JP5750626B2 - Electro copper plating method - Google Patents

Electro copper plating method Download PDF

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JP5750626B2
JP5750626B2 JP2010063785A JP2010063785A JP5750626B2 JP 5750626 B2 JP5750626 B2 JP 5750626B2 JP 2010063785 A JP2010063785 A JP 2010063785A JP 2010063785 A JP2010063785 A JP 2010063785A JP 5750626 B2 JP5750626 B2 JP 5750626B2
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electrolytic copper
copper plating
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JP2011195893A (en
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田中 薫
薫 田中
伊内 祥哉
祥哉 伊内
縄舟 秀美
秀美 縄舟
謙祐 赤松
謙祐 赤松
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石原ケミカル株式会社
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  The present invention provides an electrolytic copper plating method that can satisfactorily form a copper plating film with high adhesion to an object to be plated having a large specific resistance such as an ITO film.

The ITO film is used for the electrode of a glass substrate (panel glass), for example, a thin TV panel. At present, the formation of the conductive film on the ITO film is processed by the silver paste method. There is a demand for cost reduction by plating.
Therefore, a conventional technique for forming a conductive film on the ITO film of the glass substrate by plating is as follows.

(1) Patent Document 1
It is described that an electroless nickel-phosphorus alloy plating film is formed on an ITO film, an electroless nickel-boron alloy film is formed on the ITO film, and an electroless gold film is further formed (claims, page 2). Item of action).

(2) Patent Document 2
It is described that a nickel layer is provided on an ITO film by electroless plating, and a gold layer is provided thereon by electroless plating (claim 1, paragraphs 9 to 11).

(3) Patent Document 3
On the ITO film, cation species of organic anion species (carboxylate derived from carboxylic acid, 2,4-pentanedionate derived from acetylacetone; paragraph 24) and transition metals (titanium, vanadium, chromium, manganese; claim 2) Forming a sintered body layer of fine metal particles (gold, silver, copper, platinum, palladium; claim 5) having a predetermined particle diameter via a transition metal thin film layer for promoting adhesion including (Claim 1, paragraph 21).

(4) Patent Document 4
It is described that 1 to 40 gold thin films are deposited on an ITO film by sputtering or vacuum deposition, and a gold film is formed with a gold plating solution (claims, item of action).

In the above Patent Documents 1 and 2, there is a limit to the film thickness because it is a film formation by electroless plating, and when a noble metal such as gold or silver is used for the film as in Patent Documents 3 to 4, the above-mentioned The cost is high.
Usually, a copper film can be easily considered as a conductive film by plating. However, for a high specific resistance such as an ITO glass electrode, a copper electrode template of a solar cell panel or a barrier layer of a Si wafer, for example, copper Even when a typical acidic electrolytic copper sulfate plating bath was applied as plating, only brittle particulate precipitation could be expected, and uniform and smooth film formation could not be obtained.
Also, when a copper pyrophosphate bath (approximately pH 8-9) is used, no copper film can be obtained.

On the other hand, the present applicant has previously disclosed an electrolytic copper plating bath containing a complexing agent for copper, which can be used in a neutral or alkaline range, as shown in Patent Documents 5-6.
(5) Patent Document 5
Specific complexing agents such as EDTA and HEDTA contain additives such as formaldehyde, hydrazine compounds and polyacrylamide (Section 1) or, if necessary, specific amino acids such as glycine, alanine and lysine (Claim 2) or, if necessary, an electro copper plating bath containing an alkali metal, an alkaline earth metal, an ammonium halide or sulfate. 1st to 3rd term, page 3 lower left column, page 5 to page 7).

(6) Patent Document 6
A specific complexing agent such as EDTA or HEDTA contains a divalent organic sulfur compound selected from mercaptans, sulfides, disulfides, thiazoles, thiophene, and benzothiophene (Claim 1, Paragraph 7, Paragraph 22). ) Or, if necessary, a specific amino acid such as glycine, alanine, valine, aspartic acid, an additive for improving film stretching selected from imidazoline, pyridine, bipyridyl, pyrazole, etc. 2, paragraphs 27 to 41), or, if necessary, an additive for improving the throwing power selected from alkali metals, alkaline earth metals, ammonium halides or sulfates. An electro copper plating bath is described (Claim 3, page 3, lower left column, paragraph 43).

JP-A 63-255377 Japanese Patent Laid-Open No. 11-15008 JP 2005-293937 A JP 63-109157 A Japanese Patent Laid-Open No. 4-120290 Japanese Patent No. 2678701

  However, in the case of the electrolytic copper plating bath containing the complexing agent, for example, when EDTA as shown in Example 1 of Patent Document 5 or a copper plating bath containing EDTA and glycine is applied, copper is formed into a film. However, there is a problem in practicality because adhesion is insufficient and plating is partially removed or burnt.

  The present invention technically forms a copper film with high adhesion even on an object to be plated having a large specific resistance, such as an ITO film, a copper electrode template of a solar battery panel, and a barrier layer of a silicon wafer. Let it be an issue.

As a result of intensive research on an electrolytic copper plating bath that can be used in a neutral or alkaline region containing the complexing agent as shown in Patent Documents 5 to 6, the present inventors have found that a specific complex is used in the copper plating bath. When adding a combination of a specific conductive salt and a specific crystal modifier, a copper film can be formed while ensuring sufficient adhesion to an object to be plated with a large specific resistance such as an ITO film. Ascertaining that the film can be satisfactorily formed, the present invention has been completed.

That is, the present invention 1 includes (a) a soluble copper salt,
(b) On an object to be plated using an electrolytic copper plating bath containing at least one complexing agent selected from polyamines, aminocarboxylic acids, aminoalcohols, oxycarboxylic acids, thioureas, and polycarboxylic acids. In the electrolytic copper plating method of forming a copper electrodeposition film on
The object to be plated is an ITO film ,
In addition to the above copper electroplating bath
(c) at least one conductive salt selected from halides or sulfates of any of alkali metals, alkaline earth metals or ammonium;
(d) A crystal comprising a sulfur-containing compound selected from mercaptans, sulfides, and thiazoles, a nitrogen-containing compound selected from amino acids, phenanthrolines, triazines, pyridine, 2-vinylpyridine, morpholine, pyrazole, and imidazoline. Containing at least one regulator (d),
Moreover, the electrolytic copper plating method is characterized in that the pH of the plating bath is 4 to 10.

Invention 2 is the invention 1 , wherein the polyamines among the complexing agent components are methylene diamine, ethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, diethylene triamine, tetraethylene pentamine, pentaethylene hexamine, hexa Ethyleneheptamine,
Aminocarboxylic acids are ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), ethylenediaminetetrapropionic acid, nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), metaphenylenediaminetetraacetic acid, 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, diaminopropionic acid and salts thereof,
The amino alcohol is monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,
Oxycarboxylic acids are tartaric acid, citric acid, malic acid, gluconic acid, glycolic acid, lactic acid, glucoheptonic acid and their salts,
The electrolytic copper plating method is characterized in that the thiourea is thiourea or a thiourea derivative.

Invention 3 is an electrolytic copper plating method according to Invention 2, wherein the complexing agent is ethylenediamine, EDTA, triethanolamine or thiourea.

Invention 4 is characterized in that, in any one of Inventions 1 to 3 , the conductive salt is potassium chloride, magnesium chloride, calcium chloride, potassium bromide, potassium iodide, potassium sulfate, sodium sulfate, or ammonium sulfate. This is an electro copper plating method.

Invention 5 is any one of Inventions 1 to 4 , wherein, among the crystal modifier components, the phenanthroline is phenanthroline or bipyridyl,
Mercaptans are mercaptosuccinic acid, thioglycolic acid, thioglycol,
The sulfides are thiodiglycolic acid, β-thiodiglycol, thiodipropionic acid,
The electrolytic copper plating method is characterized in that the amino acids are glycine, N-methylglycine, alanine, glutamic acid, lysine, aspartic acid, ornithine, cysteine and salts thereof.

The present invention 6 is the copper electroplating according to any one of the present inventions 1 to 5 , wherein a compound selected from phenanthrolines, sulfides and mercaptans and an amino acid are used in combination as a crystal modifier. Is the method.

Invention 7 is an electrolytic copper plating method according to any one of Inventions 1 to 6 , wherein the electrolytic copper plating bath further contains a surfactant.

Since the electrolytic copper plating bath of the present invention contains a specific complexing agent such as ethylenediamine, a conductive salt such as ammonium sulfate , and a crystal modifier such as amino acids and phenanthrolines, it can be used as an ITO film. When applied to an object to be plated having a large specific resistance, a uniform and smooth electrodeposition film of copper can be satisfactorily formed, and adhesion of the formed copper film can be sufficiently secured.
In this case, for example, in a copper plating bath lacking a conductive salt while adding the complexing agent, the film formability can be ensured, but the adhesion is insufficient, or the uniformity and smoothness of the film is poor. Although there is a problem, in the present invention, by combining specific components of a complexing agent, a conductive salt, and a crystal modifier , copper is deposited on an object to be plated having a large specific resistance such as an ITO film, which has been difficult in the past. With regard to the film, it was possible to have both film formability and adhesion.
In this crystal modifier, a combination of an amino acid such as glycine and a compound selected from phenanthrolines, mercaptans, and sulfides is particularly effective.

The present invention comprises a soluble copper salt (a), each specific complexing agent (b), a conductive salt (c) and a crystal modifier (d), and the pH range is within a predetermined range excluding strong acidity. In this method, a copper electrodeposition film is formed on an object to be plated having a large specific resistance using a certain electrolytic copper plating bath.
The object to be plated having a large specific resistance is an ITO film. Similarly, the present invention can also be applied to a copper electrode template of a solar cell panel that is an object to be plated having a large specific resistance. In addition, since the specific resistance increases as the circuit density and integration increases, for example, a circuit with a circuit width of 50 nm or less can be a plated object to which the present invention is applied.
The specific resistance of copper, which is a representative example of the conductive material, is 1.7 μΩ · cm, and among the copper-based lead frame (made of copper alloy), for example, the specific resistance of 194 material is approximately 2.5 μΩ · cm. On the other hand, the material to be plated having a large specific resistance of the present invention specifically refers to a material to be plated having a specific resistance of approximately 10 μΩ · cm or more. The specific resistance of the ITO film is generally 100 to 150 μΩ · cm.

The soluble copper salt (a) used in the electrolytic copper plating bath of the present invention is only required to be able to supply copper ions in the plating bath, copper sulfate, copper chloride, copper oxide, copper carbonate, copper acetate, copper pyrophosphate, Examples include copper vinegar, and copper sulfate and copper oxide are preferred.
The soluble copper salt can be used singly or in combination, and the content thereof with respect to the plating bath is 0.01 to 5 mol / L, preferably 0.05 to 0.5 mol / L.

The complexing agent (b) added to the electrolytic copper plating bath of the present invention is a compound that forms a copper complex in the plating bath, and makes it easy to deposit copper by gradual change in cathode current density with respect to change in electrode potential. It is selected from the group consisting of polyamines, aminocarboxylic acids, aminoalcohols, oxycarboxylic acids, thioureas, and polycarboxylic acids.
The above polyamines include methylene diamine, ethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, diethylene triamine, (see present invention 2) tetraethylene pentamine, pentaethylene hexamine, etc. hexaethyleneheptamine and the like, especially Ethylenediamine is preferred (see Invention 3 ).
Aminocarboxylic acids are ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), ethylenediaminetetrapropionic acid, nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), metaphenylenediaminetetraacetic acid, 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, diaminopropionic acid and salts thereof ( EDTA is preferred (see Invention 2 ), particularly EDTA (see Invention 3 ).

Examples of the amino alcohols include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine (see the present invention 2 ), and triethanolamine and tripropanolamine are preferable ( present (Invention 3 )
Examples of the oxycarboxylic acids include tartaric acid, citric acid, malic acid, gluconic acid, glycolic acid, lactic acid, glucoheptonic acid, and salts thereof (see Invention 2 ).
The thioureas are thiourea and thiourea derivatives (see the present invention 2 ). Examples of thiourea derivatives include N, N′-dimethylthiourea, trimethylthiourea, diethylthiourea (eg, N, N′-diethylthiourea), N, N′-diisopropylthiourea, allylthiourea, acetylthiourea, ethylenethiourea, N, N'-diphenylthiourea, thiourea dioxide, thiosemicarbazide, S-methylisothiourea sulfate, tributylthiourea, benzylisothiourea hydrochloride, N, N'-dibutylthiourea, 1-naphthylthiourea, tetramethylthiourea, Examples include 1-phenylthiourea, 1-methylthiourea and the like. As the thioureas, thiourea is particularly preferable (see the present invention 3 ).
Examples of the polycarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, malonic acid, and salts thereof.
The complexing agent can be used alone or in combination, and the content thereof relative to the plating bath is 0.01 to 2 mol / L, preferably 0.1 to 0.6 mol / L.

The conductive salt (c) contained in the electrolytic copper plating bath of the present invention increases the electrical conductivity, promotes copper deposition, or fulfills the function of improving adhesion and uniform electrodeposition, It is selected from metals, alkaline earth metals, ammonium halides and sulfates.
Examples of the conductive salt include potassium chloride, sodium chloride, magnesium chloride, calcium chloride, potassium bromide, potassium iodide, potassium sulfate, sodium sulfate, ammonium sulfate, ammonium chloride and the like (see the present invention 4 ), particularly ammonium sulfate. Is preferred.
The conductive salt can be used alone or in combination, and its content relative to the plating bath is 0.3 to 5.0 mol / L, preferably 1.0 to 2.0 mol / L. In particular, the higher the concentration of the conductive salt, the greater the contribution to the throwing power. For example, the preferable content of ammonium sulfate is 1.2 to 1.8 mol / L centering on 1.5 mol / L. It is.

In the electrolytic copper plating bath of the present invention, in addition to the soluble copper salt, the specific complexing agent, and the specific conductive salt , in addition to the soluble copper salt, the specific complexing agent, and the specific conductive salt , further from the viewpoint of improving the film forming property and adhesion in copper deposition. Is added as an essential component.
That is, the crystal modifier adjusts the crystal growth of copper to improve the adhesion of the copper film, and also improves the smoothness and uniformity, and is selected from mercaptans, sulfides, and thiazoles. And a nitrogen-containing compound selected from the group consisting of sulfur-containing compounds, amino acids, phenanthrolines, triazines, pyridine, morpholine, pyrazole, and imidazoline.
Among the above-mentioned sulfur-containing compounds, mercaptans include mercaptosuccinic acid, thioglycolic acid, thioglycol, 4-aminobenzenethiol, 2-mercaptobenzothiazole and the like (see Invention 5 ).
Similarly, the sulfides include thiodiglycolic acid, β-thiodiglycol, thiodipropionic acid and the like (see the present invention 5 ), and thiodiglycolic acid and thiodipropionic acid are preferable.
Similarly, thiazoles include thiazole, benzothiazole, 2-mercaptobenzothiazole, 2-methylbenzothiazole, 2- (methylmercapto) benzothiazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 2- Methyl-5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 6-nitro-2-mercaptobenzothiazole, 5- Hydroxy-2-methylbenzothiazole, 2-benzothiazole thioacetic acid and the like.

Examples of the amino acids among the nitrogen-containing compounds include glycine, N-methylglycine, alanine, glutamic acid, lysine, aspartic acid, ornithine, cysteine, lysine, hydantoic acid, and salts thereof (see the present invention 5 ). Glycine, cysteine and glutamic acid are preferred.
Similarly, phenanthrolines include 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dihydroxyphenanthroline, 3,4,7,8-tetramethylphenanthroline, 4,7-diphenyl-1. , 10-phenanthroline, 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline-disulfonic acid, 4,7-diphenyl-2,9-dimethyl- 1,10-phenanthroline-disulfonic acid, 2,2'-bipyridyl (α, α'-bipyridyl), 4,4'-bipyridyl, 2,2 ', 2 "-terpyridyl, 2,2'-diquinoline, etc. Or salts thereof, such as 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, bipyridyl (2,2′-bipi Jill, 4,4'-bipyridyl) are preferred.
Similarly, triazines include triazine, 2,4-diamino-6- (2'-methylimidazolyl (1 ')) ethyl-1,3,5-triazine, 2,4-diamino-6- (2'-ethyl). -4-Methylimidazolyl (1 ')) ethyl-1,3,5-triazine, 2,4-diamino-6- (2'-undecylimidazolyl (1')) ethyl-1,3,5-triazine, etc. Is mentioned.
In these crystal modifiers, it is preferable to combine amino acids and other types of crystal modifiers in combination (see Examples below), in particular, amino acids (such as glycine) and phenanthrolines (phenanthroline, bipyridyl). Etc.), sulfides (thiodiglycolic acid, thiodipropionic acid, etc.) and mercaptans (2-mercaptobenzothiazole, 4-aminobenzenethiol) are preferred in combination (see Invention 6 ).
The above-mentioned crystal modifier can be used singly or in combination, and its content with respect to the plating bath is 0.01 to 2 mol / L, preferably 0.1 to 0.6 mol / L for amino acids such as glycine. In the case of phenanthrolines, mercaptans, sulfides, etc., 5 to 100 ppm (= mg / L), preferably 10 to 60 ppm.

A surfactant can be further added to the electrolytic copper plating bath of the present invention from the viewpoint of preventing pits and improving the wettability of the object to be plated (see the present invention 7 ).
As this surfactant, a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, or an anionic surfactant can be used alone or in combination.
Specific examples of the nonionic surfactant include polyethylene glycol (hereinafter referred to as PEG), polypropylene glycol, C 1 -C 20 alkanol, phenol, naphthol, bisphenols, (poly) C 1 -C 25 alkylphenol, (poly) aryl phenol, C 1 -C 25 alkyl naphthol, C 1 -C 25 alkoxylated phosphoric acid (salt), sorbitan esters, polyalkylene glycol, C 1 -C 22 aliphatic amines, C 1 -C 22 aliphatic such as ethylene oxide (EO) and / or propylene oxide (PO) that engaged 2-300 mols contraction or an amide, and the like C 1 -C 25 alkoxylated phosphoric acid (salt).

The C 1 -C 20 alkanol addition condensation of the above ethylene oxide (EO) and / or propylene oxide (PO), methanol, ethanol, n- butanol, t-butanol, n- hexanol, octanol, decanol, lauryl alcohol, tetra Examples include decanol, hexadecanol, stearyl alcohol, eicosanol, oleyl alcohol, docosanol and the like. Similarly, examples of the bisphenols include bisphenol A, bisphenol B, and bisphenol F. Examples of the (poly) C 1 -C 25 alkylphenol include mono-, di-, or trialkyl-substituted phenols such as p-methylphenol, p-butylphenol, p-isooctylphenol, p-nonylphenol, p-hexylphenol, 2, Examples include 4-dibutylphenol, 2,4,6-tributylphenol, dinonylphenol, p-dodecylphenol, p-laurylphenol, and p-stearylphenol. Examples of the arylalkylphenol include 2-phenylisopropylphenol, cumylphenol, (mono, di or tri) styrenated phenol, (mono, di or tri) benzylphenol and the like. Examples of the alkyl group of the C 1 -C 25 alkyl naphthol include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like, and may be at any position of the naphthalene nucleus. Examples of the polyalkylene glycol include polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene polyoxypropylene copolymer.

The C 1 -C 25 alkoxylated phosphoric acid (salt) is represented by the following general formula (a).
Ra, Rb, (MO) P = O (a)
(In the formula (a), Ra and Rb are the same or different C 1 -C 25 alkyl, provided that one of them may be H. M represents H or an alkali metal.)

Examples of the sorbitan ester include mono-, di- or triesterized 1,4-, 1,5- or 3,6-sorbitan such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan distearate, sorbitan dioleate And sorbitan mixed fatty acid ester. Examples of the C 1 to C 22 aliphatic amine include saturated and unsaturated fatty acids such as propylamine, butylamine, hexylamine, octylamine, decylamine, laurylamine, myristylamine, stearylamine, oleylamine, beef tallow amine, ethylenediamine, and propylenediamine. An amine etc. are mentioned. Examples of the C 1 -C 22 aliphatic amide include amides such as propionic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, coconut oil fatty acid, and beef tallow fatty acid. Is mentioned.

Furthermore, as the nonionic surfactant,
R 1 N (R 2 ) 2 → O
(In the above formula, R 1 represents C 5 to C 25 alkyl or RCONHR 3 (R 3 represents C 1 to C 5 alkylene), R 2 represents the same or different C 1 to C 5 alkyl) and the like. Amine oxides can be used.

As the cationic surfactant, a quaternary ammonium salt represented by the following general formula (b)
(R 1 · R 2 · R 3 · R 4 N) + · X - ... (b)
(In the formula (b), X is halogen, hydroxy, C 1 -C 5 alkanesulfonic acid or sulfuric acid, R 1 , R 2 , R 3 and R 4 are the same or different C 1 -C 20 alkyl, aryl or benzyl. Or a pyridinium salt represented by the following general formula (c).
R 6- (C 5 H 4 N-R 5 ) + · X (c)
(In the formula (c), C 5 H 4 N is a pyridine ring, X is halogen, hydroxy, C 1 -C 5 alkanesulfonic acid or sulfuric acid, R 5 is C 1 -C 20 alkyl, R 6 is H or C 1. ~C 10 represents an alkyl.)

  Examples of cationic surfactants in the form of salts include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, dimethyl benzyl lauryl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl Benzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, dimethyldiphenylammonium salt, benzyldimethylphenylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine acetate, octadecylamine acetate, etc. Is mentioned.

  Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, {(mono, di, tri) alkyl} naphthalene sulfonates, etc. Is mentioned. Examples of the alkyl sulfate include sodium lauryl sulfate and sodium oleyl sulfate. Examples of the polyoxyethylene alkyl ether sulfate include sodium polyoxyethylene (EO5) nonyl ether sulfate and sodium polyoxyethylene (EO15) dodecyl ether sulfate. Examples of the polyoxyethylene alkylphenyl ether sulfate include polyoxyethylene (EO15) nonylphenyl ether sulfate. Examples of the alkyl benzene sulfonate include sodium dodecylbenzene sulfonate. Examples of the {(mono, di, tri) alkyl} naphthalene sulfonate include naphthalene sulfonate, sodium dibutyl naphthalene sulfonate, and naphthalene sulfonate formalin condensate.

  Examples of the amphoteric surfactant include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. Further, sulfation of a condensation product of ethylene oxide and / or propylene oxide and an alkylamine or diamine, or a sulfonated adduct can also be used.

  Representative carboxybetaines or imidazoline betaines are lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, 2-undecyl-1-carboxymethyl-1 -Hydroxyethyl imidazolinium betaine, 2-octyl-1-carboxymethyl-1-carboxyethyl imidazolinium betaine, and the like. Sulfated and sulfonated adducts include sulfated adducts of ethoxylated alkylamines, sulfonated Examples thereof include lauric acid derivative sodium salt.

  Examples of the sulfobetaines include coconut oil fatty acid amidopropyldimethylammonium-2-hydroxypropanesulfonic acid, N-cocoylmethyl taurine sodium, and N-palmitoylmethyl taurine sodium. Examples of the aminocarboxylic acid include dioctylaminoethylglycine, N-laurylaminopropionic acid, octyldi (aminoethyl) glycine sodium salt, and the like.

The pH of the electrolytic copper plating bath of the present invention is 4 to 10 , and the strongly acidic region is excluded (see Comparative Example 5 described later). Preferably it is pH 8-9. Since the electrolytic copper plating bath of the present invention contains a specific complexing agent, crystal adjusting agent, etc., if the pH is inclined to the acidic side of less than 3, the plating bath cannot be smoothly constructed (that is, cannot be complexed well). In addition, since the copper film formation is hindered (see Comparative Example 5 described later) and the object to be plated is eroded, the pH is adjusted to 3 or more. On the other hand, if it is inclined to the alkali side from the proper range of the present invention, there is a possibility that plating is not deposited or adhesion is deteriorated.
The bath temperature when electroplating using the copper plating bath of the present invention is generally 70 ° C. or lower, preferably about 20 to 50 ° C., more preferably about 40 to 50 ° C.
The cathode current density is 0.01 to 150 A / dm 2 , preferably 0.1 to 10 A / dm 2 , and the plating method of the present invention has excellent adhesion in a wide region from low current density to high current density. A copper electrodeposition film is obtained.

Hereinafter, examples of the electrolytic copper plating method of the present invention will be described, and an evaluation test example of film formability for copper deposition when each plating bath is applied to an object to be plated having a large specific resistance such as an ITO film, and Examples of copper electrodeposition coating adhesion tests will be sequentially described.
The present invention is not limited to the following examples and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.

<< Embodiment of electro copper plating method >>
Of Examples 1-30 below, Example 1 complexing agent ethylene diamine, ammonium sulfate conductive salt, with a basic bath of copper glycine and bipyridyl was crystal modifier were copper plated ITO film Examples 2 to 10 and 12 to 30 below are based on Example 1 as a basic bath, and the types and concentrations of complexing agents, conductive salts and crystal modifiers, bath pH, and types of objects to be plated. Is changed as shown in FIGS.

On the other hand, among Comparative Examples 1 to 8 below, Comparative Example 1 is an example of electroplating a lead frame using a conventional acidic copper sulfate plating bath, and Comparative Example 2 is an ITO film using a conventional acidic copper sulfate plating bath. The electroplated example and Comparative Example 3 are also examples in which the copper electrode template of the solar cell panel is electroplated with a conventional acidic copper sulfate plating bath. Comparative Example 4 is an example in which an ITO film was electroplated using a conventional copper pyrophosphate plating bath. Comparative Example 5 is an example in which the ITO film was electroplated using the above-described Example 1 as a basic bath and an electrolytic copper complex bath in which the pH of the bath was adjusted to the acidic side of the appropriate range of the present invention. Comparative Example 6 contains ethylenediamine (complexing agent), and is an example of electroplating an ITO film with an electrolytic copper complex bath that does not contain a conductive salt and a crystal modifier. Comparative Example 7 contains ethylenediamine (complexing agent). This is an example in which an ITO film is electroplated with an electrolytic copper complex bath containing no conductive salt. Comparative Example 8 is an example in which Example 1 is used as a basic bath and no crystal modifier is added.

FIG. 1 is a table summarizing the composition of electrolytic copper plating baths, plating conditions and types of objects to be plated in Examples 1 to 10, FIG. 2 is a table summarizing Examples 11 to 20, and FIG. FIG. 4 is a chart summarizing Comparative Examples 1 to 7. FIG.
1 to 4, the symbol “↑” means that the conditions such as the substrate and the composition are the same as those of the examples or comparative examples in the upper column.

(1) Example 1
An electrolytic copper plating bath was constructed with the following composition (a), and electroplating was performed on an ITO film (manufactured by Geomat Co., Ltd.) under the following condition (b). The ITO film glass substrate had a thickness of 0.7 mm, and the ITO film had a thickness of 1,000 ± 200 mm. Incidentally, as described above, the specific resistance of the ITO film is generally 100 to 150 μΩ · cm.
(a) Copper electroplating bath Copper sulfate pentahydrate 0.1 mol / L
Ethylenediamine 0.3 mol / L
Ammonium sulfate 1.5 mol / L
Glycine 0.3 mol / L
α, α'-bipyridyl 30ppm
pH 7
Incidentally, 0.1 mol / L of copper sulfate pentahydrate corresponds to 25 g / L, and 0.3 mol / L of ethylenediamine corresponds to 18 g / L.
Further, as described above, glycine and bipyridyl are crystal modifiers, but for convenience, glycine is crystal modifier 1 and bipyridyl is crystal modifier 2 as described later. In this case, the concentration of glycine is in the order of mol / L (= M), but bipyridyl is in the order of ppm.
(b) Plating conditions Bath temperature: 50 ° C
Cathode current density: 1.0 A / dm 2

(2) Examples 2 to 10
As shown in FIG. 1, using Example 1 as a basic bath, the type and concentration of the complexing agent are changed, and the composition, plating conditions, and types of objects to be plated are the same as in Example 1 except for the electrolytic copper plating bath. Set to. For example, Example 2 is an example in which the ethylenediamine of Example 1 was changed to EDTA · 4Na as a complexing agent, and Example 4 was changed to NTA and the concentration was changed from 0.3M to 0.4M. This is a modified example.

(3) Example 12 to 13
As shown in FIG. 2, using Example 1 as a basic bath, Examples 12 to 13 are examples in which one of glycine and bipyridyl, which are two types of crystal modifiers, is not added.

(4) Examples 14-18
As shown in FIG. 2, using Example 1 as a basic bath, bipyridyl (= crystal modifier 2) of the two crystal modifiers is changed to another species, or the concentration is changed (glycine is changed). None), the composition of the electrolytic copper plating bath, the plating conditions, and the type of the object to be plated were set in the same manner as in Example 1.

(5) Examples 19 to 21
As shown in FIGS. 2 to 3, using Example 1 as a basic bath, glycine (= crystal modifier 1) of the two types of crystal modifiers is changed to another species, or the concentration thereof is changed ( Bipyridyl was not changed), and the composition of the electrolytic copper plating bath, the plating conditions, and the type of the object to be plated were set in the same manner as in Example 1.

(6) Examples 22 to 27
As shown in FIG. 3, using Example 1 as a basic bath, the type and concentration of the conductive salt are changed, or the concentration of ammonium sulfate is changed, and the composition of the other electro copper plating bath, plating conditions, The type of the object to be plated was set in the same manner as in Example 1.
For example, Example 23 is an example in which the conductive salt is changed from ammonium sulfate to potassium chloride, and the concentration is also changed from 1.5M to 2.0M, and Example 24 is an ammonium sulfate concentration of 1.5M to 0.1M. It is an example changed to.

(7) Examples 28-30
As shown in FIG. 3, the pH conditions were changed using Example 1 as the basic bath, and the composition of the other copper electroplating bath, the plating conditions, and the type of the object to be plated were set in the same manner as in Example 1.

(9) Comparative Example 1
An electrolytic copper plating bath was constructed with the following composition (a), and a copper-based lead frame (CDA-194 material) was electroplated under the following condition (b).
As described above, the specific resistance of the lead frame (194 material) is about 2.5 μΩ · cm.
(a) Copper electroplating bath Copper sulfate pentahydrate 60g / L
Sulfuric acid 200g / L
Chlorine ion (sodium chloride) 50ppm
SPS 10ppm
PEG # 4000 100ppm
Yanas Green B 5ppm
Incidentally, the SPS is a brightener and means bis (3-sulfopropyl) disulfide (disodium salt). Janus Green B is a leveler. PEG # 4000 is polyethylene glycol (average molecular weight 4000).
(b) Plating conditions Bath temperature: 25 ° C
Cathode current density: 1.0 A / dm 2

(10) Comparative Examples 2-3
As shown in FIG. 4, the comparative example 1 is used as a basic bath, and the object to be plated is changed to an ITO film (same as that of Example 1) or a copper electrode template of a solar cell panel. The composition and plating conditions were set in the same manner as in Comparative Example 1.

(11) Comparative example 4
An electrolytic copper plating bath was constructed with the following composition (a), and the same ITO film as in Example 1 was electroplated under the following condition (b).
(a) Copper electroplating bath Copper pyrophosphate 80g / L
Potassium pyrophosphate 300g / L
28% ammonia water 2mL / L
pH 9.5
(b) Plating conditions Bath temperature: 50 ° C
Cathode current density: 1.0 A / dm 2

(12) Comparative Example 5
As shown in FIG. 4, with Example 1 as the basic bath, the pH condition was changed to the acidic side from the appropriate range of the present invention, and the composition of the electrolytic copper plating bath, the plating conditions, and the type of the object to be plated were The same setting as in Example 1 was performed.

(13) Comparative Examples 6-8
As shown in FIG. 4, using Example 1 as a basic bath, no conductive salt is added (Comparative Example 7), or no conductive salt and a crystal modifier are added (Comparative Example 6). The composition of the electrolytic copper plating bath, the plating conditions, and the type of the object to be plated were set in the same manner as in Example 1.
In addition, as shown in FIG. 2, Comparative Example 8 uses Example 1 as a basic bath, does not add a crystal modifier, and the composition of the electrolytic copper plating bath, the plating conditions, and the types of objects to be plated are The setting was the same as in Example 1 (“Ratio 8” in the upper column in FIG. 2 means Comparative Example 8).

Then, about each to-be-plated object which performed the electrolytic copper plating of Examples 1-31 and Comparative Examples 1-7, each evaluation test of the precipitation property (namely, film formability) and adhesiveness of a copper plating film | membrane is as follows. As a result, the feasibility of electrolytic copper plating for the object to be plated having a large specific resistance was comprehensively evaluated.
<< Precipitation evaluation test example >>
The copper electrodeposition film formed on the object to be plated was visually observed, and the precipitation was evaluated according to the following criteria.
○: A copper film was uniformly formed on the object to be plated.
Δ: A film was temporarily formed on the object to be plated, but some plating omissions and burns were observed, and a uniform electrodeposition film could not be obtained.
X: Copper could not be formed into a film to be plated.

In the next adhesion test, only those for which the evaluations of .largecircle. To .DELTA. Were obtained in the above-described precipitation test were evaluated.
<< Example of adhesion evaluation test >>
A cellophane tape (made by Nichiban, 15 mm wide cellophane tape according to JIS1522) is applied to the object to be plated, and then peeled off perpendicularly to the object to be plated, with respect to the total area of the copper plating film formed on the object to be plated The ratio of the transition area of the plating film adhering to the tape was calculated, and the adhesion was evaluated as follows based on this ratio.
○: The adhesion ratio of the plating film to the tape was less than 5%.
Δ: Similarly, the adhesion ratio was 5% to 10%.
X: The adhesion rate was 10% or more.

《Example of comprehensive evaluation test》
When the above-mentioned precipitation was ◯ and the adhesion was from ◯ to △, and the precipitation was △, the adhesion was ◯.
In addition, although the comprehensive evaluation is of course x when the precipitation property is x, the adhesion property is x even if the precipitation property is ○, and the case where the precipitation property is Δ and the adhesion property is Δ to x reaches the practical level. Therefore, the overall evaluation is x.

<< Evaluation by test example >>
1 to 4 show the test results.
First, in Comparative Example 1 in which a lead frame having a small specific resistance was copper-plated using a conventional acidic copper sulfate plating bath, a copper electrodeposited film having good precipitation and adhesion was naturally obtained.
However, as shown in Comparative Example 2, when this conventional acidic copper sulfate plating bath is applied to an ITO film having a large specific resistance, no copper film can be obtained . The same applies to the application to the copper electrode template (see Comparative Example 3).
Further, as shown in Comparative Example 4, for an ITO film having a large specific resistance, a copper film could not be obtained in the same manner even when a conventional copper pyrophosphate bath was used.

On the other hand, in Examples 1 to 30, an electrolytic copper plating bath containing a specific complexing agent and a conductive salt and adjusted to a predetermined pH range is applied to an ITO film having a large specific resistance. Therefore, a copper electrodeposited film having generally good precipitation and adhesion was obtained.
Therefore, in order to examine Examples 1 to 30 in detail, in Examples 1 to 10 in which two kinds of crystal modifiers of glycine and bipyridyl were further added in addition to the specific complexing agent and the conductive salt, the precipitation property was increased. In addition, the adhesion was evaluated as “good”, and of course, a good overall evaluation was shown. In this case, the complexing agent may be variously changed from the ethylenediamine of Example 1 or the complexing agent concentration may be reduced from 0.3M to 0.2M as in Example 4. The overall evaluation was unchanged.
Moreover, even if it changed the kind of electroconductive salt variously from the ammonium sulfate of Example 1 like Examples 22-27, or even if the density | concentration was changed, there was no change in comprehensive evaluation. However, in Example 24 in which the concentration of ammonium sulfate was reduced to 0.1M, the evaluation of adhesion was worse than that in Example 1, but there was no problem in the overall evaluation. The concentration of the conductive salt is preferably adjusted to 0.5M or more.

On the other hand, even if bipyridyl (crystal modifier 2) of the two types of crystal modifiers was changed to another type of crystal modifier as in Examples 14 to 18, good comprehensive evaluation was shown.
On the contrary, even when glycine (crystal modifier 1) of the two types of crystal modifiers was changed to another type of amino acid as in Examples 19 to 21, there was no change in good comprehensive evaluation.

As for the crystal modifier, in Examples 12 to 13 in which one of the two types of crystal modifiers, glycine and bipyridyl, is not added, the evaluation of adhesiveness is also regressed. It was confirmed that a combination of two types of crystal modifiers (a combination of amino acids and other types of crystal modifiers (phenanthrolines, sulfides, mercaptans)) was preferable.

  In Examples 28 to 30, the pH of the copper plating bath was changed from Example 1 within the appropriate range of the present invention, but good overall evaluation was unchanged. However, in Example 28 where the pH of the bath is the lower limit (pH = 3) of the appropriate range of the present invention, the evaluation of the precipitation was slow (however, the overall evaluation is no problem). It was confirmed that the bath pH was preferably 4 to 10.

In Comparative Example 6 in which a complexing agent is added but no conductive salt and a crystal modifier are added, or in Comparative Example 7 in which a complexing agent and a crystal modifier are added but no conductive salt is added, the electrodeposition of copper Although the depositability of the film is ○, but the adhesion is an evaluation of ×, it is sufficient to add a complexing agent to the copper plating bath in order to obtain a good comprehensive evaluation as in Examples 1 to 30. In addition, it was confirmed that at least the addition of a conductive salt was necessary.
Further, in Comparative Example 8 in which no crystal modifier (glycine and bipyridyl) was added, the adhesion of the electrodeposition film was evaluated as Δ, so in order to obtain not only film formability but also good adhesion, In addition to the complexing agent and the conductive salt, the importance of adding a crystal modifier was confirmed.
Furthermore, in the comparative example 5 (pH = 1) in which a specific complexing agent and a conductive salt are added, but the pH of the copper plating bath is set to be more acidic than the appropriate range of the present invention, the comparative examples 2 to 4 and Similarly, copper film formation itself was not obtained. Accordingly, it was confirmed that the pH of the plating bath needs to be adjusted to 4 or more in order to obtain a copper electrodeposition film.

It is the table | surface which put together the composition of the electrolytic copper plating bath of Examples 1-10, plating conditions, and the kind of to-be-plated object. It is the equivalent figure of FIG. 1 which put together the electrolytic copper plating bath of Examples 12-20 and the comparative example 8. FIG. Reasonable view of Figure 1 summarizes the copper plating bath of Example 21-30. It is the equivalent figure of FIG. 1 which put together the electrolytic copper plating bath of Comparative Examples 1-7.

Claims (7)

  1. (a) a soluble copper salt;
    (b) On an object to be plated using an electrolytic copper plating bath containing at least one complexing agent selected from polyamines, aminocarboxylic acids, aminoalcohols, oxycarboxylic acids, thioureas, and polycarboxylic acids. In the electrolytic copper plating method of forming a copper electrodeposition film on
    The object to be plated is an ITO film ,
    In addition to the above copper electroplating bath
    (c) at least one conductive salt selected from halides or sulfates of any of alkali metals, alkaline earth metals or ammonium;
    (d) A crystal comprising a sulfur-containing compound selected from mercaptans, sulfides, and thiazoles, a nitrogen-containing compound selected from amino acids, phenanthrolines, triazines, pyridine, 2-vinylpyridine, morpholine, pyrazole, and imidazoline. Containing at least one regulator (d),
    And the pH of a plating bath is 4-10, The electrolytic copper plating method characterized by the above-mentioned.
  2. Among the complexing agent components, the polyamines are methylene diamine, ethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, diethylene triamine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine,
    Aminocarboxylic acids are ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), ethylenediaminetetrapropionic acid, nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), metaphenylenediaminetetraacetic acid, 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, diaminopropionic acid and salts thereof,
    The amino alcohol is monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,
    Oxycarboxylic acids are tartaric acid, citric acid, malic acid, gluconic acid, glycolic acid, lactic acid, glucoheptonic acid and their salts,
    The electrolytic copper plating method according to claim 1 , wherein the thiourea is thiourea or a thiourea derivative.
  3. The electrolytic copper plating method according to claim 2 , wherein the complexing agent is ethylenediamine, EDTA, triethanolamine or thiourea.
  4. The electrolytic copper according to any one of claims 1 to 3 , wherein the conductive salt is potassium chloride, magnesium chloride, calcium chloride, potassium bromide, potassium iodide, potassium sulfate, sodium sulfate, or ammonium sulfate. Plating method.
  5. Among the crystal modifier components, phenanthrolines are phenanthroline and bipyridyl,
    Mercaptans are mercaptosuccinic acid, thioglycolic acid, thioglycol,
    The sulfides are thiodiglycolic acid, β-thiodiglycol, thiodipropionic acid,
    The copper electroplating according to any one of claims 1 to 4 , wherein the amino acids are glycine, N-methylglycine, alanine, glutamic acid, lysine, aspartic acid, ornithine, cysteine and salts thereof. Method.
  6. 6. The electrolytic copper plating method according to claim 1 , wherein a compound selected from phenanthrolines, sulfides and mercaptans and an amino acid are used in combination as a crystal modifier.
  7. Furthermore, surfactant is contained in an electrolytic copper plating bath, The electrolytic copper plating method of any one of Claims 1-6 characterized by the above-mentioned.
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