating film ( 4 ) that covers the metal film ( 1 ) achieved by dry etching; and removing caustic residue ( 8th ) generated during dry etching using the cleaning composition according to any one of claims 1 to 9.