TW200930839A - Etching liquid - Google Patents

Abstract

This present invention provides an etching liquid capable of inhibiting corrosion due to metal except nickel (especially copper). The nickel etching liquid containing nitric acid or sulfuric acid, hydrogen peroxide, water, and a polymer having at least one repeated unit selected from the following formula (I), the following formula (II), and the following formula (III). In the formulas, R1-R5, represent the same or different hydrogen, amino, imido, cyano, azo, thiol, sulfo, hydroxyl, carbonyl, carboxyl, nitro, alkyl, cyclic alkyl, aryl, or benzyl. Further, amine contained in the repeated unit can be a form of quaternary ammonium salt.

Description

200930839 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a nickel etching solution comprising nitric acid or sulfuric acid, and barium peroxide, and water. [Prior Art] The electrode of a printed wiring board including a flexible substrate for TAB (Tape Automated Bonding) or a substrate for BGA (Ball Grid Array) packaging or

In the manufacturing process of the wiring or the electrode of the semiconductor article or the like, there is a step of forming a nickel film by electroplating or electroless plating. At this time, the nickel film formed in the unnecessary portion is removed by the money engraving. Since the electrode or the wiring is composed of a plurality of metals, it is required to prevent the metal other than nickel from being etched when the film is removed. For example, in the process of manufacturing a printed wiring board by a semi-additive process, a glass fiber cloth epoxy resin impregnates a substrate or a polyimide film, etc. After the key bond or the steaming key is printed, the opposite pattern of the photoresist forming circuit is formed by copper plating on the nickel without the photoresist to form a steel circuit 'and then removing the photoresist' and then exposing the exposed material. The #刻液 used in this case is required to be able to etch nickel in the absence of intrusion. The liquid is removed as the non-invasive copper (4) liquid. In the past, acid such as acid was used and the SI was prepared. The engraving liquid is the first engraving liquid. The nitric acid-hydrogen peroxide is recorded to suppress the copper (4) and the additive is added (for example, refer to Patent Documents 1 to 8). 200930839 62-1 1070#62-14034 Japanese Patent Laid-Open Publication No. JP-A No. JP-A No. Sho. :Japanese Patent Laid-Open No. 6_57454 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is such a liquid that does not sufficiently inhibit the invasion of copper. The nickel etching solution which is expected to further suppress copper etching is desired.

Suppresses the erosion of metals other than nickel. In order to achieve the above objectives, this

The long # ' particularly copper etched nickel etchant. The etching solution of the present invention is characterized in that: at least one of the hydrogen peroxide and the nickel etchant of water is at least one of the formula (I), the following formula (Π), and the following formula (dish). Unit of polymer; a CH Guang 9H-CH2 - 丄···(1) 7 '(II)200930839

One CH2—CH—CH-CH 2

CH 2

NI ❹ r I II IR2 ^ N R5 (III) r4 furnace (the second iR1 ~ R5 is chlorine, amine, imine, cyano, azo, -1 soil ^ soil base, several groups, carboxyl The nitro group, the alkyl group, the cycloalkyl group, the aryl group or the benzyl group may be the same or different 'X, and the amine contained in the repeating unit may also be in the form of a fourth-grade money salt). In addition to the above, the etching liquid of the present invention is a nickel etching liquid. However, the "nickel" is not only pure nickel but also a nickel alloy. X, the same is true for the following "copper". Here, the term "alloy" as used herein means, for example, a metal having a main metal content of 50% by weight or more. According to the etching liquid of the present invention, since a polymer having a repeating unit selected from at least one of the above formula (I), the above formula (n), and the above formula (dish) is contained, it is possible to suppress a metal other than nickel, particularly It is the erosion of copper. [Embodiment] The etching solution of the present invention is characterized in that the nickel etching solution containing nitric acid or sulfuric acid, hydrogen peroxide, and water contains the following formulas selected from 200930839 =), the following formula (8), and the following (5) At least one of the repeating units of the poly-β substance "In the etching liquid of the present invention, since the metal is an inhibitor of the residual of the metal, the (four) substance can be recorded as a J Μ from the nickel and other mounds. The processing material is ordered, and only nickel is selectively engraved. Especially when the other metals mentioned above are copper, the function of 疋 can be more effectively exerted. 4 Inhibitor of Polymer Inhibitor The acid component of the etchant of the present invention is a component which dissolves nickel oxidized by hydrogen peroxide, and has high solubility in nickel, and is used for oxidizing and rolling. Nitric acid or sulfuric acid. Further, the acid has an action of promoting oxidation of nickel. Although these acid forming knives have a role in dissolving steel in comparison with nitric acid, the effect of dissolving nickel is small. Therefore, it is preferable to use nitric acid as the acid component invented by ‘,’ but 疋α_ 攸 cooking time. " The acid in the above-mentioned surname engraving is the right concentration, although the concentration is etched, the corrosion rate is 38.5 wt%, more preferably 3 T but preferably U wt% ~ ❹ to: 2:: weight " At the time of the time, because the speed of the money will be accelerated, it can be more than %. By setting the concentration of the acid component to 38.5 weights, the upper part can easily suppress the invasion of metals other than copper (especially copper). The removal ability of the peroxygen bromine in the above-mentioned residual liquid is adjusted, and the H agricultural degree 'is preferably 0.035 weight 0 / preferably 4 〇 0. 0175 weight % ~ 17.5 weight %, depending on the speed and amount of the surname. 7. % by weight. When peroxygen is ～14.°% by weight, optimally. _35 weight, because the system speed will increase the concentration of 〇.0175% by weight or more, so nickel can be quickly removed. In another aspect of 200930839, by setting the hydrogen peroxide concentration to 17.5% by weight or less, it is possible to easily suppress the intrusion of metals other than nickel (particularly copper). The etchant A of the present invention is used as an erosion inhibitor system. Cooperating with, from the above formula (η, the above formula (Π) and the above formula (melon) a polymer of at least one repeating unit. Further, the polymer may be a repeating unit selected from the above formula (1), upper formula, formula (Π), and at least one of the above formula w and other repeating soap positions. The copolymer may be a homopolymer composed of the above formula (1), the above formula, and the above formula (melon), or may be selected from the above formula (I) and formula (II). a copolymer composed of two or more kinds of repeating units of the above formula (melon). The polymer having a repeating unit represented by the above formula (I) may, for example, be a condensation polymer using epigas oxide as a monomer. The type is not particularly limited. For example, it can be appropriately selected from commercially available surfactants. When t is selectively etched from nickel in the material to be treated in which nickel and copper coexist, 'there is a ring by S. It is preferable that the polymer of the repeating unit formed by the oxygen compound and the gas compound is preferably a polymer having a repeating unit represented by the following formula (10)).

Η Η CIO 1 2-cXI I _2 IV) wherein ur7 is hydrogen, amine, imido, cyano, azo, thio, decano, hydroxy, 丞 carbonyl, carboxy, nitro, alkyl , cycloalkyl, aryl or benzoinyl, may be the same or different. Further, X- is a gas ion, a bromine 200930839 ion, a striking ion, an acetate ion or a carbonate ion) β. By using a polymer having a repeating unit represented by the above formula αν), the rate of nickel engraving can be increased (below The ratio (called "ER1") to the etching rate of copper (hereinafter referred to as "ER2") (ER1 / ER2). Thereby, it is possible to surely etch only nickel from the material to be treated in which nickel and copper coexist. Examples of the polymer include a decylamine/epoxy-propylene oxide condensation polymer, a dimethylamine/ammonia/epoxy-propylene oxide condensation polymer, and adipic acid/dimethylamine/epoxypropane/diethylenetriamine condensation. Polymers, etc. Further, when ammonia is used as the monomer, R6 and R7 in the repeating unit represented by the above formula (JV) are fluorenyl groups. Further, when diamine is used as the monomer, both Re and r7 in the repeating unit represented by the above formula (IV) are a mercapto group. The polymer having a repeating unit represented by the above formula (Π) may, for example, be a condensation polymer which is not used as a monomer of diacrylamide, and the kind thereof is not particularly limited, and for example, it can be used from a commercially available surfactant. Appropriate choice. Specific examples thereof include a condensation polymerization Q compound composed of diacrylamide hydrochloride, a diacrylamide/acrylic acid/acrylamide polymer, and the like. Further, when diacrylamide is used as a monomer, the imaginary gas in the repeating unit represented by the above formula (11). The polymer having a repeating unit represented by the above formula (dish) may, for example, be a condensation polymer using dicyandiamide as a monomer, and the kind thereof is not particularly limited, and for example, a commercially available surfactant can be used. Choose the appropriate one. Specific examples include a diazodiamine/methylene condensation polymer and a di-amylamine/diethylenetriamine condensation polymer H when dicyandiamide is used as a monomer, as shown by the above formula (nr). It is known that R2 to Rs in the repeating unit are all hydrogen. 11 200930839 The concentration of the above polymer in the etching solution of the present invention is preferably 0.0001% by weight to 3% by weight, more preferably 0.0005% by weight to 1.5% by weight, most preferably 0.001% by weight to 1% by weight. /〇. As long as it is within the above range, corrosion of metal other than nickel can be suppressed to the extent that the etching of nickel is not hindered. ❹ Ο The ratio of the repeating unit of at least one selected from the above formula (I), the above formula (π), and the above formula (m) among the above repeating units is preferably 1 〇. ~100% by mole. The reason for this is that the erosion of metals other than nickel can be more effectively suppressed. Further, the above ratio (mole fraction) can be obtained by, for example, infrared ray analysis (IR), elemental analysis, liquid chromatography, or the like, in the above formula (1), the above formula (8), and the above formula (m). The relationship between these values and the number average molecular weight is calculated by including the molar number of the s month b basis or the characteristic element. In addition, when the monomer composition is undetermined, the monomer ratio is the molar fraction. Further, the denominator at the time when the ash is at the above-mentioned molar fraction is the total number of moles of the smallest repeating unit contained in the above polymer. The above polymer ' preferably has a weight average molecular weight of from 100 to 1,000,000, more preferably from 100 to 5,000,000. As long as it is within the above range, it is possible to suppress the invasion of metal other than the recording without hindering the degree of recording (4). In the etching liquid of the present invention, in addition to the upper component, the effect of the present invention can be added to the extent that it does not hinder the effect of the present month. For example, as a female mites for ruthenium peroxide, phenols such as phenols may be added. The concentration of benzenesulfonic acid or the like of sulfonic acid or salicylic acid is, for example, 0.01 to 5% by weight left, in order to promote the invasion of copper. As a source of chloride ions, for example, a fruit can also be added with a gas ion to give hydrochloric acid, or an aniline hydrochloride, a hydrochloride salt such as 12 200930839 pulmonate hydrochloride or ethylamine hydrochloride, or a gasification and gasification. , vaporized zinc chloride, gasified iron, vaporized copper, vaporized nickel, etc. The concentration of these gas ion sources is usually about ～6〇 plus or so in terms of gas ions. The etching solution can be easily prepared by dissolving the above components in water. As the water, the water having the ionic substance or the impurity removed is preferable, and for example, ion-exchanged water, pure water, ultrapure water or the like is preferable. The above etching liquid can be blended to a predetermined concentration at the time of use, or the concentrated liquid can be prepared in advance and diluted before use. The method of using the etching liquid and (4) the temperature of the liquid of the (four) liquid is not particularly limited, but since it is necessary to suppress the corrosion of the metal other than nickel, it is preferable to etch the nickel more quickly. [Examples] Next, the examples of the etching liquid of the present invention will be described together with the comparative examples. Further, the explanation of the present invention is not limited to the following examples. The types shown in Table 1 (A to J) The polymer 'is prepared in each of the etching liquids which are not composed of Table 2, and each item is evaluated by the measurement method shown below. For each etching liquid, first, the acid and hydrogen peroxide are dissolved in the ion exchange. After the water was added, a polymer was added to prepare the acid. For the acid to be mixed, only sulfuric acid was used in Example 14, and the other was nitric acid. In addition, the weight average molecular weight shown in Table , was low molecular weight (weight average molecular weight: 5 〇 or more) In the case of 50,000 50,000, the vapor pressure type molecule 1 measuring device manufactured by G〇n〇tec Co., Ltd. was used, and the measurement was carried out under the conditions of a sample concentration of 5 wt% (solvent: toluene). In the case of an average molecular weight of 50,000 or more and 300,000 or less, the measurement was carried out under the same conditions as above using a thin-twist molecular weight measuring apparatus manufactured by Tosoh Corporation. <etching speed with respect to nickel (ER1)> thickness 1 mm The rolled nickel plate (manufactured by High Purity Chemical Laboratory) was cut out, and a test piece to which a protective tape was attached was prepared on one side. Then, each of the etching liquids shown in Table 2 (liquid amount: 1 mL each) was respectively The beaker was poured into the beaker, and the test piece was immersed in each etching liquid (25t) using a tweezers, and the test piece was shaken horizontally in the etching liquid (period: 2 seconds), and φ-minute etching treatment was performed. ER1 (pm/min) was calculated from the weight of each test piece before and after the treatment. ER1 (μιη/mhO = (weight before treatment (g) - weight after treatment (g) + area of test piece (m2) + Nickel density (g / (10) 3) + impregnation time (min) < etch rate with respect to steel (ER2) > Copper foil of 35 μm thickness (GTMP manufactured by Furukawa Copper Co., Ltd.) cut 4 cm square side Prepare a test with protective tape Then, each of the money engraving liquids (liquid amount: 1 mL) shown in Table 2 was separately injected into a beaker, and the test piece was immersed in each etching liquid (25 〇) using tweezers while allowing the test. The sheet was shaken in the horizontal direction in the etching solution (period: 2 seconds), and etching treatment was performed for one minute. Then, ER2 (μιη / min) was calculated from the weight of each test piece before and after the treatment by the following formula. ER2 ( μιη / min )=(weight before treatment (g)—weight after treatment (g) + area of test piece (m2) + density of nickel (g / cm3) + impregnation time (min) and 'for each etching solution, Calculate the ratio between the above ER1 and ER2 200930839 (ERl / ER2). Table 2 shows the ratios (ER1 / ER2) of ER1, ER2, and the like of the respective etching liquids. [Table 1] Typed trial #No. CASNo. Weight average molecular weight monomer composition (Mohr ratio) A - - 100,000 to 120,000 adipic acid / dimethylamine / epoxide / diethylene triamine condensation Polymer (1/1/1/1) B 7-(1518) - 280,000 dimethylamine / ammonia / epoxide (1/1/2) C - 26063-69-4 110,000 propylene amine hydrochloride Salt D 7-(21) - 20,000 to 3 million dicyandiamide / diethylene triamine condensation polymer (1/1) E 6-(1898) - 420,000 propylene acrylate / acrylic acid / acrylamide 1/1/1) F 6-(1429) - 40,000 to 80,000 dimethylamine ethyl methacrylate quaternary compound G 6-(1675) 30551-89-4 6 million gasified dipropylene dimethyl bond Η 7-(741) 9002-98-6 68130-97-2 70,000 Ethyleneimine I 7-(741) 106899-94-9 300 Ethyleneimine J 7-(24) - 10,000 to 30,000 Dimethylamine/epoxypropane (1/1) *Regulations related to the examination and manufacture of chemical substances 15 200930839 [Table 2]

Polymer type Concentration of each component (% by weight) Etching rate (μιη/min) Charging speed ratio ER1/ER2 Acid hydrogen peroxide polymer ER1 ER2 Example 1 A 20 2.8 0.005 3.94 0.03 131.33 Example 2 B 20 2.8 0.005 4.86 0.04 121.50 Example 3 C 20 2.8 0.0025 6.78 0.07 96.86 Example 4 D 20 2.8 0.005 6.61 0.09 73.44 Example 5 D 20 2.8 0.01 5.51 0.06 91.83 Example 6 E 20 2.8 0.002 5.50 0.10 55.00 Example 7 D 2 7 0.005 1.23 0.02 61.50 Example 8 D 37 2 0.005 1.84 0.04 46.00 Example 9 A 20 0.05 0.0005 4.39 0.04 109.75 Example 10 A 20 7 0.005 9.02 0.04 225.50 Example 11 B 20 10 0.005 9.36 0.06 156.00 Example 12 C 20 14 0.005 11.69 0.22 53.14 Example 13 E 37 14 0.2 17.20 0.44 39.09 Example 14 B 30 7 0.05 1.05 0.01 105.00 Example 15 J 20 2.8 0.005 5.23 0.05 104.60 Comparative Example 1 F 20 2.8 0.05 5.59 1.59 3.52 Comparative Example 2 G 20 2.8 0.001 4.18 2.14 1.95 Comparative Example 3 H 20 2.8 0.003 5.50 0.65 8.46 Comparative Example 4 I 20 2.8 0.01 5.54 0.57 9.72 Comparative Example 5 Not used 20 2.8 - 6.41 3.30 1.94 16 20 0930839 As shown in Table 2, in accordance with Embodiments 1 to 5 of the present invention, in comparison with Comparative Example 15, any of the embodiments can increase the etching rate ratio (ER1 / ER2 ^ , . It is understood that, according to the present invention, it is possible to selectively record only from among the materials to be treated in which nickel and other metals (copper, etc.) coexist. [Simple description of the drawing]

[Main component symbol description] None

17

Claims (1)

200930839 X. Patent application scope: 1. A residual engraving liquid characterized in that: in a nickel etching solution containing nitric acid or sulfuric acid, hydrogen peroxide, and water, the composition has a selected from the following formula (I), the following a polymer of at least one repeating unit of the formula (Π) and the following formula (羾); -ch2~ch-ch 2 OH a) ❹ 2 —CH 2 —CH —CH—CH o h2c CH 2 (II) NI Ri H NI c 3 ΠΝ—RC = N = 2: 丨R4 N— (where 'Ri~5 is hydrogen, amine, imido, cyano, azo, thio, sulfonate' hydroxy, The carbonyl group, the carboxyl group, the nitro group, the alkyl group, the cycloalkyl group, the aryl group or the benzyl group 'may be the same or different', and the amine contained in the repeating unit may also be in the form of the fourth-order salt. 2. The etching solution according to claim 1, wherein the polymer having the repeating unit of the above formula (I) contains a polymer having a repeating unit of 18 200930839 represented by the following formula (IV); X- -N+-CH2-CH-CH2-...(IV) Re oh (where 'r6& R7 is hydrogen, amine, imido, cyano, azo, thio, benzoic acid, surface group, The carbonyl group, the carboxyl group, the fluorenyl group, the alkyl group, the cycloalkyl group, the oxime group or the benzyl group may be the same or different; further, X- is a chloride ion, a bromide ion, an iodide ion, an acetate ion or a carbonate ion). 3. The etching solution according to claim 1, wherein the polymer is contained in an amount of 0.001% by weight or more and 3% by weight or less. 4. The etching solution according to claim 1, wherein all of the repeating units of the polymer are selected from at least one repeating unit of the above formula (I), the formula (π), and the formula (m); The ratio is 1 〇~1 〇〇mol%. 5. The etching solution according to claim 1, wherein the polymer has a weight average molecular weight of 100 to 1,000,000. The remnant of claim 1 is wherein the nitric acid or sulfuric acid is again I.0% by weight to 38.5 parts by weight/❶, and the concentration of hydrogen peroxide is 00175% by weight to 1755% by weight. XI. 圏: No 19