Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
  • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
  • H05K3/061—Etching masks
  • H05K3/064—Photoresists
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
  • H05K3/067—Etchants

Definitions

• the present invention relates to a composition for removing photoresist and a method for removing photoresist using the composition.
• a metal layer called a seed layer is formed on an insulating layer partially having copper wiring
• a photoresist layer is formed on the surface of the seed layer
• a resist pattern is formed by exposure and development
• copper plating is applied to the openings of the pattern
• the photoresist and seed layer are removed to form a circuit pattern that serves as the connection terminals of the copper wiring.
• manufacturing methods for printed wiring boards and the like often include a step of removing photoresist, and the photoresist removal step typically uses an aqueous solution containing a variety of components (e.g., Patent Document 1).
• a composition for removing a photoresist for forming a copper-containing pattern after the pattern is formed comprising: Contains an alkaline agent and an azole compound,
• the alkaline agent is at least one selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic alkalis;
• the azole compound is at least one selected from the group consisting of compounds represented by the following formulas (1) to (3): The composition, wherein the pH of the composition is 10 or greater.
• R 1 to R 14 are each independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may have a substituent, or an amino group which may have a substituent.)
• the azole compound includes at least one of 4-methylimidazole, 2-methylimidazole, 5-methylbenzimidazole, 2-aminobenzimidazole, and 3-methylpyrazole.
• composition based on the total amount of the composition, 3.0 to 50% by weight of the alkaline agent, and Contains 0.001 to 1.0% by mass of the azole compound; The composition described in [1] above.
• composition described in [1] above, wherein the composition is water-soluble.
• composition described in [1] above, wherein the composition does not contain a thiol compound.
• the pattern is a circuit pattern that serves as a connection terminal portion of the copper wiring formed on an insulating layer having copper wiring at least in a portion thereof.
• a method for removing a photoresist comprising a photoresist removal step of contacting a photoresist for forming a copper-containing pattern with the composition according to any one of [1] to [8] above.
• a method for producing a printed wiring board, a semiconductor element, or a semiconductor package comprising a photoresist removal step of contacting a photoresist for forming a copper-containing pattern with the composition according to any one of [1] to [8] above.
• the present invention provides a photoresist removal composition that is excellent in terms of protecting copper-containing components while efficiently removing photoresist and does not leave any residue on the photoresist surface.
• composition of the present invention is preferably used, for example, to remove photoresist after the formation of a copper-containing pattern, and contains at least a specified alkaline agent and an azole compound.
• the composition is described in detail below.
• composition is preferably water-soluble, i.e., at least a portion of the composition is preferably soluble or suspendable in water and can be uniformly mixed with water in any proportion. More preferred. It is also preferable that at least a portion of the components other than water contained in the composition is soluble in water, and it is more preferable that the components other than water contained in the composition and water can be uniformly mixed. .
• the composition preferably contains 3.0 to 50 mass% of (A) an alkaline agent (hereinafter also referred to as component (A)) based on the total mass of the composition.
• the content of the alkaline agent in the composition is more preferably 4.0 to 40 mass%, further preferably 5.0 to 30 mass% or 6.0 to 35 mass%, and particularly preferably 7.0 to 15 mass%, 8.0 to 20 mass%, or 9.0 to 12 mass%, based on the total mass of the composition.
• component (A) the effect of improving the removability of photoresist and suppressing damage to a circuit pattern containing copper, copper alloy, etc., which serves as a connection terminal portion of copper wiring, is observed.
• the alkaline agent (A) preferably contains any one selected from (A-1) an alkanolamine, (A-2) a quaternary ammonium hydroxide, and (A-3) an inorganic alkali, more preferably contains two of these, and particularly preferably contains all of (A-1) to (A-3).
• (A-1) Alkanolamine The type of (A-1) alkanolamine that can be contained in the composition as component (A) is not particularly limited, but examples include monoalkanolamines, dialkanolamines, trialkanolamines, and alkylated products thereof (N-alkylated products, O-alkylated products).
• alkanolamines (A) examples include 2-aminoethanol (monoethanolamine), N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, 1-amino-2-propanol (isopropanolamine), N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2-amino-propan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan
• N-ethyl-2-aminobutan-1-ol 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpropan-1-ol, 2-amino-4-methylpropan-2 ...
• amino acids include 1,2-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2-(2-aminoethoxy)ethanol, etc.
• the alkanolamine is preferably one or more selected from the group consisting of 2-aminoethanol (monoethanolamine) and 1-amino-2-propanol.
• the alkanolamine content is preferably 1.0 to 50% by mass, more preferably 1.5 to 45% by mass, 1.5 to 42% by mass, 2.0 to 30% by mass, or 2.0 to 15% by mass, even more preferably 3.0 to 12% by mass, and particularly preferably 4.0 to 8.0% by mass, or 5.0 to 9.0% by mass, based on the total amount of the composition.
• (A-2) Quaternary Ammonium Hydroxide The type of (A-2) quaternary ammonium hydroxide that may be contained in the composition as component (A) is not particularly limited, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, triethylmethylammonium hydroxide, ethyltrimethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, and triethyl(2-hydroxyethyl)ammonium hydroxide. These may be used alone or in combination of two or more.
• the quaternary ammonium hydroxide is preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and triethylmethylammonium hydroxide.
• the content of quaternary ammonium hydroxide is preferably 0.3 to 10 mass% based on the total amount of the composition, more preferably 0.5 to 8.0 mass%, even more preferably 0.7 to 9.0 mass%, and particularly preferably 0.8 to 4.0 mass% or 0.9 to 5.0 mass%, etc.
• (A-3) Inorganic Alkali The type of (A-3) inorganic alkali that can be contained in the composition as component (A) is not particularly limited, and examples thereof include alkali metal compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate; alkaline earth metal compounds such as magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, and magnesium silicate; transition metal compounds such as copper hydroxide and iron hydroxide; and ammonia. Among these, potassium hydroxide, sodium hydroxide, etc. are preferred as inorganic alkali.
• the content of inorganic alkali is preferably 0.001 to 5.0 mass% based on the total amount of the composition, more preferably 0.01 to 3.0 mass%, even more preferably 0.05 to 2.0 mass%, and particularly preferably 0.1 to 0.5 mass% or 0.2 to 1.0 mass%, etc.
• the composition preferably contains 0.001 to 1.0 mass% of the azole compound (B) (hereinafter also referred to as component (B)) based on the total mass of the composition.
• the content of the azole compound in the composition is more preferably 0.005 to 0.80 mass%, further preferably 0.01 to 0.50 mass% or 0.02 to 0.60 mass%, and particularly preferably 0.02 to 0.40 mass%, 0.02 to 0.30 mass%, 0.25 to 0.40 mass%, 0.25 to 0.30 mass%, or 0.03 to 0.20 mass%, based on the total mass of the composition.
• component (B) the effect of protecting a metal layer containing copper or a copper alloy and reducing the etching rate of copper is observed.
• the azole compound in the composition preferably contains at least one of an imidazole compound, a benzimidazole compound, and a pyrazole compound.
• (B-1) Imidazole Compound The imidazole compound is not particularly limited as long as it is a compound having an imidazole ring, but it is preferable to use at least a compound represented by the following formula (1) as one component of the composition.
• R 1 to R 4 are each independently selected from a hydrogen atom, an optionally substituted alkyl group having 1 to 7 carbon atoms, and an optionally substituted amino group.
• the alkyl group preferably has 1 or more and 5 or less carbon atoms, more preferably has 1 or more and 3 or less carbon atoms, and further preferably has 1 or 2 carbon atoms, or 1 carbon atom.
• the substituent examples include a hydroxyl group, a halogen, a vinyl group, a carboxyl group, a cyano group, a nitro group, a (meth)acryloxy group, a glycidyloxy group, a mercapto group, an amino group, etc.
• the substituent also includes an amino group, for example, an amino group which may contain an alkyl group having 10 or less carbon atoms, and when any of R 1 to R 4 is an amino group, the substituent also includes an alkyl group, for example, an alkyl group having 10 or less carbon atoms.
• the above-mentioned carbon number is the total number of carbon atoms including the carbon of the substituent.
• imidazole compounds include imidazole, imidazole derivatives having the above-mentioned substituents, for example, 1-alkylimidazoles such as 1-methylimidazole, 2-alkylimidazoles such as 2-methylimidazole, 4-alkylimidazoles such as 4-methylimidazole, and imidazolium salts of these.
• (B-2) Benzimidazole Compound The benzimidazole compound is not particularly limited as long as it is a compound having a benzimidazole skeleton, but it is preferable to use at least a compound of the following formula (2) as one component of the composition.
• R 5 to R 10 are each independently selected from a hydrogen atom, an optionally substituted alkyl group having 1 to 7 carbon atoms, and an optionally substituted amino group.
• the alkyl group preferably has 1 or more and 5 or less carbon atoms, more preferably has 1 or more and 3 or less carbon atoms, and further preferably has 1 or 2 carbon atoms, or 1 carbon atom.
• substituents examples include a hydroxyl group, a halogen, a vinyl group, a carboxyl group, a cyano group, a nitro group, a (meth)acryloxy group, a glycidyloxy group, a mercapto group, an amino group, etc.
• the substituent also includes an amino group, for example, an amino group which may contain an alkyl group having 10 or less carbon atoms, and when any of R 5 to R 10 is an amino group, the substituent also includes an alkyl group, for example, an alkyl group having 10 or less carbon atoms.
• the above-mentioned carbon number is the total number of carbon atoms including the carbon of the substituent.
• imidazole compounds include benzimidazole, benzimidazole derivatives having the above-mentioned substituents, for example, 1-alkylbenzimidazoles such as 1-methylbenzimidazole, 2-alkylbenzimidazoles such as 2-methylbenzimidazole, 5-alkylbenzimidazoles such as 5-methylbenzimidazole, 1-aminobenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, and benzimidazolium salts thereof.
• the pyrazole compound is not particularly limited as long as it is a compound having a pyrazole ring, but it is preferable to use at least a compound of the following formula (3) as one component of the composition.
• R 11 to R 14 are each independently selected from a hydrogen atom, an optionally substituted alkyl group having 1 to 7 carbon atoms, and an optionally substituted amino group.
• the alkyl group preferably has 1 or more and 5 or less carbon atoms, more preferably has 1 or more and 3 or less carbon atoms, and further preferably has 1 or 2 carbon atoms, or 1 carbon atom.
• the substituent examples include a hydroxyl group, a halogen, a vinyl group, a carboxyl group, a cyano group, a nitro group, a (meth)acryloxy group, a glycidyloxy group, a mercapto group, an amino group, etc.
• the substituent also includes an amino group, for example, an amino group which may contain an alkyl group having 10 or less carbon atoms, and when any of R 11 to R 14 is an amino group, the substituent also includes an alkyl group, for example, an alkyl group having 10 or less carbon atoms.
• the above-mentioned carbon number is the total number of carbon atoms including the carbon of the substituent.
• pyrazole compounds include pyrazole, pyrazoles having the above-mentioned substituents, 1-alkylpyrazoles such as 1-methylpyrazole, 3-alkylpyrazoles such as 3-methylpyrazole, 4-alkylpyrazoles such as 4-methylpyrazole, 5-alkylpyrazoles such as 5-methylpyrazole, and pyrazole salts thereof.
• the composition preferably contains water.
• the type of water contained in the composition is not particularly limited, but may be water that has been subjected to distillation, ion exchange treatment, filtration, various adsorption treatments, etc. to remove metal ions, organic impurities, particle particles, etc.
• water from which these have been removed is used, more preferably pure water, and particularly preferably ultrapure water.
• the content of water in the composition is preferably 20% by mass or more, more preferably more than 20% by mass, even more preferably in the range of 20 to 99% by mass, based on the total amount of the composition.
• the water content is preferably 50 to 97% by mass, more preferably 60 to 95% by mass, and particularly preferably 70 to 95% by mass. In the composition in which the water content is adjusted in this manner, the reactivity with the photoresist, the photoresist The removability is improved.
• the composition may contain other components as necessary, as long as the above-mentioned effects are not impaired.
• examples of other components include a solvent, an ammonium salt, a pH adjuster, a surfactant, and a defoaming agent.
• carbonate ions, carbonates that generate carbonate ions, bicarbonates, etc. may be added to the composition. Adding carbonate ions, etc. to the composition improves copper corrosion protection.
• Specific examples of carbonates and bicarbonates include salts of ammonium ions, salts of alkali metals or alkaline earth metals, and ammonium carbonates such as tetramethylammonium carbonate may be added to the composition.
• the content of secondary components in the composition is preferably 10 mass % or less, more preferably 5.0 mass % or less, even more preferably 3.0 mass % or less, and even more preferably 2.0 mass % or less, or 1.5 mass % or less, based on the total amount of the composition. Furthermore, the content of each component of the salt that generates carbonate ions in the composition is preferably 5.0 mass % or less, more preferably 3.0 mass % or less, and even more preferably 2.0 mass % or less, or 1.5 mass % or less. Additionally, the composition is preferably a solution and does not preferably contain solid particles such as abrasive particles.
• preferred organic solvents include aromatic alcohols such as benzyl alcohol, salicyl alcohol, anisyl alcohol, anise alcohol, gentisyl alcohol, protocatechuyl alcohol, vanillyl alcohol, veratryl alcohol, syringyl alcohol, cuminyl alcohol, and phenethyl alcohol.
• aromatic alcohols such as benzyl alcohol, salicyl alcohol, anisyl alcohol, anise alcohol, gentisyl alcohol, protocatechuyl alcohol, vanillyl alcohol, veratryl alcohol, syringyl alcohol, cuminyl alcohol, and phenethyl alcohol.
• the content of the solvent is preferably 0.01 to 20 mass% based on the total amount of the composition, more preferably 0.1 to 10 mass%, even more preferably 0.2 to 5.0 mass%, and particularly preferably 0.3 to 3.5 mass% or 0.4 to 4.0 mass%, etc.
• the composition preferably contains an ammonium ion source, such as an ammonium salt, for example a quaternary ammonium salt.
• an ammonium ion source such as an ammonium salt, for example a quaternary ammonium salt.
• the use of a specific ammonium ion source can have the effect of enhancing the removability of the photoresist.
• ammonium ion source that can be included in the composition is not particularly limited, and examples include ammonia, ammonium salts such as ammonium halide salts (ammonium chloride, ammonium bromide, ammonium iodide, etc.), ammonium salts of organic acids, ammonium salts of inorganic acids, etc.
• ammonium ion source ammonium salts of organic acids are preferred, and examples of the ammonium salts of organic acids include ammonium salts of aromatic organic acids and ammonium salts of fatty acids.
• ammonium salts of aromatic organic acids include mono-, di- and triammonium salts of aromatic carboxylic acids having 6 to 30 carbon atoms. Specific examples include ammonium salts of benzoic acid, phthalic acid, salicylic acid and the like, that is, ammonium benzoate, ammonium (di)phthalate, ammonium salicylate, etc. Further, examples of fatty acid ammonium salts include mono-, di-, and triammonium salts of saturated or unsaturated fatty acids having 1 to 20 carbon atoms.
• ammonium salts of saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, tridecylic acid, palmitic acid, and stearic acid
• unsaturated fatty acids such as acrylic acid, methacrylic acid, oleic acid, linoleic acid, and linolenic acid.
• One type of ammonium ion source may be used, or two or more types may be used. Based on the total amount of ammonium ion sources in the composition, it is preferable that the composition contains 30 mass% or more of aromatic organic ammonium salt or fatty acid ammonium salt, more preferably 50 mass% or more of aromatic organic ammonium salt or fatty acid ammonium salt, even more preferably 70 mass% or more of aromatic organic ammonium salt or fatty acid ammonium salt, and particularly preferably 90 mass% or more of aromatic organic ammonium salt or fatty acid ammonium salt. It is even more preferable that the composition contains only aromatic organic ammonium salt or fatty acid ammonium salt as the ammonium ion source.
• the content of the ammonium ion source in the composition is preferably 0.1 to 20 mass% based on the total mass of the composition, and the content of the ammonium ion source in the composition is more preferably 0.15 to 10 mass%, even more preferably 0.20 to 5.0 mass%, and particularly preferably 0.25 to 2.5 mass%, 0.50 to 3.0 mass%, or 1.0 to 2.0 mass%, based on the total mass of the composition.
• compositions of the present invention there are some components that are preferably not added to the composition.
• undesirable components in the composition include thiols, organic acids containing sulfur atoms, and chelating agents.
• the residual chelating agent may have a detrimental effect on the subsequent flash etching process in which copper is etched, because the adhesion of the chelating agent to the copper surface may interfere with the etching process.
• an organic acid containing a sulfur atom is used as a component of the composition, odor due to the sulfur-containing compound may be generated and the stability of the composition may be reduced. Therefore, it is preferable that the composition of the present invention does not contain the above-mentioned compounds.
• the composition of the present invention is prepared by adding component (A), component (B), water, and, if necessary, other components, and stirring them preferably until they become completely uniform.
• the order of adding and mixing each component is not particularly limited.
• a small amount of water may be added to any of the components (A) (A-1) to (A-3), and other components other than water may be prepared as concentrated solutions, and these may be mixed at the site where the composition is used. Any of the components may be transported in such a concentrated state, i.e., in a state not containing water, and water may be added to prepare the composition.
• the pH value of the composition of the present invention is 10 or more, preferably 10.5 to 13.8, more preferably 11.0 to 13.6, and even more preferably 11.3 to 13.3.
• the pH value can be measured using a pH meter, as described in detail below.
• the composition of the present invention makes it possible to suppress damage to copper and copper alloys. Therefore, it may be possible to suppress the etching rate of copper, evaluated by the method described in detail later in the Examples section, to 0.050 ⁇ m/min or less. More preferably, the etching rate of copper, evaluated by the method described in detail later, is 0.040 ⁇ m/min or less, even more preferably 0.030 ⁇ m/min or less, and particularly preferably 0.020 ⁇ m/min or 0.015 ⁇ m/min or less.
• the composition of the present invention can effectively remove photoresist. Therefore, it may be possible to set the L.P. (lifting point) value related to the stripping speed, which is evaluated by the method described in detail later in the Examples section, to 100 seconds or less. More preferably, the L.P. value, which is evaluated by the method described in detail later, is 90 seconds or less, even more preferably 85 seconds or less, and particularly preferably 80 seconds or less or 75 seconds or less.
• the temperature at which the composition is used to remove the photoresist is not particularly limited, but is preferably 10 to 70° C., more preferably 20 to 65° C., and even more preferably 25 to 60° C.
• the temperature at which the composition is used to remove the photoresist is not particularly limited, but is preferably 10 to 70° C., more preferably 20 to 65° C., and even more preferably 25 to 60° C.
• the treatment time for the photoresist with the composition is not particularly limited, but is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and may be 30 to 240 seconds.
• the treatment time is the time the composition is in contact with the photoresist, and may be appropriately selected depending on various conditions such as the surface condition of the photoresist to be removed, the concentration of the composition, the temperature, and the treatment method.
• the composition of the present invention can be contacted with the photoresist to be removed by dropping (single-wafer spin processing) or spraying, or the photoresist to be removed can be immersed in the composition of the present invention. Either method may be used in the present invention.
• the method for removing a photoresist of the present invention includes a photoresist removing step of contacting the composition of the present invention with a photoresist for forming a copper-containing pattern.
• the method for removing a photoresist will be described below.
• composition of the present invention can be suitably used, for example, when removing a photoresist for forming a copper-containing circuit pattern that serves as a connection terminal portion of the copper wiring on an insulating layer at least partially having copper wiring, after the circuit pattern has been formed.
• insulating layer having copper wiring at least in a part is not particularly limited as long as it is an insulating layer having copper wiring embedded on the surface or inside, and examples thereof include a printed wiring board, a package substrate for mounting a semiconductor element, and a silicon insulating layer of a semiconductor wafer.
• the "circuit pattern containing copper that serves as a connection terminal portion of copper wiring” refers to a circuit pattern that serves as a connection terminal portion of copper wiring in an insulating layer, for example, for making an electrical connection with another member.
• the connection terminal portion is a connection terminal portion of a copper wiring in a printed wiring board.
• the connection terminal portion is a connection terminal portion of a copper wiring in a package substrate for mounting a semiconductor element.
• the connection terminal portion is a connection terminal portion of a copper wiring in a semiconductor element.
• the method for producing a printed wiring board or the like of the present invention includes a photoresist removal step in which the composition of the present invention is brought into contact with a photoresist for forming a copper-containing pattern.
• the composition of the present invention can also be suitably used in the photoresist removal step in the method for producing a semiconductor element or semiconductor package.
• composition of the present invention can be suitably used in the process of producing a printed wiring board (e.g., a package substrate for mounting a semiconductor element) when removing a photoresist for forming a copper-containing circuit pattern that serves as a connection terminal portion of the copper wiring on an insulating layer at least partially having copper wiring, after the circuit pattern has been formed.
• a printed wiring board e.g., a package substrate for mounting a semiconductor element
• composition of the present invention can be suitably used in the process of manufacturing a semiconductor device when removing a photoresist for forming a circuit pattern, which contains copper, which serves as a connection terminal portion of the copper wiring, and at least one type selected from the group consisting of tin and a tin alloy, on an insulating layer at least partially having copper wiring, after the circuit pattern has been formed.
• the method for manufacturing printed wiring or the like preferably further includes a cleaning step of cleaning the photoresist-containing substrate that has been subjected to the photoresist removal step.
• the cleaning step it is preferable to clean the photoresist-containing substrate using sulfuric acid or water having a concentration of, for example, 40% by mass or less, and it is more preferable to clean with water, for example pure water, after cleaning with sulfuric acid.
• the concentration of sulfuric acid may be, for example, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, etc.
• the temperature of the cleaning solution such as sulfuric acid or water is preferably 10 to 70°C, more preferably 15 to 50°C, and even more preferably room temperature of about 20 to 30°C.
• the method for cleaning the photoresist-containing substrate with the cleaning liquid is not particularly limited, and for example, a method in which the above-mentioned cleaning liquid is brought into contact with the substrate to be cleaned by dropping (single-wafer spin treatment) or spraying, or a method in which the substrate to be cleaned is immersed in the cleaning liquid can be employed.
• the spraying time is, for example, 5 seconds to 5 minutes, preferably 10 seconds to 3 minutes, more preferably 15 seconds to 1 minute, and even more preferably 20 seconds to 45 seconds.
• the spraying pressure is, for example, 0.03 to 1.0 MPa, preferably 0.05 to 0.50 MPa, and even more preferably 0.10 to 0.30 MPa or 0.10 to 0.20 MPa.
• Photoresists used in printed wiring boards include, for example, compositions containing a binder polymer, a photopolymerizable monomer, a photopolymerization initiator and other additives.
• the binder polymer include those obtained by copolymerizing at least one of methacrylic acid and acrylic acid as an essential component with several kinds of vinyl monomers such as methacrylic acid esters, acrylic acid esters, and styrene.
• the photopolymerizable monomer is preferably at least one of a methacrylic acid ester and an acrylic acid ester.
• the photopolymerization initiator may be at least one selected from the group consisting of benzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-ethylanthraquinone, benzoin, benzoin methyl ether, 9-phenylacridine, benzil dimethyl ketal, and benzil diethyl ketal.
• a bimolecular system consisting of hexaarylbiimidazole and a hydrogen donor (2-mercaptobenzoxazal, N-phenylglycine) may also be used.
• Other additives include a thermal polymerization initiator and a dye.
• Preferred photoresists for use in semiconductor elements include a combination of phenol-formaldehyde resin (collectively known as "novolac resin”) and a naphthoquinone diazide compound, which is a photosensitive component.
• novolac resin phenol-formaldehyde resin
• naphthoquinone diazide compound which is a photosensitive component.
• the resist placed between the metal wiring may be a dry film resist, a liquid resist, or the like.
• the resist is preferably a dry film resist.
• the dry film resist is made of a photosensitive resin.
• photosensitive resins include negative photosensitive resins and positive photosensitive resins.
• Negative photosensitive resins are not particularly limited, but include azide-based photosensitive resins, diazo-based photosensitive resins, acetylenic low molecular weight photosensitive resins, ethylenic low molecular weight photosensitive resins, insolubilized polymer photosensitive resins, and chromate-based photosensitive resins. These negative photosensitive resins may be used alone or in combination of two or more.
• Positive photosensitive resins are not particularly limited, but include quinone diazide photosensitive resins, solubilized polymer photosensitive resins, etc. These positive photosensitive resins may be used alone or in combination of two or more.
• the dry film resist is preferably formed from a negative photosensitive resin.
• the negative photosensitive resin is cured by exposure treatment during pattern formation and becomes insoluble in a developer, so that the exposed portion (the portion where the negative photosensitive resin is cured) remains as a dry film resist.
• the negative photosensitive resin is particularly prone to curing of the surface portion exposed to exposure, and the surface portion of the obtained dry film resist may have a particularly dense structure. For this reason, even if an attempt is made to remove the dry film resist using a composition, the composition may be difficult to penetrate into the inside of the dry film resist.
• some compositions have insufficient resist removal ability, so removal of the dry film resist may not proceed. As a result, it may take time to remove the dry film resist.
• the composition of the present invention easily permeates into the dry film resist, and therefore the dry film resist can be rapidly peeled off and removed.
• pH The pH of the aqueous compositions described in the Examples and Comparative Examples was measured using a pH meter (D-53, manufactured by Horiba, Ltd.).
• a sample for evaluating copper corrosion resistance was prepared as follows: A surface of a copper-clad laminate (manufactured by Mitsubishi Gas Chemical Company, Inc., CCL-HL832NX) was electroplated with copper (thickness: 35 ⁇ m) to obtain a sample for evaluating copper corrosion resistance.
• 5% sulfuric acid immersion Immerse in 5% sulfuric acid by mass at 25°C for 30 seconds, followed by rinsing with pure water.
• 20% sulfuric acid spray Spray with 20% sulfuric acid by mass at a spray pressure of 0.15 MPa at 25°C for 30 seconds, followed by rinsing with pure water.
• the N element of the obtained treated copper corrosion protection evaluation sample was measured using an X-ray photoelectron spectrometer (K-Alpha, manufactured by Thermo Fisher Scientific Co., Ltd.). The cleaning ability was evaluated according to the following criteria, with the maximum peak intensity of N element of the copper corrosion prevention evaluation sample before treatment being taken as 100. Cleanable (good): The maximum peak intensity of N element of the copper anticorrosion evaluation sample after treatment is 120 or less. Uncleanable (bad): The maximum peak intensity of N element of the copper anticorrosion evaluation sample after treatment is more than 120.
• ( ⁇ m/min) value was calculated as follows: the mass of the copper anticorrosion evaluation sample was measured before and after the spraying treatment with the above-mentioned aqueous composition, and the etched thickness was calculated from the mass difference, the copper density (8.93 g/cm 3 ), and the sample size (treated area [cm 2 ]; since the back surface of the copper anticorrosion evaluation sample was protected with masking tape, the treated area was the area of the sample surface), and the etching amount per minute was calculated by the following formula (I).
• Example 1 To 321 g of pure water, monoethanolamine (MEA) was added in an amount of 6 mass% (32 g of 75% MEA aqueous solution), tetramethylammonium hydroxide (TMAH) in an amount of 2 mass% (32 g of 25% TMAH aqueous solution), ethylene glycol monophenyl ether (PhGE) in an amount of 2.25 mass% (9.0 g), 4-methylimidazole in an amount of 0.09 mass% (0.36 g), and diethylene glycol monobutyl ether (DGBE) in an amount of 1.35 mass% (5.4 g) were added to prepare an aqueous composition.
• MEA monoethanolamine
• TMAH tetramethylammonium hydroxide
• PhGE ethylene glycol monophenyl ether
• 4-methylimidazole in an amount of 0.09 mass% (0.36 g
• DGBE diethylene glycol monobutyl ether
• the copper corrosion prevention evaluation sample after treatment with the obtained aqueous composition was washed with a water spray.
• the pH of the obtained aqueous composition was 13.3, the washability was good, and the Cu E.R. was 0.01 ⁇ m/min.
• the properties of the aqueous composition and the evaluation results are shown in Table 1 below.
• Examples 2 to 12 and Comparative Examples 1 to 5 As shown in Table 1 below, the type and amount of each component in the composition of Example 1, or the cleaning method for the copper corrosion protection evaluation sample was changed, and additional components were added in some of the Examples and Comparative Examples, and aqueous compositions were prepared and evaluation tests were performed in the same manner as in Example 1. The properties and evaluation results of the aqueous compositions of each Example and Comparative Example are shown in Table 1 below.
• the tetramethylammonium bicarbonate (TMBC) added to the aqueous composition of Example 6 and the like can be generated as a degradation product of tetramethylammonium hydroxide (TMAH) and can reduce the stripping performance of the dry film resist by the aqueous composition. Therefore, in order to evaluate the stripping treatment by the aqueous composition when tetramethylammonium bicarbonate is generated by long-term use, the bicarbonate was added to the aqueous composition of this example.
• TMBC tetramethylammonium bi
• the aqueous composition of the example containing a specific azole compound provided better cleaning results than the aqueous composition of the comparative example, i.e., it was possible to reduce the amount of N element remaining on the surface of the copper-containing sample. Furthermore, the example had a lower Cu E.R. (etching rate) value than the comparative example, indicating that the composition has excellent copper corrosion protection properties.
• a sample for evaluating peelability was prepared as follows. First, chemical copper plating was applied to a copper-clad laminate (Mitsubishi Gas Chemical Company, Inc., CCL-HL832NS (MT-FL) 0.1 mmtC/C) to form a copper thin film (thickness: 1.0 ⁇ m). A dry film resist (Showa Denko K.K., RD-3025, thickness: 25 ⁇ m) was attached to the surface of this copper thin film, a circuit mask pattern was applied thereon, and the circuit mask pattern was exposed and developed.
• a copper-clad laminate Mitsubishi Gas Chemical Company, Inc., CCL-HL832NS (MT-FL) 0.1 mmtC/C
• a dry film resist Showa Denko K.K., RD-3025, thickness: 25 ⁇ m
• An electrolytic copper plating (thickness: 17 ⁇ m) was applied to the circuit pattern opening formed by exposure and development of the dry film resist to obtain a sample for evaluating peelability.
• the pattern of the dry film resist applied to the sample for evaluating peelability is a dot of 100 to 300 ⁇ m ⁇ .
• aqueous composition A The aqueous composition used in Examples 6 to 8 (hereinafter, aqueous composition A), the aqueous composition used in Examples 10 to 12 (hereinafter, aqueous composition B), and the aqueous composition used in Comparative Example 5 were each sprayed onto the above-mentioned sample for evaluating peelability at a spray pressure of 0.15 MPa at 50° C. for 3 minutes to bring the sample into contact with the aqueous composition.
• the aqueous composition was then washed with pure water, washed with 5% by mass sulfuric acid, and washed again with pure water, and then thoroughly dried.
• the strippability was evaluated as follows: An optical microscope (MX-61L, 50x objective lens, manufactured by Olympus Corporation) was used to confirm the residue of the dry film resist on the strippability evaluation sample after the above-mentioned aqueous composition was sprayed, and the evaluation was performed according to the following criteria. Particularly good: Residues of dry film resists of 100 to 300 ⁇ m diameter are all 2 or less. Good: Residues of dry film resists of 100 to 300 ⁇ m diameter are all 110 or less. Poor: Residues of dry film resists of 100 to 300 ⁇ m diameter exceed 110 in some cases.
• the aqueous composition A of the example, the aqueous composition B of the example, and the aqueous composition of Comparative Example 5 were each contacted with the above-mentioned sample for evaluating peelability by spraying at a spray pressure of 0.15 MPa and 50°C.
• the time from when the aqueous composition was sprayed to when the dry film resist was completely peeled off from the substrate of the strippability evaluation sample was measured, and this was taken as L.P. (seconds).
• L.P. the dot pattern of 250 ⁇ m ⁇ applied to the strippability evaluation sample was visually observed, and the time when the dry film resist was removed was taken as the time.
• Aqueous composition A 90 (seconds)
• Aqueous composition B 90 (seconds)
• Aqueous composition of Comparative Example 5 110 (seconds)
• the aqueous composition of the embodiment containing a specific azole compound is superior in suppressing the generation of resist residues compared to the aqueous composition of the comparative example, and the time indicated by the L.P. (lifting point) value is shorter, confirming that the photoresist can be stripped quickly.

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