JP6273525B2 - Etching solution, replenisher, and method for forming copper wiring - Google Patents

Description

  The present invention relates to a copper etching solution, a replenisher thereof, and a method for forming a copper wiring.

  In the production of a printed wiring board, when a copper wiring pattern is formed by a photoetching method, an iron chloride etching solution, a copper chloride etching solution, an alkaline etching solution or the like is used as an etching solution. When these etching solutions are used, copper under an etching resist called side etching sometimes dissolves from the side surface of the wiring pattern. That is, by covering with an etching resist, a portion that is originally not desired to be removed by etching (that is, a copper wiring portion) is removed by an etching solution, and the width becomes narrower from the bottom to the top of the copper wiring. The phenomenon that occurred. Especially when the copper wiring pattern is fine, such side etching must be minimized. In order to suppress this side etching, Patent Document 1 proposes an etching solution containing an azole compound that is a heteroaromatic 5-membered ring compound.

  According to the etching solution described in Patent Document 1, side etching can be suppressed. However, when the etching solution described in Patent Document 1 is used in a normal method, there is a possibility that the side surface of the copper wiring may be rattled. . When rattling occurs on the side surface of the copper wiring, the linearity of the copper wiring (the wiring width (W2) at the top of the copper wiring) (see FIG. 1) decreases, and the copper wiring width is optically increased from above the printed wiring board. When inspecting, there is a risk of erroneous recognition, and when the linearity is extremely deteriorated, the impedance characteristic of the printed wiring board may be deteriorated. Therefore, Patent Document 2 proposes an etching solution containing a specific aliphatic heterocyclic compound and in which the linearity of the copper wiring is not easily lowered.

  Further, Patent Document 3 discloses a composition containing a halide ion source such as bromide ions, which is used for microetching for promoting adhesion of an imaging resist or a solder mask on the surface of copper and a copper alloy. The said composition is not an etching liquid used for formation of copper wiring.

JP-A-2005-330572 Japanese Patent No. 5618340 Special table 2013-527323 gazette

  On the other hand, in the etching solution, in addition to the suppression of the side etching and the decrease in the linearity of the copper wiring, it is possible to further suppress the variation in the wiring width (W1) (see FIG. 1) at the bottom of the copper wiring after etching. Things are sought. Variation in the wiring width (W1) at the bottom of the copper wiring impairs the insulation reliability with the adjacent copper wiring, leading to a decrease in yield. Further, if the wiring width variation at the bottom of the copper wiring is extremely large, the impedance characteristics of the printed wiring board may be deteriorated.

  The present invention has been made in view of the above circumstances, and is an etching solution that can suppress side etching without deteriorating the linearity of copper wiring and can suppress variations in the wiring width (W1) at the bottom of the copper wiring. And a replenisher thereof, and a method for forming a copper wiring.

  The present invention is an etching solution for copper, the etching solution comprising an acid, an oxidizing metal ion, a bromide ion, an aliphatic acyclic compound, an aliphatic heterocyclic compound, and a heteroaromatic compound. An aqueous solution containing at least one compound selected from the group consisting of: a saturated aliphatic acyclic compound having 2 to 10 carbon atoms having only two nitrogen atoms as heteroatoms. (A), the aliphatic heterocyclic compound is an aliphatic heterocyclic compound (B) containing a 5- to 7-membered ring having one or more nitrogen atoms as a hetero atom constituting the ring, and the heteroaromatic compound The group compound relates to an etching solution which is a heteroaromatic compound (C) containing a heteroaromatic 6-membered ring having one or more nitrogen atoms as heteroatoms constituting the ring.

  The present invention provides a replenisher that is added to the etchant when the etchant is used continuously or repeatedly, and the replenisher comprises an aliphatic acyclic compound, an aliphatic heterocyclic compound, and a heteroaromatic An aqueous solution containing one or more compounds selected from the group consisting of aromatic compounds, wherein the aliphatic acyclic compound is a saturated aliphatic acyclic ring having 2 to 10 carbon atoms having only two nitrogen atoms as heteroatoms A compound of formula (A), wherein the aliphatic heterocyclic compound is an aliphatic heterocyclic compound (B) comprising a 5- to 7-membered ring having one or more nitrogen atoms as a hetero atom constituting the ring, The heteroaromatic compound relates to a replenisher that is a heteroaromatic compound (C) containing a heteroaromatic 6-membered ring having one or more nitrogen atoms as heteroatoms constituting the ring.

  The present invention relates to a method for forming a copper wiring for etching a portion of a copper layer not covered with an etching resist, and a method for forming a copper wiring for etching using the etching solution.

  The “copper” in the present invention may be made of copper or a copper alloy. In the present specification, “copper” indicates copper or a copper alloy.

  According to the present invention, it is possible to suppress side etching without reducing the linearity of the copper wiring, and to suppress variation in the wiring width (W1) at the bottom of the copper wiring after etching, and an etching solution and its replenishing solution, and A method for forming a copper wiring can be provided.

It is sectional drawing which shows an example of the copper wiring after etching with the etching liquid of this invention.

<Copper etchant>
The copper etching solution of the present invention is at least one selected from the group consisting of acids, oxidizing metal ions, bromide ions, aliphatic acyclic compounds, aliphatic heterocyclic compounds, and heteroaromatic compounds. An aqueous solution containing the above compound. The aliphatic acyclic compound is a saturated aliphatic acyclic compound (A) having 2 to 10 carbon atoms having at least two nitrogen atoms as a hetero atom, and the aliphatic heterocyclic compound has a ring. It is an aliphatic heterocyclic compound (B) containing a 5- to 7-membered ring having one or more nitrogen atoms as a constituent hetero atom, and the heteroaromatic compound has one or more nitrogen atoms as a hetero atom constituting the ring. It is a heteroaromatic compound (C) containing a heteroaromatic 6-membered ring.

  FIG. 1 is a cross-sectional view showing an example of a copper wiring after etching with the etching solution of the present invention. An etching resist 2 is formed on the copper wiring 1. A protective film 3 is formed on the side surface of the copper wiring 1 immediately below the end of the etching resist 2. When copper wiring is formed with a general copper chloride-based etching solution or iron chloride-based etching solution, cuprous ions and salts thereof are generated with the progress of etching. Since the replacement of the liquid becomes slow between the wirings, the etching in the vertical direction is gradually less likely to proceed due to the influence of the cuprous ions and the salt thereof, particularly in the fine wiring, resulting in a large side etching.

  According to the etching solution of the present invention, cuprous ions and salts thereof generated as etching progresses are selected from the group consisting of the aliphatic acyclic compound, the aliphatic heterocyclic compound, and the heteroaromatic compound. At least one selected compound is trapped so that the etching in the vertical direction proceeds rapidly, and at the same time, cuprous ions and salts thereof and the aliphatic non-ring It is considered that the protective film 3 composed of one or more compounds selected from the group consisting of a formula compound, the aliphatic heterocyclic compound, and the heteroaromatic compound is uniformly formed. Since the protective film 3 formed by at least one compound selected from the group consisting of the aliphatic acyclic compound, the aliphatic heterocyclic compound, and the heteroaromatic compound is uniform, the straight line of the copper wiring 1 It is considered that side etching can be suppressed without reducing the property.

  Furthermore, according to the etching solution of the present invention, bromide ions make the protective film 3 stronger and uniformly formed to the bottom of the copper wiring, so that side etching can be further suppressed, and the bottom of the copper wiring bottom after etching is further reduced. It is considered that variations in wiring width can be suppressed.

  Therefore, according to the etching solution of the present invention, the yield in the manufacturing process of the printed wiring board can be improved. The protective film 3 can be easily removed by a treatment with a removing solution after the etching treatment. As the removal liquid, an acidic aqueous solution such as dilute hydrochloric acid aqueous solution or dilute sulfuric acid aqueous solution is preferable.

<Acid>
The acid used in the etching solution of the present invention can be appropriately selected from inorganic acids and organic acids. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like (excluding hydrobromic acid). Examples of the organic acid include formic acid, acetic acid, oxalic acid, maleic acid, benzoic acid, glycolic acid and the like. Among the acids, hydrochloric acid is preferable from the viewpoints of etching rate stability and copper dissolution stability.

  The concentration of the acid is preferably 5 to 180 g / L, more preferably 7 to 150 g / L. When the acid concentration is 5 g / L or more, the etching rate increases, so that copper can be etched quickly. Moreover, when the density | concentration of an acid is 180 g / L or less, while melt | dissolving stability of copper is maintained, the deterioration of a working environment can be suppressed.

<Oxidizing metal ions>
The oxidizing metal ions used in the etching solution of the present invention may be metal ions that can oxidize metallic copper, and examples thereof include cupric ions and ferric ions. From the viewpoint of suppressing side etching and the stability of etching rate, it is preferable to use cupric ions as the oxidizing metal ions.

  The oxidizing metal ion can be contained in the etching solution by blending an oxidizing metal ion source. For example, when using a cupric ion source as the oxidizing metal ion source, specific examples thereof include copper chloride, copper sulfate, copper bromide, copper salts of organic acids, and copper hydroxide. For example, when a ferric ion source is used as the oxidizing metal ion source, specific examples thereof include iron chloride, iron bromide, iron iodide, iron sulfate, iron nitrate, and iron salts of organic acids.

  The concentration of the oxidizing metal ion is preferably 10 to 300 g / L, more preferably 10 to 250 g / L, still more preferably 15 to 220 g / L, and still more preferably 30 to 200 g / L. It is. When the concentration of the oxidizing metal ions is 10 g / L or more, the etching rate is increased, so that copper can be etched quickly. Moreover, when the concentration of the oxidizing metal ion is 300 g / L or less, the dissolution stability of copper is maintained.

<Bromide ion>
The bromide ions used in the etching solution of the present invention can be contained in the etching solution by blending a bromide ion source. For example, hydrobromic acid, sodium bromide, potassium bromide, lithium bromide, magnesium bromide, calcium bromide, barium bromide, copper bromide, zinc bromide, ammonium bromide, silver bromide, bromine, etc. Can be mentioned. From the viewpoints of reducing the linearity of the copper wiring and side etching, and further suppressing the variation in the wiring width (W1) at the bottom of the copper wiring after etching, hydrobromic acid, sodium bromide, odor Potassium halide is preferred.

  The bromide ion concentration is preferably 10 to 150 g / L, more preferably 20 to 120 g / L, and still more preferably 30 to 110 g / L. When the bromide ion concentration is 10 g / L or more, side etching can be effectively suppressed. Further, when the bromide ion concentration is 150 g / L or less, it is possible to effectively suppress variations in the wiring width (W1) at the bottom of the copper wiring after etching.

  The etching solution of the present invention is selected from the group consisting of aliphatic acyclic compounds, aliphatic heterocyclic compounds, and heteroaromatic compounds in order to suppress side etching without reducing the linearity of the copper wiring. One or more compounds are blended.

<Aliphatic acyclic compound>
The aliphatic acyclic compound of the present invention is a saturated aliphatic acyclic compound (A) having 2 to 10 carbon atoms having at least two nitrogen atoms as heteroatoms. The aliphatic acyclic compound has a linear or branched structure. In the aliphatic acyclic compound (A), one or more of the end groups of the aliphatic acyclic compound (A) is an NH ₂ group from the viewpoint of structural stability and solubility in an acidic liquid. preferable. In addition, the aliphatic acyclic compound (A) preferably has 2 to 9 carbon atoms, more preferably 2 to 8 carbon atoms, and 2 carbon atoms from the viewpoint of structural stability and solubility in an acidic liquid. ~ 7 is more preferred. One or more of these aliphatic acyclic compounds can be added to the etching solution of the present invention.

  Examples of the aliphatic acyclic compound (A) include 1,3-diaminopropane, 1,2-diaminopropane, N, N-bis (3-aminopropyl) methylamine, 2-diethylaminoethylamine, 2,2 ′. -Diamino-N-methyldiethylamine, 1,6-diaminohexane, 1,4-diaminobutane, 1,7-diaminoheptane, 1,10-diaminodecane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, penta Examples include ethylenehexamine, 3,6,9,12,15-pentaazaheptadecane-1,17-diamine. The aliphatic acyclic compound (A) is preferably diethylenetriamine, triethylenetetramine, tetraethylpentamine, or pentaethylenehexamine from the viewpoint of further suppressing side etching without further reducing the linearity of the copper wiring.

<Aliphatic heterocyclic compound>
The aliphatic heterocyclic compound of the present invention is an aliphatic heterocyclic compound (B) containing a 5- to 7-membered ring having one or more nitrogen atoms as a hetero atom constituting the ring. Specific examples of the aliphatic heterocyclic compound include pyrrolidine compounds having a pyrrolidine skeleton, piperidine compounds having a piperidine skeleton, piperazine compounds having a piperazine skeleton, homopiperazine compounds having a homopiperazine skeleton, hexahydro-1,3,5 -A hexahydro-1,3,5-triazine compound having a triazine skeleton can be exemplified. In the compounds listed above, the aliphatic heterocycle is an amino group, alkyl group, aralkyl group, aryl group, nitro group, nitroso group, hydroxyl group, carboxyl group, carbonyl group, alkoxy group, halogen group, azo group, cyano group. , May be substituted with a substituent such as an imino group, a phosphino group, a thiol group, or a sulfo group. One or more of these aliphatic heterocyclic compounds can be added to the etching solution of the present invention.

  The aliphatic heterocyclic compound (B) is a 5- to 7-membered ring having at least one nitrogen atom as a hetero atom constituting the ring in order to suppress side etching without reducing the linearity of the copper wiring. It is preferable that it is an aliphatic heterocyclic compound (b1) containing.

  Since the compound (b1) is an aliphatic heterocyclic compound having only nitrogen as a hetero atom constituting the ring and containing a 5- to 7-membered aliphatic heterocyclic ring, structural stability and resistance to acidic liquid High solubility.

  The compound (b1) can be appropriately selected from aliphatic heterocyclic compounds containing a 5- to 7-membered aliphatic heterocyclic ring having at least one nitrogen atom as a hetero atom constituting the ring, From the viewpoint of stability in the etching solution, an aliphatic heterocyclic compound having 3 or less nitrogen atoms constituting the ring is preferable.

  Among these, from the viewpoint of improving the linearity of the copper wiring and effectively suppressing side etching, the compound (b1) includes a pyrrolidine compound, a piperidine compound, a piperazine compound, a homopiperazine compound, and hexahydro-1,3,5. -It is preferable to mix | blend 1 or more types chosen from a triazine compound.

［式中、Ｒ^１〜Ｒ^５は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ Although the said pyrrolidine compound will not be specifically limited if it is a compound which has a pyrrolidine skeleton, For example, the pyrrolidine compound shown to following formula (I) can be illustrated.

[Wherein, R ^{1 to} R ⁵ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

The amino group represents any of —NH ₂ , —NHR, and —NRR ′, R and R ′ each independently represent a hydrocarbon-derived group having 1 to 10 carbon atoms, and R and R ′ are They may be bonded to each other to form a saturated ring structure. The amino group-containing substituent refers to any of a substituent composed of an amino group and a substituent in which a part of hydrogen is replaced with an amino group in a hydrocarbon derivative having 1 to 10 carbon atoms. From the viewpoint of effectively suppressing the side etching and further improving the linearity of the copper wiring, a substituent composed of an amino group or an amino group-containing substituent composed of carbon, hydrogen and nitrogen is preferable. The same applies to the following amino groups and amino group-containing substituents.

  The hydrocarbon-derived group refers to a hydrocarbon group in which part of carbon or hydrogen may be replaced with another atom or substituent. Examples of hydrocarbon-derived groups include methyl group, ethyl group, propyl group, butyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, allyl group, acetyl group, phenyl group, hydroxyethoxymethyl group, hydroxyethoxyethyl. A hydrocarbon-derived group consisting of carbon and hydrogen is preferable from the viewpoint of effectively suppressing side etching and further improving the linearity of the copper wiring. The same applies to the following hydrocarbon-derived groups.

  Specific examples of the pyrrolidine compound include pyrrolidine, 1-methylpyrimidine, 2-pyrrolidone, 1- (2-hydroxyethyl) pyrrolidine, indoline, 1-isopropyl-3-hydroxypyrrolidine, 1,2-cyclohexanedicarboximide, 1-butylpyrrolidine, 1-ethylpyrrolidine, 2- (2-hydroxyethyl) -1-methylpyrrolidine, 2-methylpyrrolidine, 1- (2-hydroxyethyl) pyrrolidine, 1- (3-aminopropyl) pyrrolidine, 1 -(2-aminoethyl) pyrrolidine, 3-aminopyrrolidine, 2-aminomethyl-1-ethylpyrrolidine, 2- (2-aminoethyl) -1-methylpyrrolidine, 3- (dimethylamino) pyrrolidine, 3- (methyl Amino) pyrrolidine, 1- (2-pyrrolidinylmethyl) pyrrolidine, 3- (diethylamino) pyrrolidine, 1,1'-dimethyl-3-aminopyrrolidine, 3- (ethylamino) pyrrolidine, 1-methyl-2- ( 1- Peridinomethyl) pyrrolidine, 4- (1-pyrrolidinyl) piperidine, 3- (N-acetyl-N-methylamino) pyrrolidine, 3- (N-acetyl-N-ethylamino) pyrrolidine, 2-pyrrolidinecarboxamide, 3-pyrrolidinecarboxamide , 3-acetamidopyrrolidine, 1-ethyl-2-pyrrolidinecarboxamide, 3-amino-1- (tert-butoxycarbonyl) pyrrolidine, 3- (tert-butoxycarbonylamino) pyrrolidine, 1-amino-2- (methoxymethyl) Pyrrolidine, 1-benzyl-3-aminopyrrolidine, 1-benzyl-3- (dimethylamino) pyrrolidine, 1-benzyl-3- (methylamino) pyrrolidine, 1-benzyl-3- (ethylamino) pyrrolidine, 3,4 -Diamino-1-benzylpyrrolidine, 1-benzyl-3-acetamidopyrrolidine, (1s, 6s) -2,8-diazabicyclo [4.3.0] nonane and the like.

［式中、Ｒ^６〜Ｒ^１１は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ The piperidine compound is not particularly limited as long as it is a compound having a piperidine skeleton, and examples thereof include a piperidine compound represented by the following formula (II).

[Wherein, R ^{6 to} R ¹¹ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the piperidine compound include piperidine, 2-piperidone, 1-methylpiperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethyl. Piperidine, 4-piperidinecarboxylic acid, 1,2,3,4-tetrahydroquinoline, decahydroisoquinoline, 2,6-dimethylpiperidine, 2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2,2,6 , 6-tetramethylpiperidine, 4-aminopiperidine, 1-aminopiperidine, 3-aminopiperidine, 4- (aminomethyl) piperidine, 4-amino-1-methylpiperidine, 2- (aminomethyl) piperidine, 3- ( Aminomethyl) piperidine, 4-piperidinecarboxamide, 2-piperidinecarboxamide, 1- (2-aminoethyl) piperidine, 4-acetamidopiperi , 3-acetamidopiperidine, 4-amino-1-isopropylpiperidine, 1- (3-aminopropyl) -2-methylpiperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 2,2 ′ -Bipiperidine, 4,4'-bipiperidine, 4-piperidinopiperidine, ethyl 4-amino-1-piperidinecarboxylate, 4-amino-1-benzylpiperidine, 4- (2-aminoethyl) -1-benzylpiperidine 4-acetamido-1-bensylpiperidine, 3-aminoquinuclidine and the like.

［式中、Ｒ^１２〜Ｒ^１７は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ The piperazine compound is not particularly limited as long as it is a compound having a piperazine skeleton, and examples thereof include a piperazine compound represented by the following formula (III).

[Wherein, R ^{12 to} R ¹⁷ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the piperazine compound include piperazine, 1-methylpiperazine, 2-methylpiperazine, 1-allylpiperazine, 1-isobutylpiperazine, 1-hydroxyethoxyethylpiperazine, 1-phenylpiperazine, 1-aminoethylpiperazine, 1 -Amino-4-methylpiperazine, 1-ethylpiperazine, 1-piperazineethanol, ethyl 1-piperazinecarboxylate, 1-formylpiperazine, 1-propylpiperazine, 1-acetylpiperazine, 1-isopropylpiperazine, 1-cyclopentylpiperazine, 1-cyclohexylpiperazine, 1- (2-methoxyethyl) piperazine, 1-piperonylpiperazine, 1- (diphenylmethyl) piperazine, 2-piperazinone, 1,4-dimethylpiperazine, 1-methyl-3-phenylpiperazine, 1,4-bis (3-aminopropyl) piperazine, 1- (2-dimethylamino Ethyl) -4-methylpiperazine, 1- (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1,4-di Formylpiperazine, 1- (4-aminophenyl) -4-methylpiperazine, 1,4-diacetyl-2,5-piperazinedione, 1-methyl-4- (1,4′-bipiperidin-4-yl) piperazine, 1- (4-aminophenyl) -4- (4-methoxyphenyl) piperazine, 1,4-dimethylpiperazin-2-one, 1,4-diethylpiperazin-2-one, 1,4-dimethylpiperazine-2, 3-dione, 2-piperazinecarboxylic acid, triethylenediamine and the like.

［式中、Ｒ^１８〜Ｒ^２４は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ The homopiperazine compound is not particularly limited as long as it is a compound having a homopiperazine skeleton, and examples thereof include a homopiperazine compound represented by the following formula (IV).

[Wherein, R ^{18 to} R ²⁴ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the homopiperazine compound include homopiperazine, 1-methylhomopiperazine, 1-formylhomopiperazine, 1,4-dimethylhomopiperazine, 4-methyl-1-homopiperazine dithiocarboxylic acid, 1-acetylhomopiperazine 1-butyryl homopiperazine and the like.

［式中、Ｒ^２５〜Ｒ^３０は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ The hexahydro-1,3,5-triazine compound is not particularly limited as long as it is a compound having a hexahydro-1,3,5-triazine skeleton. For example, hexahydro-1,3,5-triazine represented by the following formula (V): A triazine compound can be illustrated.

[Wherein, R ^{25 to} R ³⁰ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the hexahydro-1,3,5-triazine compound include hexahydro-1,3,5-triazine, hexahydro-1,3,5-trimethyl-1,3,5-triazine, and hexahydro-2,4. , 6-Trimethyl-1,3,5-triazine, hexahydro-1,3,5-tris (3-dimethylaminopropyl) -1,3,5-triazine, hexahydro-1,3,5-tripropyl-1 , 3,5-triazine, hexahydro-1,3,5-triethyl-1,3,5-triazine, hexahydro-1,3,5-triisopropyl-1,3,5-triazine, hexahydro-1,3, 5-tribenzyl-1,3,5-triazine, hexahydro-1,3,5-tris (2-hydroxyethyl) -1,3,5-triazine, hexahydro-1,3,5-trinitro-1,3, 5-triazine, hexahydro-1,3,5-trinitroso-1,3,5-triazine, hexahydro-2,4,6-trimethyl-1,3,5-trinitro-1,3,5-triazine, hexahydro- 1,3,5-triacryloyl-1,3,5-tria Emissions, hexamethylenetetramine and the like.

  As the compound (b1), 1-methylpiperazine, 1-aminoethylpiperazine, 1,4-bis (3-aminopropyl) can be used from the viewpoint of further suppressing side etching without further reducing the linearity of the copper wiring. Piperazine is preferred.

<Heteroaromatic compounds>
The heteroaromatic compound of the present invention is a heteroaromatic compound (C) containing a heteroaromatic 6-membered ring having one or more nitrogen atoms as heteroatoms constituting the ring. As the 6-membered ring heteroaromatic compound, those having only nitrogen as a hetero atom constituting the ring are preferable from the viewpoint of structural stability and solubility in an acidic liquid. Examples of the heteroaromatic compound include pyridine compounds, pyrimidine compounds, pyrazine compounds, pyridazine compounds, 1,3,5-triazine compounds substituted with amino group-containing substituents. In addition, the heteroaromatic ring is an amino group-containing substituent, alkyl group, aralkyl group, aryl group, nitro group, nitroso group, hydroxyl group, carboxyl group, carbonyl group, alkoxy group, halogen group, azo group, cyano group, imino group. It may be substituted with a substituent such as a group, phosphino group, thiol group or sulfo group. One or more of these 6-membered heteroaromatic compounds can be blended in the etching solution of the present invention.

［式中、Ｒ^３１〜Ｒ^３５は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。ただし、Ｒ^３１〜Ｒ^３５の少なくとも１つはアミノ基含有置換基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ The pyridine compound substituted with the amino group-containing substituent is not particularly limited as long as it is a compound substituted with an amino group-containing substituent and having a pyridine ring, and examples thereof include a pyridine compound represented by the following formula (VI). .

[Wherein, R ^{31 to} R ³⁵ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. However, at least one of R ^{31 to} R ³⁵ represents an amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the pyridine compound substituted with the amino group-containing substituent include 3-aminopyridine, 2-aminopyridine, 4-aminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine. 2-amino-5-methylpyridine, 2- (aminomethyl) pyridine, 3-amino-4-methylpyridine, 5-amino-2-methylpyridine, 4-amino-3-methylpyridine, 3-amino-2 -Methylpyridine, 4-amino-2-methylpyridine, 3-amino-5-methylpyridine, 2- (methylamino) pyridine, 4- (methylamino) pyridine, 3- (aminomethyl) pyridine, 4- (amino Methyl) pyridine, 2,3-diaminopyridine, 3,4-diaminopyridine, 2,6-diaminopyridine, 2-amino-5-cyanopyridine, 2-amino-3-cyanopyridine, 2-aminopyridine-3- Carboxaldehyde, pyridine-2-carboxamide, 2-amino-4,6-dimethyl Pyridine, 4- (2-aminoethyl) pyridine, 3- (2-aminoethyl) pyridine, 2- (2-aminoethyl) pyridine, 4-dimethylaminopyridine, 2-dimethylaminopyridine, 2- (ethylamino) Pyridine, 2-amino-3- (hydroxymethyl) pyridine, 4-acetamidopyridine, 2-acetamidopyridine, 3-acetamidopyridine, 4- (ethylaminomethyl) pyridine, 2-aminoquinoline, 3-aminoquinoline, 5- Examples thereof include aminoquinoline, 6-aminoquinoline, 8-aminoquinoline, 4-dimethylamino-1-neopentylpyridinium chloride and the like.

［式中、Ｒ^３６〜Ｒ^３９は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ Although the said pyrimidine compound will not be specifically limited if it is a compound which has a pyrimidine ring, For example, the pyrimidine compound shown to following formula (VII) can be illustrated.

[Wherein, R ^{36 to} R ³⁹ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the pyrimidine compound include pyrimidine, 4-methylpyrimidine, 2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine, 2-cyanopyrimidine, 4,6-dimethylpyrimidine, 2-amino-4-methyl. Pyrimidine, 2,4-diaminopyrimidine, 4,6-diaminopyrimidine, 4,5-diaminopyrimidine, 4-methoxypyrimidine, 4-amino-6-hydroxypyrimidine, 4,6-dihydroxypyrimidine, 2-mercaptopyrimidine, 2 -Chloropyrimidine, 2-amino-4,6-dimethylpyrimidine, 4-amino-2,6-dimethylpyrimidine, pyrimidine-5-carboxylic acid, 4,6-dimethyl-2-hydroxypyridine, 2,4-dimethyl- 6-hydroxypyridine, 2-amino-4-hydroxy-6-methylpyridine, 4-amino-6-hydroxy-2-methylpyridine, 2,4,6-triaminopyrimidine, 2,4-diamino-6-hydroxy Pirimi Gin, 4,6-hydroxy-2-methylpyridine, 4,5-diamino-6-hydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-chloro-4-methylpyrimidine, 4-chloro-2- Methylpyrimidine, 2-chloro-5-methylpyrimidine, 2-amino-5-methylpyrimidine, 4-amino-6-chloropyrimidine, 4-amino-2-chloropyrimidine, 5-amino-4-chloropyrimidine, 4- Chloro-6-hydroxypyrimidine, methyl pyrimidine-2-carboxylate, 4-amino-2-methyl-5-pyrimidinemethanol, 2-amino-5-nitropyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4, Examples include 6-diamino-2-methylpyrimidine, 2-chloro-5-ethylpyrimidine, 4-amino-2-dimethylamino-6-hydroxypyrimidine, 4,5-pyrimidinediamine, 2-phenylpyrimidine, quinazoline and the like.

［式中、Ｒ^４０〜Ｒ^４３は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ Although the said pyrazine compound will not be specifically limited if it is a compound which has a pyrazine ring, For example, the pyrazine compound shown to following formula (VIII) can be illustrated.

[Wherein, R ^{40 to} R ⁴³ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the pyrazine compound include pyrazine, 2,5-dimethylpyrazine, 2-methylpyrazine, 2,3-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3, 5,6-tetramethylpyrazine, 2-cyanopyrazine, 2-tert-butylpyrazine, 2-ethylpyrazine, 2,3-dicyanopyrazine, 2-ethyl-3-methylpyrazine, 2-vinylpyrazine, 2,3- Diethylpyrazine, 2,3-dicyano-5-methylpyrazine, 5-ethyl-2,3-dimethylpyrazine, 2-propylpyrazine, 2,3-diethyl-5-methylpyrazine, 2-methyl-3-propylpyrazine, 2-acetylpyrazine, 2-methyl-3-isobutylpyrazine, 2-acetyl-3-methylpyrazine, (2-mercaptoethyl) pyrazine, 2-acetyl-3-ethylpyrazine, pyrazinecarboxylic acid, 5-methylpyrazine-2 -Carboxylic acid, methyl 2-pyrazinecarboxylate, 2,3-pyrazine Dicarboxylic acid, 5-methyl-2,3-cyclopentenopyrazine, 5,6,7,8-tetrahydroquinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline, 2-aminopyrazine, 2- (aminomethyl) -5-methylpyrazine, 5,6-diamino-2,3-dicyanopyrazine, 3-aminopyrazine-2-carboxylic acid, 3-aminocarbonylpyrazine-2-carboxylic acid, 2-amino-5-phenylpyrazine, etc. Can be mentioned.

［式中、Ｒ^４４〜Ｒ^４７は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ Although it will not specifically limit if the said pyridazine compound is a compound which has a pyridazine ring, For example, the pyridazine compound shown to following formula (IX) can be illustrated.

[Wherein, R ^{44 to} R ⁴⁷ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the pyridazine compound include pyridazine, 2-methylpyridazine, 3-methylpyridazine, 4-methylpyridazine, pyridazine-4-carboxylic acid, 4,5-benzopyridazine, 3-aminopyridazine and the like.

［式中、Ｒ^４８〜Ｒ^５０は、それぞれ独立に水素、アミノ基含有置換基、又はアミノ基含有置換基を除く炭素数１〜１０の炭化水素誘導基を示す。これら置換基は互いに結合して環構造を形成していてもよい。］ The 1,3,5-triazine compound is not particularly limited as long as it is a compound having a 1,3,5-triazine ring, and examples thereof include 1,3,5-triazine compounds represented by the following formula (X). .

[Wherein, R ^{48 to} R ⁵⁰ each independently represent hydrogen, an amino group-containing substituent, or a hydrocarbon-derived group having 1 to 10 carbon atoms excluding the amino group-containing substituent. These substituents may be bonded to each other to form a ring structure. ]

  Specific examples of the 1,3,5-triazine compound include 1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, and 2-methyl-4,6-bis. (Trichloromethyl) -1,3,5-triazine, 2,4,6-tris (pentafluoroethyl) -1,3,5-triazine, 2,4,6-triphenyl-1,3,5-triazine 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-triazine, 4,6-bis (trichloromethyl) -2- (4-methoxy Phenyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4 , 6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-triazine, 2- (1,3-benzodioxol-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tri (4-pyridyl) -1, 3,5-triazine, 2,4,6-tris (2-pyridyl)- 1,3,5-triazine, 2,4-diamino-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4-diamino-6-dimethylamino-1 , 3,5-triazine, 2,4-diamino-6-diethylamino-1,3,5-triazine, 4,6-diamino-2-vinyl-1,3,5-triazine, 2,4,6-tris [Bis (methoxymethyl) amino] -1,3,5-triazine, 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,4-diamino-6-butylamino-1,3 , 5-triazine, 2,4-diamino-6- (cyclopropylamino) -1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine and the like.

  The heteroaromatic compound (C) includes 4-methylpyrimidine, 3-aminopyridine, 2-amino-4,6-dimethyl from the viewpoint of further suppressing side etching without further reducing the linearity of the copper wiring. Pyrimidine, 2,4-diamino-6-methyl-1,3,5-triazine and 4-dimethylaminopyridine are preferred.

  The heteroaromatic compound (C) is a complex having one or more nitrogen atoms as heteroatoms constituting a ring from the viewpoint of effectively suppressing side etching without reducing the linearity of the copper wiring. A heteroaromatic compound (c1) containing an aromatic 5-membered ring is preferred.

  Each of the heteroaromatic 6-membered ring and the heteroaromatic 5-membered ring may have at least one nitrogen atom as a heteroatom, and may have a heteroatom other than nitrogen. In order to effectively suppress side etching without reducing the linearity of the copper wiring, the heteroaromatic 6-membered ring and the heteroaromatic 5-membered ring have only nitrogen as a heteroatom, or a heteroatom Those having only nitrogen and sulfur are preferred. The heteroaromatic 6-membered ring and the heteroaromatic 5-membered ring are all amino groups, alkyl groups, aralkyl groups, aryl groups, nitro groups, nitroso groups, hydroxyl groups, carboxyl groups, aldehyde groups, alkoxy groups, It may be substituted with a substituent such as a halogen group, azo group, cyano group, imino group, phosphino group, thiol group or sulfo group.

The heteroaromatic compound includes the heteroaromatic 6-membered ring and the heteroaromatic 5-membered ring in the molecule, for example, a heteroaromatic 6-membered ring and a heteroaromatic 5-membered ring such as adenine represented by the following formula (XI): May be a heteroaromatic compound (hereinafter also referred to as a heteroaromatic compound (c1-1)) formed by condensation with a heteroaromatic compound or a heteroaromatic 6-membered ring and a heteroaromatic 5-membered ring. It may be a heteroaromatic compound (hereinafter also referred to as heteroaromatic compound (c1-2)) linked by a bond or a divalent linking group.

However, the heteroaromatic compound used in the present invention does not include a cyclic compound containing carbon of a carbonyl group as an atom constituting a heterocycle, such as guanine represented by the following formula (XII).

Examples of the heteroaromatic compound (c1-2) in which the heteroaromatic 6-membered ring and the heteroaromatic 5-membered ring are connected by a single bond include 2- (4-pyridyl) benzimidazole represented by the following formula (XIII), etc. Can be illustrated.

Examples of the heteroaromatic compound (c1-2) in which the heteroaromatic 6-membered ring and the heteroaromatic 5-membered ring are linked by a divalent linking group include, for example, 2,4-diamino-6 represented by the following formula (XIV): Examples include-[2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine. Examples of the divalent linking group include a divalent hydrocarbon derivative group, —O—, —S— and the like. The hydrocarbon-derived group refers to a hydrocarbon group in which some carbon or hydrogen may be replaced with another atom or substituent.

  The divalent hydrocarbon derivative group may be not only an alkylene group but also an alkenylene group, an alkynylene group, or the like. Moreover, although carbon number of the said bivalent hydrocarbon derivative group is not specifically limited, 1-6 are preferable from a soluble viewpoint, and 1-3 are more preferable.

  Specific examples of the compound having the structural characteristics of both the heteroaromatic compound (c1-1) and the heteroaromatic compound (c1-2) include azathioprine.

  Specific examples of the heteroaromatic compound (c1) include adenine, 6-benzyladenine, adenosine, 2-aminoadenosine, 2- (4-pyridyl) benzimidazole, 2,4-diamino-6- [2- ( 2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, 3- (1-pyrrolylmethyl) pyridine, 1H-pyrrolo [2,3-b] pyridine, 2,6-bis (2-benzimidazolyl) Pyridine, imidazo [1,2-b] pyridazine, purine, 6-chloropurine, 6-chloro-7-deazapurine, azathioprine, 6- (dimethylamino) purine, 7-hydroxy-5-methyl-1,3,4 -Triazaindolizine, imidazo [1,5-a] pyridine-3-carboxaldehyde, 6-mercaptopurine, 6-methoxypurine, 1H-1,2,3-triazolo [4,5-b] pyridine, thiamine 1H-pyrrolo [2,3-c] pyridine, 1H-pyrrolo [3,2-c] pyridine, 1H-pyrrolo [3,2-b] pyridine, 7-methyl-1H-pyrrolo [2,3-c ] 6-chloro-3-[(4-methyl-1-piperazinyl) methyl] -1H-pyrrolo [3,2-c] pyridine, 2-methyl-1H-pyrrolo [2,3-b] pyridine, 3- (Piperidinomethyl) -1H-pyrrolo [2,3-b] pyridine, 3- (1-methyl-1H-pyrrol-2-yl) pyridine, 1-methyl-2- (3-pyridinyl) -1H-pyrrole, 3 -(2-pyrrolyl) pyridine, 2- (1-pyrrolyl) pyridine, 3H-imidazo [4,5-c] pyridine, 1- (2-phenylethyl) -1H-imidazo [4,5-c] pyridine, 2-Azaindolizine, 2-phenyl-1H-imidazo [4,5-b] pyridine, 3- (3-pyridinyl) -1H-1,2,4-triazole, 7-methyl-1,2,4- Triazolo [4,3-a] pyridine, [1,2,4] triazolo [1,5-a] pyridine-6-amine, 3-nitro-5- (3-pyridyl) -1H-pyrazole, 1- ( 2-Pyridyl) -1H-pyrazol-4-amine, 2,3-dimethylpyrazolo [1,5-a] pyridine, 2,3,7-trimethylpyrazolo [1,5-a] pyridine, 8-amino -2-Phenyl [1,2,4] triazolo [1,5-a] pyridy , 5- (2-pyridyl) -2H-tetrazole, 2- (2-pyridyl) benzothiazole, 2- (2-pyridyl) -4-thiazoleacetic acid, 4- (benzylamino) -2-methyl-7H- Pyrrolo [2,3-d] pyrimidine, 7-deazaadenine, 5,7-dimethylpyrazolo [1,5-a] pyrimidine, 2,5-dimethylpyrazolo [1,5-a] pyrimidin-7-amine, 4-amino-1H-pyrazolo [3,4-d] pyrimidine, 1H-pyrazolo [4,3-d] pyrimidin-7-amine, 4-[(3-methyl-2-butenyl) amino] -1H-pyrazolo [3,4-d] pyrimidine, 4H-pyrazolo [3,4-d] pyrimidin-4-amine, imidazo [1,2-a] pyrimidine, 5,7-dimethyl [1,2,4] triazolo [1 , 5-a] pyrimidine, 8-tert-butyl-7,8-dihydro-5-methyl-6H-pyrrolo [3,2-e] [1,2,4] triazolo [1,5-a] pyrimidine, 5,7-Diamino-1H-1,2,3-triazolo [4,5-d] pyrimidine, 8-azapurine, 5-amino-2- (methylthio) thiazolo [5,4-d] pyrimidine, 2,5 , 7-Trichlorothiazolo [5,4- d] pyrimidine, 6-chloro-2- [4- (methylsulfonyl) phenyl] imidazo [1,2-b] pyridazine, 2-methylimidazo [1,2-b] pyridazine, 1H-imidazo [4,5- d] pyridazine, 1,2,4-triazolo [4,3-b] pyridazine, 6-chloro-1,2,4-triazolo [4,3-b] pyridazine, 6-methyl-1,2,4- Triazolo [4,3-b] pyridazine, 6,7-dimethyl-1,2,4-triazolo [4,3-b] pyridazine, tetrazolo [1,5-b] pyridazine, 6-chlorotetrazolo [1, 5-b] pyridazine, 8-methyltetrazolo [1,5-b] pyridazine, 6-chloro-7-methyltetrazolo [1,5-b] pyridazine, 6-methoxytetrazolo [1,5-b] Pyridazine, tetrazolo [1,5-b] pyridazine-6-amine, 7-methylpyrazolo [1,5-a] -1,3,5-triazine-2,4-diamine, pyrazolo [5,1-c] [ 1,2,4] benzotriazine-8-ol, 6,7-dimethylpyrazolo [5,1-c] [1,2,4] triazine-2 (6H) -amine, 4,6-dihydro-3 , 4-Dimethylpyrazolo [5,1- c] [1,2,4] triazine, 3-hydrazino-7-methyl-5-phenyl-5H-pyrazolo [3,4-e] -1,2,4-triazine, imidazo [5,1-f] [1,2,4] triazine-2,7-diamine, 4,5-dimethylimidazo [5,1-f] [1,2,4] triazine-2,7-diamine, 2-azaadenine, 7,8 -Dihydro-5-methylimidazo [1,2-a] [1,2,4] triazolo [1,5-c] [1,3,5] triazine, 7,8-dihydroimidazo [1,2-a ] [1,2,4] triazolo [1,5-c] [1,3,5] triazine, 1,2,4-triazolo [4,3-a] [1,3,5] triazine-3, Examples include 5,7-triamine, 5-azaadenine, 7,8-dihydroimidazo [1,2-a] [1,2,4] triazolo [1,5-c] [1,3,5] triazine, and the like. . The heteroaromatic compound may be in the form of a salt such as hydrochloride or sulfate, or may be a hydrate. In the etching solution of the present invention, one or more of the heteroaromatic compounds (c1) can be blended.

The heteroaromatic compound (c1) includes adenine represented by the formula (XI) and thiamine hydrochloride represented by the following formula (XV) from the viewpoint of further suppressing side etching without further reducing the linearity of the copper wiring. Is preferred.

  The concentration of at least one compound selected from the group consisting of the aliphatic acyclic compound, the aliphatic heterocyclic compound, and the heteroaromatic compound suppresses side etching and improves the linearity of the copper wiring. The range of 0.01 to 100 g / L is preferable, 0.02 to 80 g / L is more preferable, and the range of 0.05 to 30 g / L is more preferable.

  In addition to the components described above, other components may be added to the etching solution of the present invention to the extent that the effects of the present invention are not hindered. For example, you may add surfactant, a component stabilizer, an antifoamer, etc. When the other components are added, the concentration is about 0.001 to 5 g / L.

  The etching solution can be easily prepared by dissolving the components described above in water. As the water, water from which ionic substances and impurities have been removed is preferable. For example, ion-exchanged water, pure water, ultrapure water, and the like are preferable.

  The etching solution may be blended so that each component has a predetermined concentration when used, or a concentrated solution may be prepared and diluted immediately before use. Although the usage method of the said etching liquid is not specifically limited, In order to suppress side etching effectively, it is preferable to etch using a spray so that it may mention later. Further, the temperature of the etching solution during use is not particularly limited, but it is preferably used at 20 to 60 ° C. in order to effectively suppress side etching while maintaining high productivity.

  The replenisher of the present invention is a replenisher that is added to the etchant when the etchant of the present invention is used continuously or repeatedly, and the aliphatic acyclic compound, the aliphatic heterocyclic compound, and An aqueous solution containing one or more compounds selected from the group consisting of the heteroaromatic compounds. Each component in the replenisher is the same as the component that can be blended in the above-described etching solution of the present invention. By adding the replenisher, each component ratio of the etching solution is maintained appropriately, so that the effect of the etching solution of the present invention described above can be stably maintained.

  Moreover, the replenisher of the present invention may contain an acid such as hydrochloric acid in a range not exceeding the concentration of 360 g / L. The replenisher may contain a cupric ion source such as cupric chloride in a range not exceeding a cupric ion concentration of 14 g / L. Further, the replenisher may contain a bromide ion source such as sodium bromide in a range not exceeding 800 g / L in terms of bromide ion concentration. In addition to the above components, the replenishing solution may contain a component added to the etching solution. The components that may be contained in the replenisher are not directly contained in the replenisher, but are added directly to the etchant of the present invention when the etchant of the present invention is used continuously or repeatedly. You can also.

  The concentration of each component in the replenisher is appropriately set according to the concentration of each component in the etching solution. From the viewpoint of stably maintaining the effect of the etching solution of the present invention described above, the aliphatic It is preferable that the concentration of at least one compound selected from the group consisting of an acyclic compound, the aliphatic heterocyclic compound, and the heteroaromatic compound is 0.05 to 800 g / L.

  The copper wiring forming method of the present invention is characterized in that in the copper wiring forming method of etching a portion of the copper layer not covered with the etching resist, etching is performed using the above-described etching solution of the present invention. Thereby, as described above, side etching can be suppressed without reducing the linearity of the copper wiring, and variations in the wiring width (W1) at the bottom of the copper wiring can be suppressed. Moreover, in the copper wiring formation process which employ | adopted the formation method of the copper wiring of this invention, when using the etching liquid of this invention continuously or repeatedly, it is preferable to etch, adding the replenishing liquid of this invention mentioned above. This is because each component ratio of the etching solution is appropriately maintained, so that the effect of the etching solution of the present invention described above can be stably maintained.

  In the method for forming a copper wiring according to the present invention, it is preferable that the etching solution is sprayed on a portion of the copper layer not covered with the etching resist. This is because side etching can be effectively suppressed. When spraying, the nozzle is not particularly limited, and a sector nozzle, a full cone nozzle, a two-fluid nozzle, or the like can be used.

  When etching by spraying, the spray pressure is preferably 0.04 MPa or more, and more preferably 0.08 MPa or more. When the spray pressure is 0.04 MPa or more, the protective film can be formed on the side surface of the copper wiring with an appropriate thickness. Thereby, side etching can be effectively prevented. The spray pressure is preferably 0.30 MPa or less from the viewpoint of preventing damage to the etching resist.

  Next, examples of the present invention will be described together with comparative examples. In addition, this invention is limited to a following example and is not interpreted.

  Each etching solution having the composition shown in Tables 1 and 2 was prepared, etched under conditions described later, and each item was evaluated by an evaluation method described later. In addition, in each etching liquid of the composition shown to Tables 1-2, the remainder is ion-exchange water. Moreover, the density | concentration of hydrochloric acid shown to Tables 1-2 is a density | concentration as hydrogen chloride.

(Test board used)
A copper clad laminate was prepared by laminating a 12 μm thick electrolytic copper foil (trade name 3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.), and the copper foil was treated with a palladium catalyst-containing treatment solution (Okuno Pharmaceutical Co., Ltd., trade name: Ad Copper). After treatment with an electroless copper plating solution (Okuno Pharmaceutical Co., Ltd., trade name: Adcopper series), an electroless copper plating film was formed. Subsequently, an electrolytic copper plating film (Okuno Pharmaceutical Co., Ltd., trade name: Top Lucina SF) is used to form an electrolytic copper plating film having a thickness of 10 μm on the electroless copper plating film, and the total thickness of the copper layer is 22.5 μm. It was. The surface of the obtained electrolytic copper plating film was covered with a dry film resist having a thickness of 25 μm. Then, it exposed using the glass mask of line / space (L / S) = 36micrometer / 24micrometer, and the etching resist pattern of L / S = 36micrometer / 24micrometer was produced by removing an unexposed part by a development process.

(Etching conditions)
Etching was performed using a fan-shaped nozzle (manufactured by Ikeuchi Co., Ltd., trade name: ISVV9020) under conditions of a spray pressure of 0.20 MPa and a processing temperature of 45 ° C. The etching processing time was set as a target when the wiring width (W1) at the bottom of the copper wiring after etching reached 30 μm. After etching, washing and drying were performed, and the following evaluation was performed.

(Side etching amount)
Each test substrate subjected to the etching treatment was immersed in a 3% by weight aqueous sodium hydroxide solution at 50 ° C. for 60 seconds to remove the etching resist. Thereafter, the protective film was removed using hydrochloric acid (hydrogen chloride concentration: 7% by weight) with a fan-shaped nozzle (manufactured by Ikeuchi Co., Ltd., trade name: ISVV9020) at a spray pressure of 0.12 MPa, a treatment temperature of 30 ° C., and a treatment time of 10 seconds. . Then, a part of each test substrate was cut, embedded in a cold embedding resin made of polyester, and polished so that the cross section of the copper wiring could be observed. Then, the cross section is observed at 200 times using an optical microscope, the wiring width (W2) at the top of the copper wiring is measured, and the difference (W1-W2) from the wiring width (W1) at the bottom of the copper wiring is side-etched. The amount (μm) was used (see FIG. 1). The results are shown in Tables 1-2. The side etching amount is preferably 10 μm or less, and more preferably 7 μm or less.

(Top width linearity)
Similar to the evaluation of the side etching amount, the etching resist was removed and the protective film was removed. Then, using an optical microscope, the top surface of the test board was observed at 200 times, and the wiring width (W2) at the top of the copper wiring was measured at 40 μm intervals, 8 rows of 5 wirings per wiring, for a total of 40 locations, The standard deviation was defined as the top width linearity (μm). The results are shown in Tables 1-2. The top width linearity is preferably 1.0 μm or less, and more preferably 0.7 μm or less.

(Bottom width variation)
Similar to the evaluation of the side etching amount, the etching resist was removed and the protective film was removed. Then, using an optical microscope, the top surface of the test board was observed at a magnification of 200 times, and the wiring width (W1) at the bottom of the copper wiring was measured at 40 μm intervals, 8 rows of 5 wirings per wiring, for a total of 40 locations, The standard deviation was defined as the bottom width variation (μm). The bottom width variation is preferably 1.5 μm or less, and more preferably 1.2 μm or less.

  As shown in Table 1, according to the examples of the present invention, good results were obtained for any of the evaluation items. On the other hand, as shown in Table 2, the results of the comparative examples were inferior to those of the examples in some evaluation items. From this result, it was found that according to the present invention, side etching can be suppressed without reducing the linearity of the copper wiring, and variation in the wiring width (W1) at the bottom of the copper wiring can be suppressed.

1 Copper wiring 2 Etching resist 3 Protective film

Claims (9)

A copper etchant,
The etching solution is an aqueous solution containing an acid, an oxidizing metal ion, a bromide ion, and an aliphatic acyclic compound,
The said aliphatic acyclic compound is etching liquid which is a C2-C10 saturated aliphatic acyclic compound (A) which has only two or more nitrogen as a hetero atom.   The etching solution according to claim 1, wherein the acid is hydrochloric acid.   The etching solution according to claim 1, wherein the oxidizing metal ion is cupric ion. The etching solution according to any one of claims 1 to 3, wherein one or more terminal groups of the aliphatic acyclic compound (A) are NH ₂ groups.   The aliphatic acyclic compound (A) is 1,3-diaminopropane, 1,2-diaminopropane, N, N-bis (3-aminopropyl) methylamine, 2-diethylaminoethylamine, 2,2′- Diamino-N-methyldiethylamine, 1,6-diaminohexane, 1,4-diaminobutane, 1,7-diaminoheptane, 1,10-diaminodecane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene The etching solution according to any one of claims 1 to 4, which is at least one selected from the group consisting of hexamine and 3,6,9,12,15-pentaazaheptadecane-1,17-diamine.   The etching liquid according to claim 1, wherein the concentration of the aliphatic acyclic compound (A) is 0.01 to 100 g / L.   The etching solution according to claim 1, wherein the bromide ion concentration is 10 to 150 g / L. A replenisher that is added to the etching solution when continuously or repeatedly using the etching solution according to claim 1,
The replenisher is an aqueous solution containing an aliphatic acyclic compound,
The replenisher, wherein the aliphatic acyclic compound is a saturated aliphatic acyclic compound (A) having 2 to 10 carbon atoms and having only two nitrogen atoms as heteroatoms. A method for forming a copper wiring for etching a portion of a copper layer not covered with an etching resist,
The formation method of the copper wiring etched using the etching liquid in any one of Claims 1-7.

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