TW201131023A - Copper electrolytic plating bath and copper electrolytic plating method - Google Patents

Abstract

Disclosed herein is a copper electrolytic plating bath including copper sulfate used in an amount of 50 to 250 g/liter calculated as copper sulfate pentahydrate, 20 to 200 g/liter of sulfuric acid, and 20 to 150 mg/liter of a chloride ion, and a sulfur atom-containing organic compound and a nitrogen atom-containing organic compound serving as organic additives. The nitrogen atom-containing organic compound includes a nitrogen atom-containing polymer compound obtained by a two-stage reaction including reacting one mole of morpholine with two moles of epichlorohydrin in an acidic aqueous solution to obtain a reaction product and further reacting one to two moles, relative to one mole of the morpholine, of imidazole with the reaction product.

Description

201131023 VI. Description of the Invention: [Technical Field] The present invention relates to a copper electrolytic plating bath and a copper electrolytic plating method which enable an object to be electroplated to be electroplated, particularly an article having a perforation, a via hole or a column. [Prior Art] At the time of copper electrolytic plating on a flat surface such as a laminated copper foil on a substrate, high-speed plating is currently performed by increasing the temperature of the electric ore bath and the cathode current density (see Japanese Patent No. 3 75 6 8 52). . However, in the case of copper electrolytic plating on a substrate having perforated (TH) or blind via holes (through holes), due to the ability to plate thickness (TP: the ability of the electrolytic solution to deposit metal in a uniform thickness) and the physical properties of the deposit Due to the requirements of properties (such as appearance, tensile strength, elongation, etc.), it is not easy to accelerate plating. When the substrate has a small aspect ratio (AR) of perforations or blind via holes, high speed plating may be achieved by enhancing plating agitation and increasing the plating temperature. However, if the aspect ratio becomes large, there arises a problem that the plating thinning ability deteriorates together with the physical properties of the deposit. Therefore, there is a limit to the type of substrate to be plated for high-speed electric ore by enhancing agitation and increasing the plating temperature. In the conventional copper electrolytic plating bath, if the plating temperature is lower than 30 t and the cathode current density is less than 5 A/dm 2 , electroplating has been performed by increasing the agitation while ensuring the plating thickening ability and the physical properties of the deposit within an allowable range. However, by applying a further acceleration of at least 5 A/dm2, the temperature of the ore must be raised due to limitations in starting agitation. The increase in temperature has been shown to be -5-201131023 for the electroplating of conventional organic additives with perforated and ruthenium access holes to lose their effectiveness. In the case of column plating which is plated by the recessed portion formed by the protective agent film, if the protective agent film has individual openings of a low height and a large size (i.e., a small aspect ratio), such as a blind via hole, As long as the agitation is enhanced, an electrolytic plating bath can be used to ensure the plating uniformity and the physical properties of the deposit. However, if the aspect ratio becomes large, it is expected that there will be no good plating even if strong agitation is performed. Even if plating is performed at a high speed by enhancing the agitation and increasing the plating temperature, there is still a problem that the deposit cannot be flattened. In any case, it is necessary to increase the plating temperature when plating on a column (bump) having a large aspect ratio at a high speed. In any of electroplating on a substrate having perforated or blind via holes and plating on a pillar (bump), an additive suitable for a high temperature electric shovel has been required. [Invention] The present invention has been accomplished under the circumstances of the present technology, Further, it is an object of the present invention to provide a copper electrolytic plating bath which enables high-speed plating on a substrate on which perforations, blind via holes, pillars, and the like are formed while maintaining good plating uniformity and ensuring physical properties of deposits. Another object of the present invention is to provide a copper electrolytic plating bath containing an organic additive which is effective in promoting high temperature electroplating. Another object of the present invention is to provide a copper electroplating method using the above copper electrolytic plating bath. The advantages of high speed plating include the possibility of shortening the plating time and increasing the number of outputs per unit time -6 - 201131023. If the production time can be shortened, the output will increase. In addition, in terms of the same amount of output, the space of the electroplating equipment can be saved and the size of the electroplating equipment can be made smaller (for example, the number of pipelines and electroplating equipment can be reduced). For example, if the cathode current density can be doubled, the length of the line, the number of plating baths, the number of plating baths, and the plating time can be substantially reduced by half. Therefore, the acceleration of electroplating is important from the viewpoint of reducing the electroplating cost. First, the inventors assumed in the following manner that the substrate of the high-speed electric ore having perforations, blind via holes, and the like has not been conventionally performed (i.e., due to the problem of high-speed electroplating). (1) The shovel's ability to be thickened by perforated or blind via holes is degraded and therefore does not meet the requirements of high-speed electric mines. The column geometry is poorly altered and therefore does not meet this requirement. (2) The physical properties of the sediment deteriorate. In particular, the gloss is not desirable. (3) When a soluble anode is used, the anode is converted to non-conducting. When the current density is increased at 25 ° C, the concentration of copper in the vicinity of the anode becomes high. In this case, the crystal of copper sulfate pentahydrate tends to deposit on the anode, thereby making the anode non-conductive. (4) There are no organic additives, especially a homogenizer which can be used at high temperatures. On the other hand, if the plating temperature becomes high, the solubility of copper sulfate pentahydrate is improved, so that crystallization cannot occur, and there is a concomitant advantage that non-conductivity is unlikely to occur. 201131023 As a compound suitable as a homogenizing agent for a high-speed copper electrolytic plating bath, a compound (i) which is maintained as a homogenizer when strongly stirred and elevated in plating temperature has been studied to obtain a compound (i) as an effective additive. The effect, that is, a compound which exhibits a high plating uniformity for a perforation and a blind via hole and which can form a plating film having good physical properties, or a compound which can be plated by a flat column (bump). Further, if the effect of either of the accelerator or the inhibitor of the organic additive is too large under the elevated temperature condition, the physical properties of the deposit deteriorate, and the plating thickness is lowered. In order to avoid this, the inventors have conducted research to obtain a compound which can balance the effect of the accelerator and the inhibitor of the organic additive contained in the plating bath under the conditions of increasing the plating temperature as an effective additive. The present inventors have conducted thorough research to solve the above problems, and as a result, found to have perforation in the presence of copper sulfate, sulfuric acid, and chloride ions, and as an organic additive, a sulfur atom-containing organic compound and a nitrogen atom-containing organic compound, which are adjusted to supply electroplating. In a copper electrolytic plating bath of a substrate such as a blind via hole or a column, when a specific polymer compound is used as the nitrogen atom-containing organic compound, high-speed copper electrolytic plating can be satisfactorily performed. More specifically, the polymer compound as a nitrogen atom-containing organic compound obtains a reaction product by reacting a monomoric porphyrin with an epichlorohydrin of an Ermo in an acidic aqueous solution, and one to two moles are obtained. It is obtained by a two-stage reaction in which the imidazole (relative to a mole of miso) is further reacted with the reaction product. The polymer compound effectively functions as a homogenizer', particularly in a copper electrolytic plating bath at a temperature of up to 35 t or higher. As a result, high-speed copper electroplating can be performed on a substrate having perforations, blind via holes, pillars, etc., from -8 to 201131023, while maintaining the plating uniformity and ensuring the physical properties of the deposit. Accordingly, the present invention provides the following copper electrolytic plating bath and copper electrolytic plating method. [1] A copper electrolytic plating bath comprising copper sulfate (calculated as copper sulfate pentahydrate) in an amount of 50 to 250 g/l, sulfuric acid of 20 to 200 g /1, and 20 to 150 mg a chloride ion of /1, and an organic compound containing a sulfur atom as an organic additive and an organic compound containing a nitrogen atom, the organic compound containing a nitrogen atom being a polymer compound containing a nitrogen atom, which is obtained by including in an acidic aqueous solution The tyrosine of the ear is reacted with epichlorohydrin of dimol to obtain a reaction product' and a two-stage reaction of one to two moles (relative to one mole of porphyrin) to further reaction of the reaction product is obtained. [2] The copper electrolytic plating bath according to [1], wherein the nitrogen atom-containing polymer compound is present in an amount of from 1 to 1,000 mg/Torr. [3] The copper electrolytic plating bath according to [1], wherein the sulfur atom-containing organic compound is selected from the group consisting of sulfur atom-containing organic compounds represented by the following formulas (1) to (4) and is present in an amount of from 0.001 to 100 mg/ 1

H—S—(CH2)a—(〇)b—S〇3M S—(CH2)

~(0)b-S03M

(S)c—(CH2)a- (0)b-S03M Ri\ d ^N_C-S-(CH2)-(CH0H)d-(CH2)a-(0)b-S03M R2 S (1) (2) (3) R3~〇-C~S-(CH2)a-(CHOH)d-(CH2)a-(〇)b-S03M (4)

Wherein R!, R2 and R3 independently represent an alkyl group having 1 to 5 carbon atoms, -9-201131023 Μ represents a hydrogen atom or an alkali metal, a is an integer from 1 to 8, and b, c and d are respectively 〇 Or 1. [4] A copper electrolysis electrolysis method comprising electroplating a workpiece to be shovel at a temperature of 30 to 50 ° C in a copper electrolytic plating bath according to any one of [1] to [3]. [5] The copper electrolytic plating method according to [4], wherein the object to be electroplated is a substrate having perforations, blind via holes or pillars. [6] The copper electroplating method according to [5], wherein the perforation has a diameter of 0.05 to 2.0 mm, a height of 〇.〇1 to 2.0 mm, and an aspect ratio of 0.1 to 1 〇, and the diameter of the blind via hole is 20 to 300 μηη and a height of 20 to 150 μπι, and the column has a diameter of 30 to 300 μηι, a height of 25 to 200 μηι and an aspect ratio of 0.2 to 3. Advantageous Effects of Invention The nitrogen atom-containing polymer compound as an organic additive and serving as a homogenizing agent has an unchanging quality at an electroplating temperature and can maintain an accelerator caused by an organic additive present in an electroplating bath under an elevated temperature condition. A good balance between the effect and the inhibitor effect. Therefore, the copper electrolytic plating bath of the present invention has the ability to plate the perforation or blind via holes and to maintain the physical properties of the deposit when the plating temperature is raised. With the copper electrolytic plating bath of the present invention, high speed plating can be performed even under weak agitation such as air agitation than the jet stream. In the past, high-speed electroplating has hitherto been carried out by applying plating temperature and cathode current density conditions which substantially require vigorous agitation (such as jet flow). -10- 201131023 [Embodiment] Now, the present invention will be described in more detail. The copper electrolytic plating bath of the present invention contains copper sulfate, sulfuric acid and chloride ions. The amount of copper sulfate contained is 50 to 250 g/丨', preferably 100 to 200 g/l, based on copper sulfate pentahydrate. The amount of sulfuric acid contained is 20 to 200 g/l', preferably 50. Up to 200 g/1, and the amount of chloride ions contained therein is 20 to 150 mg/1, preferably 30 to 100 mg/l. The copper electrolytic plating bath of the present invention additionally contains an organic compound containing a sulfur atom and an organic compound containing a nitrogen atom. The sulfur atom-containing organic compound may be a sulfur atom-containing organic compound which is conventionally used for perforation or blind via copper electroplating. More specifically, an organic compound containing a sulfur atom of the following formulas (1) to (4) can be used: H-S-(CH2)a-(0)b-S03M (1)

S—(CH2)a-(0)b-S03M I (2)

(S)-(CH2)a-(0)b-S03M

Ri\ .N-C-S-(CH2)a-(CH0H)d-(CH2)-(0)b-S03M (3) O’ It

K2 S R3—〇-C-S-(CH2)-(CHOH)d-(CH2)a-(〇)b-S〇3M (4)

S wherein Ri, R2 and R3 independently represent an alkyl group having 1 to 5 carbon atoms, Μ represents a hydrogen atom or an alkali metal 'a is an integer of 1 to 8, and b, c and d are respectively 〇 or 1. The concentration of the compound in the copper electrolytic plating bath is usually from 0.001 to 100 mg/inch. The nitrogen atom-containing organic compound used in the copper electroplating bath of the present invention is a polymer-11 - 201131023 compound which is obtained by reacting a monomoric porphyrin with an epichlorohydrin of an Ermo in an acidic aqueous solution. The product is obtained in a two-stage reaction in which one to two moles of imidazole (relative to one mole of morpholine) is further reacted with the reaction product. The nitrogen-containing polymer compound acts as a so-called homogenizer' and does not undergo a quality change when the plating temperature is raised (e.g., to 30 ° C or higher, particularly to 35 to 50 C). The polymer compound maintains a good balance between the accelerator effect and the inhibitor effect caused by the organic additive contained in the plating bath under high temperature conditions. The nitrogen-containing portion is formed on a non-flat portion (such as a perforation or tantalum via hole) formed on a substrate, or during copper electroplating on a non-flat portion such as a resist film formed when a pillar (bump) is formed. The polymer compound serves as an effective homogenizing agent for maintaining the plating thickening ability and the physical properties of the deposit as the plating temperature is raised. The nitrogen atom-containing polymer compound is conventionally known as CAS 109?82-76-0' It is considered to be a polymer compound having a poly-structure. The polymer compound is subjected to a first-stage reaction between a molar salt comprising a molar and an epichlorohydrin of dimor and is preferably one to two moles (preferably about two moles, more preferably 1.8 to two) Mole) Imidazole is added to the two-stage reaction of the second-stage reaction of the reaction product of the first stage to provide a polymer compound. More specifically, for example, a mole of porphyrin is dissolved in distilled water of about 37.5 m 1 and adjusted to pH 5.5 by HCl. Dimorone epichlorohydrin was dropped into the solution at a reaction temperature of about 5 (rc), and then kept at 4 Torr to 5 ° C until no free epichlorohydrin was detected (stage - stage) Next, a mole of imidazole is added to the reaction product obtained in the first stage, wherein -12-201131023 is added with 50 g of NaOH dissolved in 125 ml of water, followed by reaction at 55 ° C to 60 ° C for 6 hours ( In the second stage), water is added to the obtained solution, whereby a total amount of 1 liter of the solution can be used. Ralu (registered trademark) Plate MOME (manufactured by Raschig GmbH) or the like can be proposed as the polymer. Commercially available product of the compound. The concentration of the nitrogen atom-containing polymer compound in the copper electrolytic plating bath is from 1 to 1,000 mg/m, preferably from 10 to 500 mg/1. The copper electrolytic plating bath of the present invention may additionally comprise oxygen. An organic compound comprising a polyether organic additive for copper electroplating for perforation or blind via holes, such as polyethylene glycol. The concentration of the oxygen-containing organic compound in the copper electrolytic plating bath is preferably 〇_〇〇1 to 5,000 mg / 1. It should be noted that it can be used in this hair The polyethylene glycol is a molecular weight of from 200 to 200,000. The molecular weight of this example is measured according to the method described in Japanese Pharmacopoeia. It can be applied in copper electrolytic plating using the copper electrolytic plating bath of the present invention. Conventional plating conditions, in particular, when using a plating temperature of not lower than 35 ° C (preferably 35 ° C to 50 ° C) and a cathode current density of not less than 5 A / dm 2 (preferably 5 to 20 A) /dm2), it is possible to obtain a more stable plating thicknessing ability and better sediment characteristics than those obtained in conventional copper electrolytic plating. The anode used is preferably an insoluble anode. For example, titanium may be coated with platinum, An anode of yttrium oxide or the like. Various types of agitation which can be used by conventional agitation tools include, for example, jet agitation or cyclic agitation by a pump, or air agitation by an air pump, and by paddles and cathodes. Mechanical agitation generated by a locking tool, etc. -13- 201131023 A copper-electrolytic electrolysis bath of the present invention is formed by a resist film on or in which a non-flat portion (such as a perforation or a column (bump)) is formed. The non-flat object (such as a printed circuit board) copper electrolytic plating. The surface of the via hole (via hole comprises a blind side thereof and the bottom surface of the case (the copper ore is not applied by the blind via hole electroplating case) is particularly effective.

The present invention is suitable for copper electrolytic plating of substrates having large aspect ratio blind via holes. For example, the present invention has a diameter of preferably 0.1 to 1.0 mm, a sheet thickness (height), preferably 0.05 to 1.6 mm, and an aspect ratio (AR) of 0.1 to 10, preferably 0.1 to 5.0, 300. Ππι, preferably 30 to 200 μηι, height (depth, preferably 40 to 1 〇〇μηι, and aspect ratio (AR, I is 0.2 to 1.5, preferably 0.4 to 1.0) When electroplating forms a column (bump), there are two main methods: the surface of the object to be formed into the column (bump) and the portion of the column (bump) formed by the protective agent film is protected with a protective agent film and then the protective agent is removed. The protective agent film on the surface of the article forms a column in which the plating protection is formed (bump) and a method of removing the protective agent film is performed in the opening portion. In the former method, it is possible to form a column having a large aspect ratio (AR). (Long plating is particularly suitable for the blind via hole of the substrate) or the copper plating to be electroplated on the tantalum portion is formed on the blind surface. The perforation of the deposited via hole filling (AR) is 0.05 to 2.0 mm from 0.01 to 2.0. Mm, ie height/diameter and diameter 20 to) high-speed electroplating of 20 to 150 μηι, height/diameter) effective use of the method of forming an electroplated copper on the following surface, followed by etching the uncoated film; and borrowing a pattern to electroplate the copper to be shaped, and then moving Accelerate copper plating. At the same time, the periphery of the column (bump) which has been formed -14-201131023 is taken along the central portion of its height by the morning coil, and the accompanying problem is that the local verticality is lowered. When the column (bump) is high, it takes a long time to etch. When a column (bumping) is formed by copper electrolytic plating according to the present invention, the method using a plating resist film is used. More particularly, the copper electrolytic plating has a column (bump) diameter of 30 to 300 μm, preferably 50 to 200 μm, and a height (preservation) of 25 to 200 μm, preferably 30, for a large aspect ratio (AR). High Speed Electricity to 150 μηι and Columns (Uplift) with a Diameter of 0.2 to 3, preferably 0.3 to 2 In this example, it will be noted that the plating causes the deposit to fill the recessed portion of the electrical opening. EXAMPLES The examples and comparative examples are shown to more clearly illustrate that the present invention should not be construed as being limited by the following examples. Examples 1 to 4 and Comparative Examples 1 to 3 Laminate substrates having the perforations (four types) or blind types shown in Table 2 were used, and copper electroforms using the following formulations were perforated under the following plating conditions. Or an electrical layer is formed in the blind via hole. It should be noted that copper electrolytic plating is carried out in a manner of performing a known pretreatment in which copper deposition is to be formed, on which no (thickness of 0.3 μηι) is formed as a lower layer, and then copper electrolysis is performed: heavy erosion is formed. Preferably, the present invention, for example, a straight: protective film high ratio (AR) plating is effective. The plating protection agent is clear, the opening hole of the present invention (: electroplating bath: copper plating: part of the material: electroplated copper film crucible. -15- 201131023 <copper electroplating bath> copper sulfate pentahydrate: 150 g/l sulfuric acid : 150 g/1 chloride ion: 50 mg/1 organic additive: shown in Table 1 < plating conditions> Cathodic current density: 15 ASD (A/dm2)

Temperature: 4 0 °C Plating time: 8 minutes (corresponding to the thickness of the copper layer of 26 μηι) Stirring: Slightly strong air agitation Table 1 Organic additive m _ Comparative example 1 2 3 4 1 2 3 SPS (mg/1) 15 15 15 15 15 3.0 3.0 PEG#6000 (mg/1) 300 0 300 0 300 300 300 Homogenizer Polymer Compound 1 PAS-A-5 JGB Zero (mg/1) 50 50 1 10 500 50 1.0 Zero SPS: Two Disodium bis (3- sulfopropyl ) disulfide disodium PEG #6000 : Polyethylene glycol 6000 (manufactured by Wako Pure Chemical Industries, Ltd.) Polymer Compound 1 : Ralu (trademark) Plate MOME (by Raschig

PAS-A-5 : Copolymer of diallyldialkylammonium and sulfur dioxide (by

Nitto Boseki Co., Ltd., and the average molecular weight is 4,000) JGB : Janus green black -16- 201131023 It will be noted that the number of PAS-A-5 and JGB is set to be the best when tested by Hertz battery. An additive concentration in the potential region sufficient to provide gloss. The appearance after copper electrolytic plating was visually observed, and the plating thinning ability (TP ) was evaluated in the following manner. The results are shown in Table 2. [Evaluation of plating thickness (TP)] (1) Perforation (T Η ) Measure the thickness of the copper layer at the portion of Fig. 1 (Α) to F, and then calculate the ratio according to the following equation (%) Evaluation. It should be noted that the thicknesses of the central portions of the perforations indicated by E and F' measurements of Examples 1 to 4, Comparative Examples 丨, 3, and Fi, and Comparative Example 2 were measured for the upper end portions of the perforations indicated by e2 thickness of. TP (%) = 2 X (E+F)/(A+B+C+D) X 100 E = Ei.Es and F = F| or F2. (2) Blind via hole The thickness of the copper layer at the portions α to C in Fig. 1 (B) was measured, and then the ratio (%) calculated by the following equation was evaluated. TP (%) = 2 XC / (A + B) X 1 〇〇 In Figure 1 (A) and 1 (B), 1 is the substrate (insulation layer), 2 is laminated copper, 3 is An electroless copper layer, 4 is an electroplated copper layer, t is a perforation, and v is a blind via hole. -17- 201131023 Table 2 Real _ Control actual capture 1 2 3 4 1 2 3 Appearance Glossy Glossy Glossy Glossy Part of the uneven part Coking TP Perforation (TH) Sheet thickness (mm t) Hole diameter (mm φ) 0.10 0.10 98% 99% 97% 100% 103% 32% 148% 0.20 0.10 97% 98% 97% 99% 101% 35% 111% 1.6 0.6 70% 68% 67% 69% 65% 35% 42% 1.6 0.8 75% 73% 72% 76% 69% 38% 45% Blind path 3 FL (through hole) Depth (^md) Hole diameter (μιηφ) 85 150 74% 75% 73% 75% 53% 37% 21% 85 125 72% 72% 70% 71% 35% 41% 16% It will be noted that in Comparative Example 2, the thickness of the copper layer is the smallest at the corner of the open side of the blind via hole, except for the thickness of the copper layer. The corner portion on the bottom side is the smallest. <Perforation> Examples 1 to 4, Comparative Example 1: In the case where the thickness of the substrate is small (or the length of the perforation is short), current concentration is suppressed inside the perforation, so that the thickness of the copper layer inside the perforation is substantially the same as the surface. Therefore, the plating uniformity is about 100%. When the thickness of the substrate is thick (or the length of the perforation is long), the current plating thickness reduction ability inside the perforation is small, so that the plating uniformity is suppressed from deteriorating. Comparative Example 2: The homogenizer inhibited the deposition of the perforated corner portion to form a small thickness of -18-201131023. Comparative Example 3: When the thickness of the substrate was small (the length of the perforation was short), the current was concentrated on the perforated portion, so that the thickness of the copper layer inside the perforation was thick, so that the plating thickening ability was much lower than 100%. On the other hand, when the thickness of the substrate is large (or the length of the perforation is long), the current does not flow through the inside of the perforation, so that the thickness of the copper layer in the central portion of the perforation becomes small, thereby deteriorating the plating uniformity. <Blind via hole> Examples 1 to 4: The copper deposition on the surface was suppressed by a proper uniform effect, and the current passed through the inside of the blind via hole. The suppression effect of the corner portion of the bottom side of the blind via hole is weak, so that the current also flows to the corner portion of the bottom side of the via hole. Comparative Example 1: The uniformity effect was weak, and the plating portion of the bottom side of the crucible passage hole through which the current could not flow was poor in plating uniformity. Comparative Example 2: The uniform effect was too strong, so that the uniform agent inhibited the deposition of the corner portion of the open side of the blind via hole to form a film. Comparative Example 3: Since there is no homogenizer, the plating thickness of the bottom side of the blind via hole which the current cannot flow to is very poor. The physical properties of the copper layer were evaluated using the copper electrolytic plating baths of Examples 1 to 4 and Comparative Examples 1 to 3 according to the following procedures. -19* 201131023 [Evaluating the physical properties of the copper layer] Plating. This electric and extension was subjected to the following pretreatment of the SUS sheet, and the copper plating layer was formed on the SUS sheet under the following plating conditions using the above copper electrolytic bath, and the foil was peeled off from the SUS sheet after the following post treatment. Plating. The plating film (layer) was evaluated for tensile strength according to the following method. <Preprocessing>

Co., (1) Acid detergent treatment (MSC-3-A, manufactured by Uyemura & LTD.) (2) Hot water cleaning (3) Water cleaning (4) Pickling (5) Water cleaning & plating Condition > Cathode current density: 15 ASD (A/dm2)

Temperature: 40 ° C Plating time: 15 minutes (corresponding to 50 μηι of copper layer thickness agitation: slightly stronger air agitation <post treatment> (1) water cleaning -20- 201131023 (2) prevention of discoloration (ΑΤ-21 (manufactured by Uyemura & Co., Ltd.) (3) Water cleaning (4) Drying <Measurement of tensile strength and elongation> The copper film prepared above was punched into a dumbbell shape test of the size shown in Fig. 2. The elongation and tensile strength before fracture at the clamp distance of mm and the elongation of 4 mm/min were evaluated by the following equation 〇T[kgf/mm2] = F[kgf]/( 10[mm] xd[mm]) where T = tensile strength, F = maximum tensile strength, and d = film thickness at the center of the test piece E [%] = AL [mm] / 20 [mm] where E = elongation, and AL = elongation length before film breakage. Table 3 Example of actual sun control 1 2 3 4 1 2 3 Tensile strength (kg weep mm2) 32 33 33 32 34 40 34 Elongation (%) 29 28 28 30 26 15 22 Examples 5 to 8 and Comparative Examples 4 to 6 A layer of a depressed portion having a diameter of 80 μΐΏ and a height (depth) of 1 μm was formed on the surface by a plating resist film. The substrate was subjected to copper electrolytic electrowinning on the depressed portion of the laminated substrate to be formed at the column of -21,310,023 using the copper electrolytic plating bath shown in Table 1 under the following conditions. It will be noted that an electrolytically plated copper layer is to be formed. The pretreatment is carried out in advance, and then an electroless copper layer having a thickness of 0.3 μm is formed as a lower layer and subjected to copper electrolytic plating. <Plating conditions> Cathodic current density: 10 ASD (A/dm2) Temperature: 3 5 t : Plating time: 36 minutes (corresponding to the height of 80 μηι column) Stirring: Slightly strong air agitation The shape of the column after copper electroplating is evaluated for the column profile (ie, the section along the height). The maximum and minimum 値 are calculated and the difference between them is calculated. The results are shown in Table 4. Table 4 m paid comparison example 5 6 7 8 4 5 6 column height difference (μπι) 3.2 3.3 3.5 3.2 13 56 42 The above shape is substantially Substantially slightly slightly flattened flat flattened flat projections Examples 5 to 8: Based on a suitable uniform effect, a substantially flat column can be obtained, but only the end portion of the copper layer Comparative Example 4: The uniform effect is too weak, so the copper layer at the end portion is thin -22- 201131023 Comparative Example 5: The uniform effect is too strong, so the copper layer at the end portion is extremely thick. Comparative Example 6: The copper layer of the end portion became too thin due to the non-uniform effect. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 (A) and 1 (B) are cross-sectional views of a portion of a substrate, respectively, illustrating the measurement of the thickness of the deposit to evaluate the plating thickening capability of the examples and comparative examples, wherein Figure 1 (A) is a cross-sectional view of the perforation and FIG. 1 (B) is a cross-sectional view of the blind via hole; and FIG. 2 is a view showing the shape and size of the test piece for measuring the physical properties of the deposit of the embodiment and the comparative example. Schematic diagram. [Main component symbol description] 1 : Substrate 2 : Laminated copper 3 : Electroless copper plating layer 4 : Electroplated copper layer A/B/C/D/E/F : Part v : Blind via hole t : Perforated -23-

Claims (1)

201131023 VII. Patent application scope: 1. A copper electrolytic plating bath comprising copper sulfate (calcium sulfate pentahydrate) in an amount of 50 to 2 50 g/l, sulfuric acid of 20 to 200 g/l, and a chloride ion of 20 to 150 mg/1, and a sulfur atom-containing organic compound and a nitrogen atom-containing organic compound as an organic additive, the nitrogen atom-containing organic compound being a nitrogen atom-containing polymer compound, which is included in an acidic aqueous solution A two-stage reaction in which a monomolecular morpholine is reacted with epichlorohydrin of dimorin to obtain a reaction product, and one to two moles (relative to one mole of morpholine) imidazole is further reacted with the reaction product. And get. 2. The copper electrolytic plating bath according to claim 1, wherein the nitrogen atom-containing polymer compound is present in an amount of from 1 to 1000 mg/1 ° 3 as in the copper electrolytic plating bath of claim 1 Wherein the sulfur atom-containing organic compound is selected from the group consisting of the sulfur atom-containing organic compound represented by the following formulas (1) to (4) and is present in an amount of 0.001 to 100 mg/1 H-S-(CH2)a-(0) b—S03M (1) S—(CH2)a-(0)b-S03M I (2) (S)-(CH2)a-(0)b-S03M Ri\ ^ N— |T ~ S—(CH2 ) a~ (GHOH)d—(CH2)a—(0)b—S 03M (3) D ^ II K2 S R3—O—S—(CH2)a—(CHOH)d—(CH2)a—( 0) b—S03M (4) It s wherein R!, R 2 and R 3 independently represent an alkyl group having 1 to 5 carbon atoms, Μ represents a hydrogen atom or an alkali metal, a is an integer from 1 to 8, and b, c And d are respectively 〇 or 1. A copper electroplating method comprising electroplating an object to be electroplated at a temperature of from 3 Torr to 5 Torr in a copper electrolytic plating bath according to any one of claims 1 to 24 201131023 to 3. 5 The copper electrolytic plating method of claim 4, wherein the object to be electroplated is a substrate having a perforation, a via hole or a pillar. 6. The copper electrolytic plating method according to claim 5, wherein the perforation has a diameter of 〇.〇5 to 2.0 mm, a height of 0.01 to 2.0 mm, and an aspect ratio of 0.1 to 1 〇, the blind via hole The diameter is 20 to 300 μπι and the height is 20 to 150 μηι, and the column has a diameter of 30 to 300 μηι, a degree of 25 to 200 μηι and an aspect ratio of 〇.2 to 3. -25-