KR20120049177A - Wet etching system for copper-containing material, and patterning method - Google Patents

Abstract

The present invention has exposure means for exposing a copper-containing material having a pattern of a positive photosensitive resist formed thereon and wet etching means for wet-etching the copper-containing material exposed by the exposure means. Etching system. According to the wet etching system of the present invention, fine circuit patterns (circuit wiring) required for TapeBGA, TCP, COF, and the like can be formed without shape defects (particularly, maintaining the upper width of the circuit wiring).

Description

Wet etching system for copper-containing material, and patterning method

The present invention relates to a wet etching system and a patterning method for patterning a copper-containing material, and in particular, copper-containing which can form fine circuit patterns (circuit wiring) required for TapeBGA, TCP, COF, and the like without defects. A wet etch system and patterning method of a material.

BACKGROUND A printed wiring board (or film) having circuit wiring formed on its surface is widely used for mounting electronic components, semiconductor devices, and the like. In recent years, in accordance with the demand for miniaturization and high functionalization of electronic devices, high density and thinning are also desired for circuit wiring of printed wiring boards (or films).

As a method of forming a high-density circuit wiring, a method called a subtractive method or a semiadditive method is known, and wet etching is performed in these methods.

In order to form fine circuit wiring, there should be no residual film at the bottom of the etching, the side surface of the circuit wiring viewed from the top should be straight (straight), the cross section of the circuit wiring should be rectangular, and the high etching factor Although it is abnormal, in reality, shape defects, such as a residual film, linear dizziness, side etching, undercut, and fall of the etching factor by narrowing of the circuit wiring upper width (henceforth "top width") generate | occur | produce. For this reason, in wet etching, it is desired to suppress these shape defects. In particular, in the fine circuit wiring required for TapeBGA, TCP, COF, and the like, in order to maintain the bonding area and to improve heat dissipation, the circuit wiring upper width must be maintained.

Regarding the shape defects of the circuit wiring as described above, various techniques have been reported to improve by studying the components of the etchant composition.

For example, Patent Document 1 discloses a circuit pattern formation method by a semiadditive method using an etchant composition containing divalent iron ions, hydrochloric acid, a copper-containing material etching accelerator, and a copper-containing material etching control agent as essential components. Is disclosed. Here, as a copper-containing material etching control agent, the compound which added propylene oxide and ethylene oxide to the active hydrogen group of an amine compound is disclosed, and also using phosphoric acid as a component which improves the cleaning effect and leveling property of a copper surface is disclosed. have.

Further, Patent Document 2 includes an aqueous solution containing a polymer selected from the group consisting of an acid selected from the group consisting of oxidizing agents of copper, hydrochloric acid and organic acid salts, polyalkylene glycols and copolymers of polyamines and polyalkylene glycols. The etching agent composition of the copper or copper alloy which suppressed narrowing of side etching and the upper part of a circuit wiring is disclosed. Here, as copper oxidant, 2nd copper ion and 2nd iron ion are disclosed, and as a compound which produces 2nd copper ion, copper (II) chloride, copper bromide (II), copper hydroxide (II), ferric iron As the compound for generating ions, iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate and iron (III) acetate are disclosed. Moreover, as a polyalkylene glycol, polyethyleneglycol, polypropylene glycol, an ethylene oxide propylene oxide copolymer are disclosed, As a copolymer of a polyamine and a polyalkylene glycol, ethylenediamine, diethylenetriamine, triethylenetetramine The copolymer of ethylenediamine, such as tetraethylene pentamine, pentaethylene hexamine, and N-ethylethylenediamine, and a polyethyleneglycol, a polypropylene glycol, an ethylene oxide propylene oxide copolymer is disclosed.

In addition, Patent Document 3 discloses an etchant composition comprising an aqueous solution containing an azole having only nitrogen atoms as an acid selected from an oxidizing metal ion source, an inorganic acid or an organic acid, and a hetero atom in a ring, and suppressing undercutting. have. Here, the second copper ion and the ferric ion are disclosed as the oxidizing metal ion source, and the phosphoric acid is disclosed as the acid. It is also disclosed to use nonionic surfactants such as block polymers of polyoxyethylene and polyoxypropylene in order to perform etching with a uniform surface shape.

Japanese Patent Laid-Open No. 2003-138389 Japanese Patent Application Laid-Open No. 2004-256901 Japanese Patent Laid-Open No. 2005-330572

However, the etching agent compositions disclosed in Patent Literatures 1 and 2 cannot uniformly etch fine circuit patterns required for TapeBGA, TCP, COF, and the like, and as a result, poor circuit shape (especially poor linearity) and There is a problem that a short or the like occurs. Moreover, since the etching agent composition disclosed in patent document 3 has low dispersibility and bad liquid drainage property to a fine circuit pattern, circuit peeling resulting from a circuit shape defect (especially partial undercut), phosphoric acid, and copper Alternatively, there is a problem that a short occurs due to the generation of sludge derived from a salt with iron.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and provides a wet etching system and a patterning method of a copper-containing material capable of forming a fine circuit pattern without shape defects (particularly, maintaining the upper width of the circuit wiring). It aims to do it.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, the present inventors wet-etched after exposing again the copper containing material which has the patterned photosensitive resist formed on the surface by exposure and image development, and solves the said problem. The present inventors have found that they can solve the problem.

In other words, the present invention includes exposure means for exposing a copper-containing material having a pattern of a positive photosensitive resist formed thereon, and wet etching means for wet etching the copper-containing material exposed by the exposure means. Wet etching system of the material.

In addition, the present invention, after exposing the copper-containing material formed on the surface of the pattern of the positive photosensitive resist (0.1) 15% by mass of at least one oxidant component selected from (A) second copper ions And (B) wet etching using an etchant composition comprising an aqueous solution comprising 0.001 to 5% by mass of a compound obtained by adding at least one selected from ethylene oxide and propylene oxide to active hydrogens of the (poly) amine compounds. It is a patterning method of the copper containing material used.

According to the present invention, it is possible to provide a wet etching system and a patterning method capable of forming a fine circuit pattern without shape defects (particularly, maintaining the upper width of the circuit wiring).

1 is a schematic diagram of the wet etching system of the present invention.
2 is a schematic diagram of a roll-to-roll wet etching system of the present invention.

Carrying out the invention  Form for

Embodiment 1

The wet etching system of the present invention has exposure means for exposing a predetermined copper-containing material and means for wet etching the copper-containing material exposed by the exposure means.

As for the copper containing material supplied to this wet etching system, a desired pattern (resist image) is formed by photolithography using a positive photosensitive resist. Here, photolithography is known in the art and is a technique of forming a desired pattern by exposure and development. Formation of a desired pattern by this photolithography can be performed according to a well-known method. In this photolithography, the exposure means is distinguished from the exposure means in the wet etching system of the present invention.

As a positive photosensitive resist which can be used by this invention, it does not specifically limit, A well-known thing in the art can be used. As a positive photosensitive resist, For example, Phenol novolak resin; Cresol novolac resins; Other alkyl group-containing novolak resins; Bisphenol A novolac resin; Bisphenol F novolak resins; Biphenol novolak resins; Polyamide phenol resins of polybenzoxazole precursors; Novolac resists such as hydroquinone novolac resins and the like; Polyhydroxystyrene and its derivatives; Polyacrylic acid and derivatives thereof; Polymethacrylic acid and its derivatives; Copolymers of three or more substances selected from hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof; Copolymers of three or more materials selected from cycloolefins and derivatives thereof, maleic anhydride, and acrylic acid and derivatives thereof; Copolymers of at least three substances selected from cycloolefins and derivatives thereof, maleimide, and acrylic acid and derivatives thereof; The resist represented by the high molecular polymer which partially substituted the acid labile group which has alkali dissolution control ability to the 1 or more types of high polymers chosen from a polynorbornene and a metasense ring-opening polymer is mentioned. Among these, the novolak-type resist mainly used in manufacture of TapeBGA, TCP, COF, etc. is preferable.

A general wet etching system has wet etching means for wet etching a copper-containing material in which a pattern (resist image) of a forged photosensitive resist is formed on the surface, but the wet etching system of the present invention further includes an exposure means before the wet etching means. Have This exposure means exposes the copper-containing material in which the pattern (resist image) of the positive photosensitive resist is formed on the surface, and causes alteration such as softening of the resist phase or change in solubility. The modified resist protects the angle of the upper portion of the circuit wiring at the time of wet etching to control the narrowing of the upper width of the circuit wiring, thereby preventing a shape defect of the circuit pattern.

The wet etching system of the present invention can be configured in accordance with a generally known wet etching system of a copper-containing material, except that the exposure means is provided.

The wet etching system of the present invention has a wet etching means having an exposure means, an etchant composition tank, an etching bath, and an etchant composition discharging device as a basic configuration, and means for removing the pattern of the positive photosensitive resist after the wet etching means. Can provide. In addition, before and after these means, a washing | cleaning means or a drying means may be provided, and the conveyance means taken from an etching tank may be used while introducing an etching process object (copper containing material) into an etching tank. The wet etching method may be either a batch type or a flow type, and may provide an autocontrol system in accordance with the redox potential, specific gravity, or pH of the etchant composition. When providing an auto control system, it is necessary to provide the detection control apparatus for controlling the composition of an etchant composition, an etching component supply liquid supply apparatus, etc.

An example of the wet etching system of the present invention is shown in FIG. 1. The wet etching system of the present invention has the exposure means 1 and the wet etching means 2 in a basic configuration. The wet etching means 2 has an etchant composition tank, an etching tank, and an etchant composition discharge apparatus (not shown), and the wet etching means 2 includes a detection control device 3 and an etching component supply liquid tank. (4) is connected. The etchant composition supplying apparatus 6 is supplied to the detection control apparatus 3 from the wet etching means 2 through the liquid feeding pipe 7. The detection control apparatus 3 performs an analysis or the like which is an index of the composition of the redox potential, specific gravity, pH, etc. of the etchant composition, and etches the control signal 10 so that the composition of the etchant composition is in a predetermined range. It transmits to the component supply liquid supply apparatus 5. The etching component replenishing liquid feeding device 5 supplies the etching component replenishing liquid from the etching component replenishing liquid tank 4 to the wet etching means 2 in accordance with the received signal. In addition, the etchant composition analyzed by the detection control device 3 is returned to the wet etching means 2 through the liquid feed pipe 8.

In the wet etching system of the present invention, the copper-containing material in which the pattern of the positive photosensitive resist that is the wet etching treatment object is formed on the surface of the wet etching system sequentially exposes the exposure means 1 and the wet etching means 2. Through the furnace, it is returned to the next step. The conveying means is not particularly limited, and for example, conveying apparatuses such as various conveyors, robot arms, and loaders and unloaders can be used.

Since the wet etching system of the present invention can form a fine circuit pattern while controlling the narrowing of the upper width of the circuit wiring, patterning with a thickness of 1 to 20 μm and an etching space of 1 to 20 μm corresponding to the processing size of TapeBGA, TCP, and COF Applicable to In particular, the wet etching system of the present invention is suitable for the production of COF tapes having a thickness of 1 to 10 µm and an etching space of 1 to 10 µm.

An example of the wet etching system of the present invention suitable for these productions is shown in FIG. 2. 2 is a roll-to-roll wet etching system. You may add the structure of 3-10 of FIG. 1 to the said wet etching system.

In the wet etching system of the present invention, the light source of the exposure means 1 is not particularly limited, and the same light source as that of general photolithography can be used. For example, as a light source, a fluorescent lamp, a CRT, a xenon lamp, a tungsten lamp, a carbon arc lamp, an LED, a metal halide lamp, an ultrahigh pressure mercury lamp, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, a YAG laser And excimer lasers and semiconductor lasers.

The radiation to be irradiated is not particularly limited as long as it is in the UV region, and examples thereof include i-rays, h-rays, and g-rays. These may be irradiated selectively, respectively, and may be irradiated as the bright line containing 3 wire | line.

If the amount of light to be irradiated is too small, a sufficient effect cannot be obtained. If the amount of light to be irradiated is too long, the wet etching treatment time becomes long, so 10 to 400 mJ / cm ² is preferable, and 50 to 250 mJ / cm ² is more preferable.

Embodiment 2

The patterning method of the copper containing material of this invention is performed by wet-etching using a predetermined etching agent composition, after exposing the copper containing material in which the pattern (resist image) of the positive photosensitive resist was formed in the surface. According to this method, the resist image deteriorated by exposure can protect the angle of the upper portion of the circuit wiring during wet etching, suppress the narrowing of the upper width of the circuit wiring, and suppress the shape defect of the circuit pattern.

The exposure method is the same as that of general photolithography, and has been described above.

The etchant composition used for the wet etching includes (A) at least one oxidant component selected from the second copper ions and the ferric ions (hereinafter referred to as "(A) component"), (B) ethylene oxide and propylene It consists of an aqueous solution containing the compound (henceforth "(B) component") which added at least 1 chosen from an oxide to the active hydrogen of a (poly) amine compound.

The reason why the narrowing of the upper width of the circuit wiring is suppressed by the etchant composition is not clear, but the component (B) penetrates into the resist to promote softening, thereby protecting the angle of the upper portion of the circuit wiring, or the component (B). It is presumed that this is attributable to the localization of the copper-containing material and the resist phase in the vicinity of the interface specifically to effect partial etching suppression.

(A) A component is a component which has a function which oxidizes a copper containing material, and performs etching, A 2nd copper ion and a 2nd iron ion can be used individually, or can mix and use them. These 2nd copper ion and 2nd iron ion can be contained in an etching agent composition by mix | blending copper, a copper (II) compound, and an iron (III) compound as a source, respectively. As a copper (II) compound, copper (II) chloride, copper (II) bromide, copper (II) sulfate, copper (II) hydroxide, etc. are mentioned, for example. Moreover, as iron (III) compound, iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate, iron (III) acetate, etc. are mentioned, for example. have. These compounds can be used individually or in mixture of 2 or more types. Among these second copper ions or ferric ion sources, copper, copper (II) chloride, copper (II) sulfate and iron (III) chloride are selected from the viewpoints of cost, stability of the etchant composition, and controllability of the etching rate. Preference is given to copper, copper (II) sulfate and iron (III) chloride.

The concentration of the component (A) in the etchant composition is 0.1 to 15% by mass, preferably 1 to 10% by mass in terms of ions. Here, the ion conversion means conversion of 2nd copper ions or conversion of ferric ions when using only 2 copper ions or ferric ions, and mixes 2nd copper ions and 2nd iron ions. In the case of using, the ion conversion of both the second copper ions and the ferric ions means. When the concentration of the component (A) is less than 0.1% by mass, the etching time is long, so that the resist deteriorates and the productivity decreases. On the other hand, when the density | concentration of (A) component exceeds 15 mass%, it becomes impossible to control an etching rate and it becomes difficult to hold | maintain a top width.

(B) A component is a compound which added at least 1 chosen from ethylene oxide and a propylene oxide to active hydrogen of a (poly) amine compound. Examples of the (poly) amine compounds constituting this compound include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethanol isopropanolamine, diethanol isopropanolamine, and ethanol diisopropanol. Alkanolamines such as amines; Alkyl alkanolamine which substituted these alkanolamine by alkyl; And the compound etc. which are represented by following General formula (1) are mentioned:

In said formula (1), R <^1> represents a C2-C6 alkylene group, X <^1> -X <^4> is a hydrogen atom or a C1-C4 alkyl group, and at least 1 of X <^1> -X <^4> is Hydrogen and n is a number of 0-5. Here, as the alkyl group of X ¹ to X ⁴ , methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl and the like can be given. Moreover, ethylene, propylene, butylene, butylene, pentylene, pentylene, hexylene etc. are mentioned as an alkylene group of R <^1> .

When both ethylene oxide and propylene oxide are added to the active hydrogen of the (poly) amine compounds, block addition may be sufficient as ethylene oxide and propylene oxide, and random addition may be sufficient as it. In addition, (B) component can be used individually or in mixture of 2 or more types.

Especially, the compound represented by following General formula (2) which component (B) is most excellent in the maintenance result of a top width is preferable.

In said formula (2), R <^1> represents a C2-C6 alkylene group, X <^5> -X <^7> represents group represented by following General formula (3), X <^8> is a hydrogen atom or following General formula (3) Represents group represented by), and n represents the number of 1-5.

In said formula (3), R <^2> , R <^3> represents an ethylene group or a propylene group, p and q show the number whose number average molecular weight of a compound becomes 200-10,000.

In particular, it is preferable that R ² is a propylene group and R ³ is an ethylene group because the retention effect of the top width is remarkable, n is 1, and all of X ⁵ to X ⁸ are represented by the formula (3). Compound is preferred because it is readily available.

Moreover, when the number average molecular weight of (B) component is smaller than 200, sufficient circuit shape improvement may not be obtained, and when larger than 10,000, sufficient etching rate may not be obtained and etching may be inadequate. Therefore, 200-10000 are preferable for the number average molecular weight of (B) component. In particular, since the etching rate is favorable when the number average molecular weight of (B) component is 200-5,000, it is the most preferable.

In the etching agent composition, the concentration of the component (B) is 0.001 to 5% by mass, preferably 0.05 to 2% by mass. If the concentration of component (B) is lower than 0.001 mass%, sufficient use effect cannot be obtained. On the other hand, when (B) component # density | concentration is higher than 5 mass%, pattern shape defects etc. by penetration into a resist interface arise.

The etchant composition may contain well-known components contained in an etchant composition other than the said (A) component and (B) component. As well-known components, For example, an inorganic acid, an organic acid, a glycol ether compound, surfactant, an amino acid compound, an azole compound, a pyrimidine compound, a thiourea compound, an amine compound, an alkylpyrrolidone compound, an organic chelate compound, A polyacrylamide compound, hydrogen peroxide, a persulfate, an inorganic salt, a 1st copper ion, and a 1st iron ion are mentioned. Although the density | concentration at the time of using these well-known components is not specifically limited, Generally, it is the range of 0.001 mass%-10 mass%.

An inorganic acid is a component which has the function of removing the copper oxide film and copper chloride of the surface of the copper containing material to be etched, the function of stabilizing an oxidizing agent, and the leveling property with respect to a copper containing material, and promotes etching. Examples of the inorganic acid include nitric acid, hydrogen chloride, sulfuric acid, phosphoric acid and polyphosphoric acid. These can be used individually or in mixture of 2 or more types. Among these, hydrogen chloride is preferable because it is easy to control etching. Phosphoric acid is also preferable because it has an effect of promoting etching to the Ni—Cr seed layer on the copper back surface.

When mix | blending an inorganic acid with an etching agent composition, it is preferable that the density | concentration of an inorganic acid is 0.05-10 mass%. If the concentration of the inorganic acid is lower than 0.05% by mass, sufficient use effects may not be obtained. On the other hand, when the concentration of the inorganic acid is higher than 10% by mass, etching may be excessive and the etching rate cannot be controlled, resulting in poor shape of the circuit wiring.

Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, crotonic acid, isocrotonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeline acid, maleic acid, and fumaric acid. Carboxylic acids such as malic acid, tartaric acid, citric acid, glycolic acid, lactic acid, sulfamic acid, nicotinic acid, ascorbic acid, hydroxypivalic acid, levulinic acid, and β-chloropropionic acid; And organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, 2-hydroxyethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid. These can be used individually or in mixture of 2 or more types.

Examples of the glycol ether compounds include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and triethylene glycol. Monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Low molecular glycol ether compounds such as dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and 3-methyl-3-methoxy-3-methoxybutanol; And high molecular glycol ether compounds such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, and polyethylene glycol monobutyl ether. These can be used individually or in mixture of 2 or more types.

As surfactant, anionic surfactant, nonionic surfactant other than (B) component, cationic surfactant, amphoteric surfactant, etc. are mentioned, for example.

As the anionic surfactant, for example, higher fatty acid salts, higher alcohol sulfate ester salts, sulfide olefin salts, higher alkyl sulfonates, α-olefin sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, phosphoric acid ester salts and fatty acid esters Sulfate ester salts, glyceride sulfate ester salts, sulfonates of fatty acid esters, α-sulfofatty acid methyl ester salts, polyoxyalkylene alkyl ether sulfate ester salts, polyoxyalkylene alkyl phenyl ether sulfate ester salts, polyoxyalkylene alkyls Sulfate ester salts of ether carboxylates, acylated peptides, fatty acid alkanolamides or alkylene oxide adducts thereof, sulfosuccinic esters, alkyl benzenesulfonates, alkylnaphthalene sulfonates, alkyl benzoimidazole sulfonates, polyoxyalkylene sulfosuccinic acids Salts, salts of N-acyl-N-methyltaurine, N-acylglutamic acid or salts thereof, acyloxye Sulfonates, alkoxyethanesulfonates, N-acyl-β-alanine or salts thereof, N-acyl-N-carboxyethyltaurine or salts thereof, N-acyl-N-carboxymethylglycine or salts thereof, acyl lactates, N- Acyl sarcosine salt, alkyl or alkenylamino carboxymethyl sulfate, etc. are mentioned.

As the nonionic surfactant, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether (additional form of ethylene oxide and propylene oxide may be random or block-shaped. ), Polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or ethylene oxide adduct thereof, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or Ethylene oxide adducts thereof, fatty acid-N-methylmonoethanolamide or ethylene oxide adducts thereof, fatty acid diethanolamides or ethylene oxide adducts thereof, sucrose fatty acid esters, alkyl (poly) glycerol ethers, polyglycerol fats Acid esters, polyethylene glycol fatty acid esters, fatty acid methyl ester ethoxylates, and N-long chain alkyl dimethylamine oxides.

As the cationic surfactant, for example, an alkyl (alkenyl) trimethylammonium salt, a dialkyl (alkenyl) dimethyl ammonium salt, an alkyl (alkenyl) quaternary ammonium salt, a mono or dialkyl (alk) containing an ether group or an ester group or an amide group Kenyl) quaternary ammonium salt, alkyl (alkenyl) pyridinium salt, alkyl (alkenyl) dimethylbenzyl ammonium salt, alkyl (alkenyl) isoquinolinium salt, dialkyl (alkenyl) morphonium salt, polyoxyethylene alkyl (al Kenyl) amine, alkyl (alkenyl) amine salt, polyamine fatty acid derivative, amyl alcohol fatty acid derivative, benzalkonium chloride, benzetonium chloride, etc. are mentioned.

Examples of the amphoteric surfactant include carboxybetaine, sulfobetaine, phosphobetaine, amide amino acid, and imidazolinium betaine-based surfactant.

Said surfactant can be used individually or in mixture of 2 or more types.

Examples of the amino acid compounds include glycine, alanine, valine, leucine, serine, phenylalanine, tryptophan, glutamic acid, amino acids such as aspartic acid, lysine, arginine, histidine, alkali metal salts thereof, and ammonium salts. These can be used individually or in mixture of 2 or more types.

As an azole compound, For example, Alkyl imidazole, such as imidazole, 2-methylimidazole, 2-undecyl-4-methylimidazole, 2-phenylimidazole, 2-methylbenzoimidazole; Benzoimidazoles such as benzoimidazole, 2-methylbenzoimidazole, 2-undecylbenzoimidazole, 2-phenylbenzoimidazole, and 2-mercaptobenzoimidazole; 1,2,3-triazole, 1,2,4-triazole, 5-phenyl-1,2,4-triazole, 5-amino-1,2,4-triazole, 1,2,3- Benzotriazole, 1-aminobenzotriazole, 4-aminobenzotriazole, 1-bisaminomethylbenzotriazole, 1-methyl-benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 5-methyl Triazoles such as -1H-benzotriazole and 5-chlorobenzotriazole; 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto Tetrazole such as -1H-tetrazole, 1-cyclohexyl-5-mercapto-1H-tetrazole, 5,5'-bis-1H-tetrazole; Benzothiazole, 2-mercaptobenzothiazole, 2-phenylthiazole, 2-aminobenzothiazole, 2-amino-6-nitrobenzothiazole, 2-amino-6-methoxybenzothiazole, 2- And thiazoles such as amino-6-chlorobenzothiazole. These can be used individually or in mixture of 2 or more types.

Examples of the pyrimidine compounds include diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, mercaptopyrimidine and the like. These can be used individually or in mixture of multiple.

Examples of thiourea compounds include thiourea, ethylene thiourea, thiodiglycol, mercaptan and the like. These can be used individually or in mixture of 2 or more types.

Examples of the amine compounds include diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethanol isopropanolamine, and diamine. Ethanol isopropanolamine, ethanol diisopropanolamine, polyarylamine, polyvinylpyridine, hydrochlorides thereof and the like. These can be used individually or in mixture of 2 or more types.

Examples of the alkyl pyrrolidone compounds include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone and N-amyl 2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Examples of the organic chelate compound include ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, triethylenetetramine hexaacetic acid, tetraethylenepentamine chilacetic acid, pentaethylenehexamine palmacetic acid, nitrilo triacetic acid, and alkali metal salts thereof. And ammonium salts. These can be used individually or in mixture of 2 or more types.

As a polyacrylamide compound, polyacrylamide, t-butyl acrylamide sulfonic acid, etc. are mentioned, for example. These can be used individually or in mixture of 2 or more types.

As persulfate, ammonium persulfate, sodium persulfate, potassium persulfate, etc. are mentioned, for example. These can be used individually or in mixture of 2 or more types.

Examples of the inorganic salts include sodium chloride, potassium chloride, ammonium chloride, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, sodium carbonate, potassium carbonate, ammonium sulfate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, and nitric acid. Ammonium, ammonium chlorate, sodium chlorate, potassium chlorate and the like. These can be used individually or in mixture of 2 or more types.

Examples of the compound that provides the first copper ion include cuprous chloride, cuprous bromide, cuprous sulfate, cuprous hydroxide, and the like. Examples of the compound that provides ferrous ions include ferrous chloride, ferrous bromide, ferrous iodide, ferrous sulfate, ferrous nitrate, ferrous acetate, and the like. These can be used individually or in mixture of 2 or more types.

An etchant composition can be manufactured by mixing the said component and water. The mixing method is not particularly limited and may be mixed using a known mixing device.

In the patterning method of this invention, the etching of the copper containing material using the said etchant composition can be performed by a well-known general method. Examples of the copper-containing material as the material to be etched include copper alloys such as silver copper alloys and aluminum copper alloys, and copper, and copper is particularly suitable. Moreover, it does not specifically limit also about an etching method, Dipping method, a spraying method, etc. can be used, What is necessary is just to adjust suitably according to the etching agent composition and etching method to be used also about the conditions of etching. Moreover, you may use well-known various methods, such as a batch type | mold, a flow type, the redox potential of a etchant, specific gravity, and auto-control type by an acid concentration.

The various conditions at the time of performing a wet etching are not specifically limited, What is necessary is just to select suitably according to the kind of etchant composition to be used. When performing etching by the spray method using the said etching agent composition, it is preferable that the processing temperature of wet etching is 30-50 degreeC, processing pressure is 0.05-0.2 MPa, and processing time is 20-300 second.

In addition, a replenishment liquid may be added to the etchant composition used for the wet etching in order to recover the deterioration of the liquid by repeating the wet etching. In particular, when employing the wet etching method by the autocontrol system, the replenishment liquid is previously set in the etching system and added to the etchant composition. The replenishment liquid is (A) component, (B) component, an inorganic acid component, and water, for example, and the density | concentration of (A) component and an inorganic acid is about 1 to 20 times these concentrations in the etching agent composition used for wet etching. to be.

After the wet etching is performed, the pattern of the positive photosensitive resist is removed. The removal of the resist pattern may be performed using a suitable resist remover according to the kind of the positive photosensitive resist. As a resist remover, the thing similar to the resist remover used at the time of photolithography can be used. As a resist remover, alkaline aqueous solution remover etc. are mentioned, for example. Examples of the alkali component of the aqueous alkali solution remover include sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate. The aqueous alkali solution remover may contain various organic amines, hydrazines, organic solvents, surfactants, and the like as auxiliary agents and additives.

Since the patterning method of the copper containing material of this invention can form a fine circuit pattern without a shape defect, it can be used for various manufacturing uses, such as a printed wiring board, a package board | substrate, COF tape, and TAB.

Example

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these.

(Preparation of Etching Agent Composition)

Compound shown in Table 1, 4.9 mass% ferric chloride (content of ferric ions: 1.7 mass%), 6.6 mass% of cupric chloride (content of ferric copper ions: 3.1 mass%), 0.2 mass The etchant composition a-h was obtained by mix | blending% hydrogen chloride, 0.94 mass% phosphoric acid, and water. It shows in Table 2 regarding content of the compound of Table 1 in an etching agent composition. Remainder of content in an etching agent composition is water.

compound Structure or designation  Number average molecular weight Ethylene oxide groups
Content (mass%) One Propylene Oxide of Ethylenediamine and Block Additives of Ethylene Oxide
Compound of formula (2) wherein R ¹ = ethylene,
n = 1, R ² = propylene, R ³ = ethylene,
X ⁸ is not a hydrogen atom
280 40 2 〃 500 40 3 〃 3,500 20 4 〃 5,000 40 5 Propylene Oxide of Ethylenediamine and Block Additives of Ethylene Oxide
Compound of formula (2) wherein R ¹ = ethylene,
n = 1, R ² = ethylene, R ³ = propylene,
X ⁸ is not a hydrogen atom
4,350 30 6
Ethylene Oxide Adduct of Polypropylene Glycol 2,200 40 7 C ₁₃ H ₂₇ O (C ₃ H ₆ O) ₃ (C ₂ H ₄ O) ₁₀ H
800 50 8 Ethylene Glycol Monomethyl Ether
- -

(Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-11)

After coating and drying a novolak-based forged photosensitive resist (PMER-P; manufactured by Tokyo Oka Co., Ltd.) on a COF tape substrate (50 mm x 50 mm) having a copper thickness of 8 µm, an exposure apparatus (UFX-2458B; manufactured by Ushio Electric Co., Ltd.) was applied. It exposed by using, and developed and rinsed, and the resist pattern of pitch 25 micrometers and space 6 micrometers was formed.

Subsequently, the COF tape base material on which the resist pattern was formed was subjected to exposure treatment under the exposure conditions shown in Table 3 using an exposure apparatus (ultra high pressure mercury lamp). Then, using the said etchant composition, wet etching was performed by spraying between the number of seconds (60-100 second) which becomes just etching on the conditions of process temperature 45 degreeC, and process pressure 0.05MPa. And the resist pattern was removed using the resist remover (acetone), and the copper circuit pattern was obtained. The following evaluation was performed about the shape of the obtained copper circuit pattern.

(1) Wiring Upper Width (Top Width)

Measurement was made from a laser microscope. The unit is μm.

(2) Wiring lower width (bottom width)

Measurement was made from a laser microscope. The unit is μm.

(3) etching factor

It calculated from the following formula.

Etch Factor = Copper Thickness (μm) / {(B-T) / 2}

In formula, T is a top width (micrometer), B is a bottom width (micrometer).

Table 3 and 4 show these evaluation results.

As shown in the results of Tables 3 and 4, after exposing, Examples 1-1 to 1-5 wet-etched using etchant compositions a to e containing Compound Nos. 1 to 5 are the top widths. There was little reduction and the etching factor improved. In particular, Examples 1-1 to 1-4 wet-etched using the etchant compositions a to d have a much smaller decrease in top width than Example 1-5 wet-etched using the etchant composition e. The improvement of the etching factor was also large.

On the other hand, Comparative Examples 1-1 to 1-5 which wet-etched without performing exposure were not able to fully suppress the reduction of a top width, and the etching factor fell. In addition, the comparative examples 1-6 to 1-11 which wet-etched using etchant composition f-h could not fully suppress the reduction of a top width, regardless of the presence or absence of exposure, and the etching factor fell.

(Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-5)

After coating and drying a novolak-type forged photosensitive resist (PMER-P; manufactured by Tokyo Oka Co., Ltd.) on a COF tape substrate (50 mm x 50 mm) having a copper thickness of 8 µm, an exposure apparatus (UFX-2458B; manufactured by Ushio Electric Co., Ltd.) was applied. It exposed using, and then developed and rinsed, and the resist pattern which has the pitch and space of Table 5 was formed.

Subsequently, the COF tape base material in which the resist pattern was formed was exposed to exposure conditions shown in Table 5 using an exposure apparatus (ultra high pressure mercury lamp). Thereafter, using the etchant composition d, wet etching was performed by spraying for 90 seconds under a condition of a treatment temperature of 45 ° C. and a treatment pressure of 0.05 MPa. And the resist pattern was removed using the resist remover (acetone), and the copper circuit pattern was obtained. About the shape of the obtained copper circuit pattern, evaluation of said (1)-(3) was performed.

As shown in the results of Table 5, even if the etching time was kept constant and the exposure conditions and the resist pattern (pitch and space) were changed, the decrease in the top width was small and the etching factor was improved.

As can be seen from the above results, according to the present invention, it is possible to provide a wet etching system and a patterning method capable of forming a fine circuit pattern without shape defects (particularly, maintaining the upper width of the circuit wiring).

Since this international application claims priority based on Japanese Patent Application No. 2009-162713 filed on July 9, 2009, the entire contents of this Japanese patent application are incorporated into this international application.

Claims (2)

Exposure means for exposing a copper-containing material having a pattern of a positive photosensitive resist formed on a surface thereof;
And a wet etching means for wet etching the copper-containing material exposed by the exposure means. After the pattern of the positive photosensitive resist is exposed to the copper-containing material formed on the surface, (A) 0.1 to 15% by mass of at least one oxidant component selected from the second copper ions and the ferric ions, and (B) ethylene oxide And wet etching using an etchant composition comprising an aqueous solution containing 0.001 to 5% by mass of a compound in which at least one selected from propylene oxide is added to active hydrogens of the (poly) amine compounds. Patterning method.

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