TW200918686A - Etching solution and method for forming conductor patterns - Google Patents

Abstract

The invention provides a copper etching solution capable of maintaining top shapes of patterns and etching at the same time even being used continuously or repeatedly, and a method for forming conductor patterns by using the etching solution. The etching solution is characterized in that the copper etching solution contains a copper ion source, acid and water, azole and an aromatic compound, wherein the azole only has a nitrogen atom as a hetero atom existed in a ring, and the aromatic compound is at least one selected from phenols and aromatic amines. In addition, the method for forming the conductor patterns is characterized by comprising the step of using the etching solution to etch the part of a copper layer not covered by etchant (3), so as to form the conductor patterns (2).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching solution for copper and a conductor pattern forming method using the same. [Prior Art] In the manufacture of a printed circuit board, when a conductor pattern (wiring pattern, terminal pattern, etc.) made of copper is formed by photo-inscription, a ferric chloride system is used (four)

A liquid, a copper chloride-based etching solution, an alkaline etching solution, or the like is used as an etching liquid. However, in these characterizations 9, # copper is dissolved from the side under the etchmg resist called undercut. That is, a phenomenon occurs in which a portion (i.e., a wiring portion) which is not originally removed by etching by a resist is desired to be removed by side etching, and is tapered from the bottom of the wiring: the top. In the case of the undercut, in particular, the wiring pattern is fine, and the undercut of the sample must be as small as possible. In the past, an etching liquid capable of suppressing the undercut was studied. For example, in Patent Document 1 below, it is proposed to contain copper chloride. A technical solution of an aqueous solution of a compound of hydrochloric acid, 2-aminobenzoxime, polyethylene glycol, and a specific sub-hospital polyamine compound. Further, in the following Patent Document 2, an etching liquid is obtained by blending a top portion of a specific azole wiring. In the case of the pattern forming type, the undercut is less, and the copper can be prevented from being protected. Patent Document 1: Patent Document 2: [Patent Document 2] Patent Publication No. Hei 6-57453, Japanese Patent Laid-Open No. 2005-330572 Japanese Patent Publication No. 200918686. However, in the conventional etching liquid described in Patent Document 1, there is a case where the undercut is not sufficiently suppressed, and an etching liquid which can be further suppressed is required. Sickle The money engraving liquid described in the above Patent Document 2 has the following problems. If the (four) ions are used as the oxidation of the surname engraving, in the process of engraving, the copper ions react with the metal copper which is engraved to form cuprous ions, and the concentration of ::: rises. If the concentration of the cuprous ion exceeds -, the etch is lowered. Therefore, an oxidation such as hydrogen peroxide is usually added to the rice cultivating liquid to carry out a reaction for regenerating cuprous ions into copper ions. However, if urethane is added, the azole contained in the etching solution is also pulverized, and the top of the wiring pattern becomes fine. The above two prevent this situation, and it is necessary to manage so that the salivation concentration is etched at the fixed side, and the management is rather complicated. Case 2 = Seeing to provide, engraving and using the conductor diagram hydrogen peroxide' is such that when the (four) can be lowered, the top shape of the case is added, and the shape can be easily cut in the state of less undercut. The salivary concentration is maintained: -= and even if it is used continuously, it can be shaped in a part-by-side. And capable of maintaining the top of the pattern: the (4) liquid system of the invention contains a copper ion source liquid, characterized in that it contains and owes copper (4) having a nitrogen atom as (4): a fragrant compound present in the ring. The saliva is only a hetero atom of the genus and the aromatic amine, and the scent compound is selected from the group of the genus. 200918686 The "copper" in the above invention may be made of pure copper or may be made of a copper alloy. Further, in the present specification, "copper" means pure copper or a copper alloy. The method for forming a conductor pattern of the present invention is characterized in that the copper layer of the electrically insulating material is not blocked by using the etching liquid of the present invention described above. The portion covered by the etchant is patterned to form a conductor pattern. The etching solution of the present invention and the method for forming the conductor pattern using the same can

In a state where the side etching is small, the top shape of the pattern is etched into a desired shape, and even if the etching liquid is continuously or repeatedly used, the azole concentration can be easily maintained at -1 or more while maintaining the top shape of the pattern. Carry the last name. [Embodiment] The present invention is directed to a copper etching solution of the type which is a copper etching liquid which generates cuprous ions during etching and has a reduced etching property. - An oxidizing agent such as hydrogen peroxide is added to the cuprous copper. Ion regeneration is a type of copper ion '-side repeated use. The components and the like constituting the pure engraving liquid will be described in detail below. (Copper ion source) The copper ion source is a component added as an oxidizing agent for oxidizing metallic copper. The type of the copper ion source may, for example, be copper chloride, copper sulphate, copper oxide, a copper salt of an organic acid, or copper oxyhydroxide. Among them, due to high solubility: silver engraving speed is fast and particularly preferred is copper chloride. Further, the concentration range of the copper ion source is preferably in the range of copper ion concentration of 14 to 155 g/L, particularly preferably in the range of 33 to mg/L. As long as it is: in the range of 200918686, the etching rate can be prevented from decreasing, and since the solubility of copper ions is good, the etching rate can be stably maintained. When a preferred copper ion source, i.e., copper chloride, is used, the concentration of copper chloride is preferably in the range of 30 to 33 Å/L, more preferably 70 to 260 g/L. The (acid) acid is a component added to dissolve copper metal oxidized by copper ions. The type of the acid to be used may be at least one selected from the group consisting of inorganic acids and organic acids. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, acid, and acid. The organic acid may, for example, be citric acid, acetic acid, oxalic acid, maleic acid, benzoic acid or glycolic acid. Among them, hydrochloric acid is preferred from the viewpoint of stability of etching rate and dissolution stability of copper (in the case where cuprous ions and copper ions are held in an etching solution). The concentration of the acid is preferably from 7 to 180 g/L, more preferably from 18 to 11 g/L, still more preferably from 18 to 80 g/L. As long as the acid concentration is 7 g/L or more, an etching rate of stable t, and a decrease in the solubility stability of copper can be prevented. On the other hand, if the concentration of the acid is below 18 〇g/L, the etching solution can be prevented from eroding between the corrosion inhibitor and the copper, and the reoxidation of the copper surface can be prevented. (Azole having only a nitrogen atom as a hetero atom present in the ring) To suppress the undercut, an azole having only a nitrogen atom as a hetero atom existing in the ring is added to the etching solution of the present invention (hereinafter, also referred to as " Oxazole"). The mechanism by which carbazole inhibits undercutting is still unclear. We believe that the reason is as follows: by the top of the conductor pattern and the cuprous ion 姅200918686 film in the liquid near the side, and thus, from the top of the conductor pattern, the side is formed on the side. Protection inhibits undercutting. μ ° YiW composition, can also be condensed into a compound. It is especially good for saliva Li ^ 1 compound, triazole car and tetra-salt compound, you can also use more than 2 kinds of these saliva Examples of the above-mentioned taste-like compound can be exemplified by sputum, methyl salic, 2-indolyl-alkyl-4-mercaptoimidazole, 9-inch pot, ', *^ 2 base (four), etc. Benzopyrene

Salivary, 2-methylbenzimidazole, 2-undecane, hydrazine, imidazole, 2-phenylbenzimidazole, 2-mercaptobenzimidazole, and the like. Examples of the above-mentioned tri-salt compound include tris, 1,2,4-tris, 5-phenylindole, tris-sodium, 5-amino], 2,4-triazole, benzotriazole , 1-methyl-benzotriazole, tolyltriazole, and the like. Examples of the above tetrazole compound may, for example, be a tetrazole, a 5-amino group, a tetrasodium 5-methyl-1 fluorene-tetrazole, a 5-phenyl-1-indole-tetrazole, a 5-amino group, and a Saliva, 1-phenyl-5-weiyl-1Η-tetrazole, κcyclohexyl·5υ_ΐΗ_tetrasaine, 5bis-1Η-tetrazole, and these ammonium or Na salts, Ζη salts, Q salts , κ salt and other metal salts. Among the exemplified azoles described above, tetrazole compounds are particularly preferred. This is because the performance of not only suppressing the undercut is high, but also the pattern can be clearly formed. Further, among the four-degree sitting compounds, 1H-tetrabit, 5-phenyl-1Η»: azole, 5-amino-1H-tetrazole, 5,5, _bis-115-tetrazole, and The ammonium salt or the genus salt or the like is particularly preferably 1H-tetrazole, 5-amino-1H-tetrazole, and the ammonium-L, is metal salts. It is assumed that these tetrazole compounds can form a protective film thinly and uniformly on the side from the top of the conductor pattern. 200918686 In addition, 5-amino-1H-tetrazole, and its ammonium or metal salt, decomposed by hydrogen peroxide, in the case of regenerating cuprous ions into copper ions and two in the presence of chlorine peroxide, concentration with time Change:: The direction. Therefore, the effect of the aromatic compounding and the inclination described later is added, and the effect is more remarkable than in the case where it is not added. The concentration of H is suitable for the saliva is preferably (M~50g/L, more preferably 〇ι~r is preferably 〇.2~10g/L. As long as the concentration of strontium is at . On the other hand, the concentration of saliva is a decrease in the etching rate below 5 tracks, and it can be confirmed that the portion 8 to be etched is prevented from being etched to prevent short circuit (poor insulation). ^, Object) In order to prevent the oxidizing agent such as hydrogen peroxide, the aromatic compound is added to the aromatic compound in the present invention (hereinafter, also referred to as ": ^ class". At least - "aromatic compounds, excluding heart% compounds". It is not clear that the above aromatic compound inhibits oxygen (4), but we believe that the reason is as follows: (4) The mechanism of knife disintegration is captured by the addition of an oxidizing agent such as chlorine peroxide: a fragrance compound having a strong oxidation effect The role. It is called the fungic radical decomposition, but by pre-adding the upper (four), it will be captured by the aromatic radical by the radical, so that it can inhibit the decomposition of the azole by the hydroxyl radical.吏 氧化 氧化 氧化 , 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 - Tris(diamidodecyl) phenol (monohydric), benzene, acid or its salt (mono), cresol sulfonic acid or its salt (mono), salicylic acid or its salt (mono), wood sulfonate Acid or its salt (mono), phenol (mono), catechol (binary, hydroxyl asymmetric), xylene hope (mono), gallic acid (ternary), phenylbenzene (one dollar), both Pyrogallol (ternary), o-benzene triazole (ternary), hydroquinone (binary, hydroxy symmetric), 2.6-di-t-butyl-p-nonylphenol (mono), 2,6- — a second butyl-4-ethyl group (unary), 3-butyt-4-yl-p-anisole (mono), etc. In the above, the number of elements corresponds to the number of hydroxyl groups. Among the phenols, a one-component substance is particularly effective compared with a substance of two or more. In addition, in the case of binary (a phenol having two hydroxyl groups) In the case of the case, it has a tendency to be more asymmetric with respect to the center of the ring, and has a higher effect than the phenol having a hydroxyl group symmetrically. Further, the effect of dissolving the high-temperature phenol of 200918686 in water is high. Among the above phenols, the effect of inhibiting the decomposition of the azole by the oxidizing agent is high, and particularly preferred is a benzoic acid or a salt thereof, cresol sulfonic acid or a salt thereof, salicylic acid or a salt thereof, lignosulfonic acid or The salt thereof, 2,4,6-tris(dimethylaminofluorenyl)benzene are classified, etc. Specific examples of the aromatic amines may be exemplified by naphthalene diamine, aniline, cedaramine, methyl strepamine, and dimethyl Aniline, phenylethylamine, benzylamine, dibenzylamine, phenylenediamine, tris-aniline, %y' toluenediamine, diphenylamine, triphenylamine, o-nitro-p-chloroaniline, Anthranil or the like. Among these aromatic amines, the effect of inhibiting the decomposition of saliva by the oxidizing agent is high, and particularly preferred are naphthalene diamine, strepamine, naphthylamine, etc. The concentration of the aromatic compound is preferably丨 丨 丨 0.01~2〇g/L, better 12 200918686 is (M~10g/L. As long as it is in this range, you can It is possible to prevent the decomposition of the severance and prevent the etch rate from being lowered. (Hydrogen peroxide) & If the (4) liquid of the present invention is used for the copper (4), the copper ions and the metal copper in the etchant are changed during the etching process. The produced cuprous copper increases from the enthalpy. Therefore, hydrogen peroxide can be added as a heart to oxidize the cuprous ion to regenerate into an oxidizing agent for steel ions. fl = hydrogen peroxide can be added to the etching solution in advance, or can be etched: Alternatively, it is also possible to use a button in which hydrogen peroxide is added in advance to add hydrogen peroxide in the middle of (4). Usually, hydrogen peroxide is often added to the system. Hydrogen peroxide is preferred. The amount of addition, the root enthalpy changes, and thus the amount of cuprous ion produced by t, the value of the month b is generally specified, for example, if the concentration in the (iv) liquid ranges from 0.01 to 20 /L, The cuprous ion that can be easily produced by Chiang is regenerated into copper ions. After the production, in response to the change in the amount of cuprous ion: test: increase the ratio of the amount of the above and the state of the elephant, and the second consideration of "quote (four) accurate, as long as the technical field of the invention = Adjusted for the base. Of course, it is possible to add a peroxidation when the cuprous ion concentration is increased, and to change the '- side to determine the cuprous ion concentration in advance. Hydrogen peroxide was added based on this. What kind of change in 仃X is not used as a oxidant for copper etching. In a small amount, it has the function of assisting the wah to suppress undercutting. 200918686 The range of the influence of the sub-steel ion is preferably 5 § / B

The following, more preferably 2 n is more preferably 2.5 g / L, more U 2.0 g / L or less, and even better, the cuprous ion concentration is below 5 g / L, that is, .... ρ - Γ ^ prevents the lowering of the speed of the surname" to etch the portion of the portion to be etched (poor insulation). The cuprous ion is used to prevent short-term, and the lower limit of the enthalpy/morning is not particularly limited, as described above, by the presence of a micro-cutting function. ^There is a chlorine peroxide added to assist in maintaining the cuprous ion concentration in the above range. As described above, it can be appropriately adjusted. For example, in order to regenerate the cuprous ion into copper ions, it is necessary to 2.7 g of hydrogen peroxide, so that hydrogen peroxide can be added depending on the concentration of the cuprous ion produced. However, if the amount of hydrogen peroxide in the surname is excessive, chlorine gas or heat generation is generated, which is dangerous. Therefore, it is preferable to add the cuprous ion concentration within the above range. The management method for the surname engraving for maintaining the cuprous ion concentration in the above range can directly measure the concentration of cuprous ions, or can also measure the redox potential of the surname engraving, and convert it into cuprous ions. concentration. (Other additives) In order to improve the stability of the liquid, uniform etching is performed, and the surface shape after etching is made uniform, and a cationic surfactant, a glycol, and the like may be blended in the etching liquid of the present invention as needed. At least one of the glycol ethers, various additives such as an alcohol, a guanamine, an anionic surfactant, a solvent, a nonionic surfactant, an amphoteric surfactant, and a cationic polymer. Specific examples of these additives are as follows. 14 200918686 ) 1⁄4 ionic surfactant, benzaik〇njum chloride, alkylated quaternary ammonium salt such as vaporized alkyltrimethylammonium. Monoterpene alcohol: ethylene glycol, diethylene glycol, propylene glycol, polyalkylene glycol (the number of carbon atoms of the alkylene group is about 4 to 500), and the like. Diol ether: propylene glycol monoethyl ether, ethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, dipropylene glycol methyl ether, diethylene glycol butyl ether, and the like. Alcohols. Methanol, ethanol, 1-propanol, 2-propanol, butanol, benzyl alcohol, 2_

Phenoxyethanol and the like. Indoleamines: hydrazine, hydrazine-dimethylformamide, dimethylimidazolidinone, N-mercaptopurine, and the like. Anionic surfactants: fatty acid salts, alkyl sulfate salts, alkyl phosphate salts, and the like. Solvents, such as sulfoxides such as dimethyl hydrazine, etc. Nonionic surfactants: polyoxyethylene alkyl ethers, polyoxypropylene alkyl groups, block polymers of polyoxyethylene and polyoxypropylene, and the like. Amphoteric surfactant: lauryl dimethylamino acetic acid betaine, octadecyl dimethylamino acetic acid betaine, lauryl hydroxy sulfobetaine and other betaine 'lauryl dimethylamine oxide, amino carboxylic acid Acid, etc. Further, the cationic polymer is preferably a substance which exhibits a cationic behavior in water and has a molecular weight of 1,000 or more. More preferably, it is a polymer compound having a molecular weight of several thousands to several millions. Specific examples thereof include polyethyleneimine, polyalkylene polyamine, quaternary ammonium salt type styrene polymer, and quaternary ammonium salt type aminoalkyl (mercapto) acrylic polymer. , a grade 2 ammonium salt type diallylamine polymer, a quaternary ammonium salt type diallylamine and an acrylonitrile 15 200918686 amine copolymer, an amine alkyl acrylamide salt polymer, a cationic cellulose derivative Wait. The above salt may, for example, be a hydrochloride. The yttrium &5' is preferably a polyethyleneimine or a polyalkylene polyamine. These cationic polymers may be used in combination of two or more kinds. Further, as the above cationic polymer, commercially available ones such as a resin, an antistatic agent for fibers, a high eight agglomerate for wastewater treatment, and a conditioner for hair rinsing can be used. A knife and an etching solution of the present invention are easily prepared by dissolving the above components in water. The water is preferably water such as ion-exchanged water or pure water from which ionic substances and impurities are removed. . 1 When managing the liquid (for the sake of the concentration of each component), you can use the replenisher. In the case of liquid supply, each component in the etching solution is held by using a supply containing the following components. a) acid b) having only a nitrogen atom as a hetero atom present in the ring, the salivation selected from the group consisting of phenols and aromatic amines, and the various components are preferably used and etched. Recognize liquid d night the same kind of substance. It is preferable that the liquid is only contained in the component a, and the component b is 0]^, ”, 7 to 36〇g/L, and the concentration range is 4 〇·1 to 5〇g/; the concentration range of L, 〇

Replenisher in the concentration range. The knives 4 〇 _ 〇 1 ~ 20g / L by adding the replenishing liquid, the appropriate ratio, so that the components of the undercutting less liquid can be stably formed in the money, from the dissolution stability of steel _ consideration 16 200918686 acid. In the replenishing liquid, copper chloride may be further contained in a concentration range in which the copper ion concentration does not exceed 14 liters. Further, the above additives may also be contained. In general, when hydrogen peroxide is added as described above, the azole is decomposed by hydrogen peroxide and the concentration is drastically lowered. In the present invention, the reduction of the azole caused by hydrogen peroxide can be suppressed by the addition of the above aromatic compound. Therefore, even when the respective concentrations are adjusted by using the above-mentioned replenishing liquid, it is possible to carry out the concentration management of each component without considering the decrease due to the oxidizing agent such as hydrogen peroxide, and the concentration management of the etching liquid becomes easy. Further, although it is not particularly limited, in this case, when the azole concentration is maintained at 〇1 to 5 〇g/L, as described above, not only the undercut can be surely suppressed, but also the reduction in the residual speed can be prevented. . Simu uses this hair ... μ called the team to match the green tea, you can get the bottom copper wire (also including the copper alloy wiring 'the same below). Specifically, for example, it is possible to stably form an engraving factor (Etching faet()r) of more than 5, and a .s-six line, and it is easy to manage the concentration of the engraving liquid when performing the engraving. Here, the private surname factor is #, and the thickness (height) of the copper wiring is set to τ, and the width of the copper wiring is set to be *'

When the towel is W1 and the width of the bottom of the copper wiring is W2, 2T/(W2 屮 屮 ,, A uses the surface engraving of the present invention and t. ®1 is a wiring for nine nights. The cross-section of an example of a pattern is not intended. The reference symbol is a glass epoxy substrate impregnated with epoxy resin in a glass fiber fabric, a resin paper substrate, and an aromatic The so-called aroma of so-called resin in which 3 is impregnated with a secret resin = a substrate impregnated with an epoxy substrate in an amine-based non-woven fabric (electrical flash-free edge material). Reference numeral 2 is a copper wiring. Reference 17 200918686 Symbol 3 is a contact agent resin (money suppressant). Further, W1 indicates a wide width at the top of the copper wiring 'W2' indicates the width of the bottom of the copper wiring. If the etching liquid of the present invention is used to form the steel wiring, the bottom of the copper wiring can be made The difference between the wide width W2 and the width W! at the top of the copper wiring is reduced (W2-W), and the etching factor can be increased. [Embodiment] Hereinafter, in order to facilitate the understanding of the present invention, examples and comparative examples will be described. The invention will be further described, but the invention is not limited thereto. (1) Decomposition of saliva by hydrogen peroxide The components shown in Tables 1 and 2 were dissolved in ion-exchange water to prepare etching solutions of Examples 1 to 13 and Comparative Example u. And the concentration of hydrogen chloride in the hydrochloric acid shown in Table 2 is 35 wt%. On the other hand, it is prepared to adhere a copper foil having a thickness of 12 μηι on a glass epoxy substrate (GEA67N manufactured by Hitachi Chemical Co., Ltd.). A copper laminate (substrate for printed circuit board) is adhered to a dry film inhibitor (SUNFORT SPG_152, manufactured by Asahi Kasei) having a thickness of 15 μm to form a line width and a pitch (1) and space) ~ 25μηι/25μηι ( The width of the line is 25 μm, and the gap between the lines and the line is 25 μm.) Then, using the residual solution of Example 13 and Comparative Example 8, at 4 〇C, the 胄G. Spraying was carried out under the conditions of 15 MPa, and copper coupons not covered by the above-mentioned resisting agent pattern were formed to form a copper wiring pattern, and then a 3 % by weight aqueous sodium hydroxide solution was sprayed to remove the dry film inhibitor. The laminate is cut, and the cross-sectional shape of the formed copper wiring pattern is observed (10)丨 _ shape), determine the difference between the width (I) at the bottom of the copper and the width (W1) at the top, and set it as shown in Table 18 and the initial 18 200918686 value 0 in Table 2. After the etching liquids of Comparative Examples 1 to 8 were prepared, 25 g/L of hydrogen chloride water (concentration of hydrogen peroxide: 35 wt%) was added to each etching liquid, and the material obtained by the method was placed at room temperature for 24 hours. Then, using the etching liquid, the same line pattern as described above was used to measure the difference between the bottom of the copper wiring 乂''5 (w2), the width M 2) and the width of the top (π). And the value of the table after the emulsifying hydrogen is placed (after the addition), and the stock is shown. The chromatographic method was used to determine the saliva residue at this time, so it was only shown that it was difficult to measure by liquid chromatography. 19 200918686 Table 1 Composition Residue & oxazolium (g/u component 1 degree te/U initial addition after placement Example L gasified copper. 1H - tetradecyl o-cresol-4-sulfonic acid 150 100 12 0, 3 3.3 3.4 can not be analyzed Example 2_ gasification phase hydrochloric acid 5-amino-1H-tetrazole 2-cupyl Ethanol 2, 4, 6 " Tris(dimethylaminomethyl)benzene powder m 20 1-5 1 3 a.2 3.1 U8 Example 3 Vaporized copper · Hydrochloric acid 5 - stupyl ~ 1H ~ tetrahydropropylene glycol monoacetic acid Sodium sulfonate* 130 m ais ί5 1.5 4,5 4.4 0.13 Example 4 Gasification pin 5,5'-bis-1H-tetrazole hydrochloride. o-cresol-4-sulfonic acid 100 40 αΐ2 0; 4Λ A3 0Λ2 Example 5 Gasification copper ruthenic acid 5 ~ - 1H - 29^ Phenol sulfonic acid fine 70 8 3 4 7.93 Example 6 Gasification copper. Hydrochloric acid 5-amino-1H - tetrasodium sulphonate* 70 40 0,5 1.S a,9 4 0.44 Example? Vaporized copper hydrochloric acid 5-air-based-1H-four biting o-to-be--4-jing acid 140 70 2 0.3 Μ 32 1M Example 8 gas culvert hydrochloric acid 5 —-Nitrogen-1H—Four blowing water 1979 30 1.8 η 3.2 32 173 EXAMPLES Gassing Copper Bond Acid 5,5, ~Double-1H-Y-Phenyl Base m 40 ύΛΖ 0Λ 4.5 4.7 0.11 Example 10 Gas Holder Copper 5-Phenyl-Chloro-tetrazole and Fermented Single Tea T30 60 ΰΛΒ 15 0.3 46 0J 0Λ1 Example 11 Vaporized copper hydrochloric acid 1,8-decanediamine 140 70 2 0.1 11 S.2 121 Example 12 Vaporized copper hydrochloric acid 5-赛^-iH-tetrasylamine 270 30 1.8 0.1 3.2 8.9 1.34 Example 13 Gasification of steel acid-based 5-amino-111-tetrahedyl α-methylamine 70 40 Οδ 0.1 4J 10.5 029 *Nippon Paper Chemical Co., Ltd. "SANX P252" 20 200918686 Table 2 Composition residual amount _ | Component concentration (g/U initial addition after placement (g/u comparison example 1 gas fine 150 hydrochloric acid 1H-tetrazol 100 1.2 3, 2 13.3 can not be analyzed & example 2 gas also steel 300 hydrochloric acid 20 5-amino-1H - Sijun 1.5 3 its α.〇4 2-phenoxy& alcohol 1 Comparative Example 3 Vaporized copper 130 Hydrochloric acid 60 S - stupid, 1H - tetraindole α 4 4,4 m 0.08 Propylene glycol Ether 15 comparison pin 4 gasification copper ioa hydrochloric acid 40 5, 3'-double-Π1 biliary sputum W2 4'3 14.6 0.06 Comparative Example 5 vaporized copper 200 3-amino-1Η-tetrazole 70 8 3.S 13』 0.G8 70 Hydrochloric acid 40 5 -Amino_ 1H -Tetraindole 0.5 3.8 147 0,01 &Comparative Example 7 Vaporized copper 140 Hydrochloric acid 70 5 _Amino- 1H-tetrazole 2 3 Ϊ45 0.04 Comparative Example 8 Vaporized copper. 270 30 5 - gas base-11 丨 - Sijun 2 3,1 iU 0,03 As shown in Table 1 and Table 2, each example is compared with each In comparison with the example, the shape of the copper wiring can be maintained in a good state even after leaving hydrogen peroxide for 24 hours. I think this is because even after adding hydrogen peroxide, various kinds of saliva remain. (2) Change in concentration of azole in continuous use Next, the change in concentration of azole when the etching solution was continuously used was measured. The etching liquid of Comparative Example 2 shown in Example 2 and Table 2 shown in Table 1 was prepared. Further, the components shown below were dissolved in ion-exchanged water to prepare a replenishing liquid. <Composition of replenishing liquid> 21 200918686 Hydrochloric acid (hydrogen chloride indifference: 35 183 heart 5-amino-1 Η-tetrasodium i.5g/L 2-phenoxyethanol ig/L 2,4,6-three After (dimethylaminomethyl) phenol 3 ga, the etching liquids of the shell examples 2 and 2 were separately charged into the spray tank. In the spray tank, the copper ore plates were placed in the respective spray tanks, and the side machine and the spray were sprayed. Under the condition of pressure a, the copper concentration is measured every 20 seconds (the cuprous ion concentration) every 20 seconds, and 0± chen, if the cuprous concentration exceeds 〇.65g/jL, then add Hydrogen peroxide (hydrogen peroxide nipple/length: 35 wt%) 250 μΙ> The copper bond plate described above was obtained by attaching a thickness to a glass epoxy substrate (GEA 67N manufactured by Hitachi Chemical Co., Ltd.). 35 (4) Copper-clad laminate of copper box (substrate for printed circuit board), which is obtained by electrolysis copper plating of 4 18 μm, and the above spray treatment, for 1 piece of steel The plate was allowed to stand for 2 minutes until the copper was completely dissolved. During this period, the average dissolution rate of copper was Q 29 g/L per minute. In addition, for the etchant of Example 2, the copper plate for each treatment was processed. The above-mentioned replenishing liquid was added. Then, 'the above-mentioned operations were repeated for the engraving liquids of Example 2 and Comparative Example 2 until the 62 sheets of the 锢月钔 plating were processed. Next, after the end of the treatment, Example 2 and comparison In the etchant pan φ ^ α etchant of Example 2, the residual amount of carbazole was measured by liquid chromatography to calculate the residual ratio. Thousand, , and ° are not in the graph of Fig. 2. In the graph of the sound, it is possible to maintain the concentration of the azole by continuously adding a specific compound to the rhyme solution of the second embodiment, even if hydrogen peroxide is added. According to the present invention, the present invention provides a method for forming a steel etching solution and a conductor pattern using the same, and the steel etching solution can easily maintain the azole concentration at a constant level or more even if it is used continuously or repeatedly. The etching is performed without changing the top shape of the pattern. Further, the present invention is applicable to the conductor pattern on the glass substrate and the conductor on the surface of the plastic substrate, in addition to the formation of the conductor pattern suitable for the printed circuit board. FIG. 1 is a schematic cross-sectional view showing an example of a wiring pattern obtained by using the etching liquid of the present invention. FIG. 2 is a cross-sectional view showing an example of a wiring pattern obtained by using an etching solution of the present invention. And the change in the concentration of azole and the change in cuprous copper during continuous etching of the copper plate used as the base of the etching solution of Comparative Example 2. [Description of main components] 1 substrate 2 copper wiring 3 resist resin T copper Wiring thickness (height) W! Wide width of the top of the copper wiring W2 copper wiring at the bottom of the width 23

Claims (1)

200918686 lies in the patent application circle: u kind of etching liquid, which contains copper ion source, acid and water, its characteristic = there is a fabric family compound κ only has nitrogen source in the soil. . 2. The etching solution according to claim 1, wherein the etching solution further comprises at least one of the fragrant compounds selected from the group consisting of a hydrogen peroxide and an aromatic amine. 3. The etching solution according to the scope of the patent application. The concentration of the compound ranges from 0.01 to 2 〇g/L. 4. If you apply for a patent, use copper ion concentrate A ^ inscription, which contains the copper ion source 1 ~ 5Og / L. 5. If applying for a patent system compound.一片· 1 piece of 14~155 hearts, the acid 7, L, and the etchant of the Wow circumference item 1, wherein the azole is tetrazole 6. The chelating agent is etched according to the first item of the phenolic compound. The liquid liquefied liquid of the sixth aspect of the invention, wherein the phenolphthalein total 'West phenol sulfonic acid or its salt, formazan _ # phenolic phenolic selection #甲盼~acid or its salt, salicylic acid hydrazine, sulfonic acid or its salt, and 24a_h 鲛: 3⁄4 with salt, wood species, bis(dimethylaminomethyl)phenol A8 If you apply for a patent map 'The hydrogen peroxide system uses the etchant for the target target 2, the straight concentration range is 0. 〇l~2〇g/; L. /, T 9 _ A method of forming a conductor pattern, characterized by 24 200918686 Patent Nos. 1 to 8 - a case where the upper copper layer is not covered by a corrosion inhibitor. The etchant of the item is partially etched to electrically insulate the material into a conductor pattern, and a method of forming a peroxide pattern is added to the etchant, and the concentration of cuprous ions generated in the etchant is ^ The line is inscribed so that 1 I is as shown in the figure g of the ninth application of the patent scope, and the side-by-side method is formed by the method of forming the same liquid. The concentration of ... is maintained in a pattern forming method, in which the 'replenishing liquid contains at least one of the aromatic amines present in the ring, and the aromatic compound is added, and the aromatic compound is added, and the azole has only the aromatic compound. Heteroatom, 哕靟+ — μ Fang fragrant compound is selected from the phenolic weight 0 申 凊 凊 凊 凊 凊 凊 凊 凊 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The concentration of the acid is in the range of 7 to 36 〇g/L, and the sputum is 0.01 to 20 g/b to 5 〇g/L, and the concentration of the aromatic compound is in the range of eleven.