TW201109478A - Electrolytic plating equipment and electrolytic plating method - Google Patents

Abstract

An electrolytic plating equipment includes: a plating tank for holding plating solution; and a separate tank apart from the plating tank, for holding the plating solution circulating between the plating tank and the separate tank. The separate tank contains a first space and a second space located downstream from the first space. The plating solution in the first space in an amount exceeding a specific height flows from the first space into the second space, and the plating solution falls through air in the second space.

Description

201109478 IV. Designated representative map: ) The representative representative of the case is: (1). The symbol of the symbol of the representative figure is briefly described: 1 plating device; 13~ plating groove; 15~ his groove; 17~ first space 19~2 space; 20~ his groove body 21~1st partition; 2 3 ~ upper edge; 2 9 ~ transport side piping; 29a ~ supply 〇 41 ~ return side piping; 4 la ~ end; 4 lb ~ end; 41 c ~ end; 47 ~ slot body; 49 ~ overflow slot; 51 ~ side wall; 5 3 ~ upper edge; 5 5 ~ anode; 57 ~ cathode; 59 ~ anode bag; 61 ~ nozzle; 63 ~ pump; 64 ~ pump; 6 5 ~ filter. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇 6. Description of the invention: [Technical Field of the Invention] The present invention relates to a plating apparatus and a plating method. 2 201109478 [Prior Art] The electric clock system uses 丨&lt;for the use of a wiring pattern for forming a wiring pattern on a printed circuit board, etc., for example, in copper sulfate plating, for gloss, film properties, drape, and conduction The filling of the hole is also the result of the purpose of adding a lightening agent, a softening agent, a sturdy agent, a scenting agent, or a promoter of the fourth agent. Various additives such as inhibitors. The additives act effectively on the surface of the circuit board and act to promote the filling of the via holes or the filling of the via holes by the effective action of the promoter in the via holes and the via holes. However, when the accelerator is excessively formed in the plating solution, the effect of suppressing the growth of the active nucleus by the inhibitor is lowered, and the physical properties of the pleats which are not caused by Φ are lowered. Further, the effect of suppressing the precipitation on the surface of the board is lowered, and the coverage of the via hole is deteriorated, and the hole filling property of the via hole is deteriorated. In addition, if the accelerator in the plating solution is insufficient, the effect of promoting the production of the active nucleus is lowered, and the dense film is not obtained, and the physical properties of the film are lowered. In addition, the outer surface of the through hole or the via hole is insufficient for the effect of the effect, and the coverage of the through hole is deteriorated, and the hole filling property of the via hole is deteriorated. Therefore, it is very important that the various additives in the plating solution are added in an appropriate balance. Further, the concentration of dissolved oxygen in the plating solution is known to be one of the main factors affecting the performance of the plating film. For the reason, a case of using a bis(3-thiopropyl) disulfide (sps) of a general brightener plated with copper sulfate will be described. That is, the following series of redox reactions occur in the plating treatment. The surface SPS on the cathode was reduced to 3_mercaptopropane-sulfuric acid (MPS). SPS acts as a promoter by reducing copper ions by 3 201109478 when two mps are returned to an SPS near the cathode. (4) that does not participate in the reaction will be oxidized by dissolved oxygen to recover into SPS. However, if the dissolved oxygen is insufficient, the MPS and Cu + bonds are connected by Cui-ΜΡς, and the MPS accumulates. Cu + -MPS accumulates, the concentration of the brightener becomes excessive, and the right public is not able to be presented... When the oxygen concentration becomes excessive, the amount of oxygen-oxidized MPS is increased and the amount of reduced copper ions is decreased, so that the promotion effect is not obtained, and the target film performance cannot be sufficiently obtained. In the ground, it is necessary to adjust the dissolved oxygen concentration in the plating solution to a proper range I'M. When the soluble anode is used for the anode, the dissolved oxygen is consumed due to the dissolution of the metallic copper, and the dissolved oxygen concentration in the plating solution is easily changed to 16 When an insoluble anode is used as the anode, the concentration of dissolved oxygen in the solid ore is likely to increase due to the production line from the anode. Therefore, various techniques have been proposed in which the concentration of dissolved oxygen in the liquid solution is adjusted within a predetermined range. Japanese Patent Publication No. 20-144478 discloses a plating apparatus using a soluble anode as an anode. The apparatus 'includes: (4) a tank for blocking the plating solution; and a tank for the other side of the coating tank. Slot with his slot There is a structure of a mineral liquid circulation. In this device, the air is blown into the plating solution through the air blowing pipe, and the dissolved oxygen concentration of the plating solution can be maintained at 5 ppm or more to solve the deterioration of the quality of the film. JP-A-2007-1 69700 discloses a method of electroplating using an insoluble anode. In this method, the plating bath is used to mix the bath with air or an inert gas to maintain the dissolved oxygen concentration of the money at 30 mg. In the case of a printed circuit board or the like, the wiring of a printed circuit board or the like is thinned due to the miniaturization of the through holes and the via holes. The required quality is also improved. For example, if there is foreign matter floating in the plating solution, the foreign matter nucleates and a part of the bell coating is formed in the bellows (the tumor-like portion), and the plating device is provided with plating. a filter for separating foreign matter in the key liquid in the liquid. The filter separates the various foreign matters in the ore liquid from the plating solution by a plating solution. However, if many metal particles such as copper particles are attached to the filter, Due to this The metal particles consume dissolved oxygen in the plating solution, and the additives contained in the plating solution (for example, a sulfur-based additive) are deteriorated. Therefore, in order to suppress the deterioration of the quality of the plating film, it is necessary to frequently exchange the filter. SUMMARY OF THE INVENTION The purpose of the present month is to provide an electric ore device and an electric ore method which can reduce the dissolved oxygen concentration of the key liquid; the electric chain device and the electric ore method which are caused by the cost of exchanging the filter. : The money storage tank for storing liquid recording; and the groove of the L-series and the dead money-slotting tank, the above-mentioned clock liquid is circulated between the above-mentioned rhodium-plating and the above-mentioned other tank, which is located in the interior thereof. The first space chamber and the second space F曰1 on the downstream side have: the portion s and the portion of the plating solution that exceeds a predetermined height are inserted into the second space by the first door machine, and the plating is performed The liquid is in a configuration in which the space of the crucible 2 flows down in the air. Milk [Embodiment] 5 201109478. Hereinafter, each embodiment of the embodiment of the present invention will be described in detail with reference to the drawings, and a case where silver or copper is to be plated is described as an example. <First Embodiment> As shown in Fig. 1, a plating apparatus ii according to an i-th embodiment of the present invention includes a plating tank 13; a tank 15 having a separate body from the plating tank 13; and a plating tank 13 The plating solution is transported to the transport side piping 29 of the other tank 15; the plating liquid is returned from the other tank 15 to the return side piping 41 of the plating tank 13. The key application groove 13 has a groove body 47 having a substantially rectangular parallelepiped shape with an upper opening, and an overflow groove 49 provided integrally with the groove body 47. An anode 55 is disposed inside the tank body 47. Further, a groove body 47 constituting a cathode 57 to which a plated object can be placed is formed. The anodes 55 are disposed on both sides of the cathode 57, respectively. As the anode, a soluble anode or an insoluble anode is used. As the soluble anode, for example, a copper plate can be used. Further, the soluble anode can be accommodated, for example, in a mesh-shaped storage container formed of spherical copper (copper:) or the like. These steel sheets or copper may, for example, be formed by containing a gamma. As the insoluble anode, for example, a coating of indium oxide on Ti-Pt may be used. Each anode 55' is disposed so that the plating solution can be circulated without causing The anode potential is passed from the gentry β to “the inside of the crucible. The anode pouch 59 is formed, for example, of a material such as ethylene. The polycathode 57 and each anode 55 are provided with a mouthpiece 6 along the cathode. Each of the nozzles 61 is provided with a plurality of chain liquids which are sent by the groove 15 in the direction of the direction to the side of the ...: a wide range of 41 - by "---: 6 201109478 卜" plating solution around the cathode 57 Stirring, in addition to the above-mentioned stirring, the mechanical properties of the stirring knife and the stirring paddle type weighing machine shown in the figure (4) may be omitted. In addition, it can also be used in combination with jetting = mechanical agitation. &lt;Stirring is applied between the anode 55 and the cathode 57, and electricity is applied by an illustration (not shown). Thereby, the electric forging 1 and the extraction groove 49' of the cathode 57 as the mineral can be integrally attached to the side portion of the tank body 47. In the "extraction groove 49", the plating solution in the groove body 47 flows in beyond the upper edge portion 53 of the side wall 51 of the groove body 47. In the overflow #49, a liquid level sensor (not shown) that senses the liquid level in the tank is provided. The liquid level of the overflow tank 4 can be adjusted by controlling the driving or stopping of the pump 63 according to the level sensor and the sensor. The other groove 15' has a groove body 2 of a slightly rectangular parallelepiped shape having an upper opening; and an i-th partition wall 21 for dividing the internal space of the other groove body 20 into two. The first partition wall 2 has a substantially rectangular shape and is erected from the bottom side of the groove body 2〇. The inside of the other tank 21 is divided into an upper space 17 and a second empty space 9 located on the downstream side of the crucible 17 by the first partition wall 21. As shown in Fig. 2 and Fig. 2, the second partition wall 2 has a partition main flange 25 extending upward from the bottom side of the groove, and a protruding piece 2 extending from the upper end of the partition main body 25 toward the second space 19 side. 7. The upper edge portion 23 of the first partition 21 is set on the upper tank body 20

The edge is a low stiletto.卩 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他 他2 The structure of the space 19. In the other groove 15, 201109478, only the upper edge portion 23 of the first partition wall 21 is a space above, and the first space 17 of the 坌7 + j is in communication with the second space 19. In addition, the groove 15 is lower than the upper edge portion 23 of the upper oyster weight to prevent the plating solution from moving between the first space 17 and the second space 19 ^ ^ • ^ ^ ^ to move the first two 17 and the first 2 space 19 isolated structure. The plating solution flowing into the second space 19 is such that the second space 丄9 is in the air to the lower portion. In order to adjust the liquid level of the plating solution in the second space i 9 in the air in the second space 19, the plating solution is adjusted so that the predetermined height of the upper edge portion 23 of the first partition 2 is lower. s position. The liquid level of the clock liquid in the second space 19 can be adjusted by, for example, controlling the driving or stopping of the pump 64 provided on the return-side pipe 41. Further, in the second space 196, a liquid level sensor that senses the level of the liquid level in the space may be provided. The liquid level of the control unit 64 can be controlled or stopped according to the sensing result of the liquid level sensor, and the liquid level of the second chamber 19 can be adjusted. The protruding piece 27 is extended from the upper end of the partition main body 25 toward the second space, and the tip end thereof is separated from the side surface of the partition main body 25 (four) 2 on the space 19 side. By providing such a protruding piece 27, the plating liquid 'flowing into the second space 19 from the i-th space 17 leads to the leading end portion along the protruding piece 27, and the front surface of the leading end portion is separated from the protruding piece 27 to be discharged to the air. in. Since the tip end portion of the protruding piece 27 is separated from the side surface of the partition wall main body 25, the plating solution can be prevented from flowing down along the side surface of the partition wall main body 25. In the present embodiment, the case where the first partition wall 21' has the protruding piece 27 as shown in FIG. 2 is taken as an example, but the protruding piece 27 having the modified example shown in FIGS. 2β to 2D may be used. The form 'may also be in the form of a protruding piece having a modification as shown in FIG. 8 201109478 and FIG. 2F. In the modification of Fig. 2B, the projecting piece 27 is extended from the upper end of the partition main body 25 toward the second space 19 side and obliquely upward. Also in the case of this modification, the tip end portion of the dog pull piece 27 is separated from the side surface of the partition wall main body 25 in the same manner as the embodiment of Fig. 2A. Therefore, it is possible to prevent the plating solution from flowing down along the side surface of the partition main body 25, but the plating liquid tends to flow down along the surface (lower surface) on the second space 19 side of the protruding piece 27 as compared with the embodiment of Fig. 2A. The protruding piece 27 of the modification 1 of Fig. 2C is extended from the upper end of the partition main body 25 toward the second space 19 side and obliquely downward. The case of this modification is also the same as the embodiment of Fig. 2A. The tip end portion is spaced apart from the side surface of the partition wall main body 25, so that the plating solution can be prevented from flowing down along the side surface of the partition wall main body 25. Further, since the protruding piece 27 is inclined obliquely downward, it is possible to substantially prevent the plating liquid from flowing into the lower surface (inner surface) of the protruding piece 27. The modification of Fig. 2C is better than the form of Fig. 2A. In the modification of Fig. 2D, the protruding piece 27 has a lateral portion 27a extending from the upper end of the partition main body 25 toward the second space 19 and extending in the lateral direction, and a vertical portion 27b extending downward from the tip end of the lateral portion 27a. The tip end of the vertical portion 27b is separated from the side surface of the partition main body 25. Also in the case of this modification, the tip end portion of the protruding piece 27 is separated from the side surface of the partition wall main body 25 in the same manner as in the embodiment of Fig. 2A, so that the plating solution can be prevented from flowing down along the side surface of the partition wall main body 25. Further, in this form, the ore liquid which has flowed into the second space 19 from the first space 17 is guided to the tip end portion along the lateral portion 27a, and then flows downward along the vertical portion 27b. The tip end portion has a large distance from the side surface of the partition main body 25. Therefore, the inflow of the mineral liquid into the inner surface of the protruding piece 27 can be substantially prevented. At this point, the modification of 201109478 2D is better than the form of FIG. 2A. In the modification of Figs. 2E and 2F, the first partition wall 21 does not have a protruding piece. In the modification of Fig. 2E, the first partition 21 is arranged in the vertical direction. In the modification of Fig. 2F, the partition wall 21 is disposed obliquely to the vertical direction. The first partition wall 21 of the document example is inclined on the downstream side from the upper side to the lower side. The transport side piping 29 is the upstream side end. The portion is connected to the bottom portion of the overflow groove 49 and the lower portion of the side wall 51 of the groove body 47, and communicates with the overflow groove 49 and the groove body 47. On the downstream side of the conveying-side pipe 29, a supply port 29a for supplying plating liquid to the other groove 15 is provided. As shown in Fig. 1 and Fig. 3A, the supply port 29a is located higher than the liquid level of the plating solution in the i-th space, and is not in contact with the plating solution. Therefore, the plating solution discharged from the supply port 29a is When the supply port 29a flows downward and comes into contact with the plating solution stored in the first space 17, the plating solution is caused to have a certain degree of impact. This causes the plating solution in the i-th space 丨7 to flow somewhat. 3B to 3E, the return-side pipe 2 &lt;the supply port 29a is located below the predetermined height. J is the plating solution in which the supply port 29a is located in the first space 17. The liquid surface is submerged in the form of a plating solution. In these variants, the spit is spit from the supply port. The mineral liquid 'will be directly supplied to the liquid of the plating liquid stored in the second space 17 * This can be left in the plating liquid of the first space 17 by the supply port 29a once it is discharged into the air. In the form of Fig. 3A, the impact on the liquid recording of the first space 17 is reduced. In the modification of Fig. 3C, the downstream side end of the return side pipe 29 is bent by 10 201109478 into a clock liquid supply port. The direction of the discharge of 29a is applied to the inner side of the groove body 2G. In this modification, the shape of the plating liquid is lower than that of the discharge direction of the plating liquid, which can inhibit the storage of the flute 1 in the pq 1 7 in the first two The flow of the plating solution between the two, in particular, the flow of the plating liquid on the lower side. In the modification of Fig. 3D, the end portion on the downstream side of the conveying-side pipe 29 is erected (the modification is six), the wheel The supply-side pipe Μ has a supply port 29a for discharging a plurality of plating solutions. The discharge rate of the plating solution discharged from each of the supply ports 29a is smaller than that of the modification of Fig. 3B. Therefore, storage in the first space can be suppressed. The flow of the plating solution of 17, especially the flow of the plating liquid on the lower side. The modification of Fig. 3E The return-side piping 29' has a structure in which the other side of the downstream side is in a large structure. Thereby, the discharge speed of the plating liquid discharged from the supply port Ma becomes smaller than the modification of Fig. 3B. The flow of the plating liquid stored in the first space 17, in particular, the flow of the liquid liquid on the lower side. As shown in Fig. 1, the upstream side end portion of the return-side piping 41 is connected to the side of the tank body 20. In the second space 19, the end portion of the downstream side is divided into a plurality of (three in the present embodiment). Two end portions 41a of the plurality of side ends of the plurality of pipes, 41b is connected to the upper V nozzle 61 and communicates with each nozzle 61. Multiple piping ends. The remaining end portion 41c is connected to the bottom of the groove body 47 and communicates with the inside of the groove body 47. The end portion 41c is disposed on the side surface of the groove body 47 on the side opposite to the overflow groove 49. The return-side pipe 41 on the upstream side is provided with a filter 11 201109478 6 5. The return-side pipe 41 on the upstream side of the filter 65 is provided with a pump 64. By driving the pump 64 and the above The robbery of 4 driving Pu 63' is circulated between the plating tank 13 and the tank 1 5 . The liquid separator β ζ 'filters the plating solution and separates various foreign materials in the plating solution from the forging liquid. 13 is the ratio of S to his groove 15 (the volume of the plating tank 13: the volume of his groove 15) is 〇. ι:1~3〇.ι .丄 is better, 〇· 3:1~1〇:1 More preferably. The grain product of the ore tank 13 is less than 0.1 times for the valley product of the tank, and the size of the groove 15 is too large and not true - on the other hand, the plating tank 13 The volume of grain in the tank 15 exceeds 3, and there is a case where the oxygen storage in the tank is insufficient in the adjustment capacity of the tank 15. The circulation amount (rotation) is the speed of the circulation (liters per minute) x60 (minutes/time) King Bath set (liters) calculation, for the whole bath · t n. A; fe (the total amount of plating solution by the % plating device) to 5~1〇〇, to 1〇~8〇10 production t If the amount of sputum is less than 1 〇 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The pump or a lot of circulating pumps are used as a plating solution, for example, a copper sulfate bond is used to add a copper source to a copper source, and the copper is added to the copper ore liquid, and the liquid can be used as a sulphuric acid. The steel plating is referred to as a brightener=species additive. The additive may, for example, be an additive. The organic sulfur-adding organic compound such as a promoter or an inhibitor of the hydrazine organic A softener may, for example, be a nitrogen-containing organic compound. The compound containing 3 oxygen, etc., and the compound of the compound, can be exemplified /, and the sulfur-containing organic b is selected from the sulfur-based compounds of the following general formulae (1) to (4). 12 201109478 • H-S - (CH2 ) a—(〇)b—s〇3M d)

^ —(CH2)a—(〇)b—SO3M (S)c—(CH2)a—(0)b—S03M (2) R1\ S—(CHs)il—(CH〇H)Guang (CH2)e— (9) b—S〇3M (3) s I(10), prepared „ (wherein R&gt;, R2 and R3 are respectively alkyl groups having a carbon number, M is a hydrogen atom or a metal test, and a is an integer representing b, b. In addition, as a nitrogen-containing organic compound, a conventional one may be used, and, for example, a tertiary amine compound, a tertiary compound, or the like may be used. As the oxygen-containing organic compound, a conventional one may be used. For example, a polyether compound such as polyethylene glycol may be used. Each component of the copper sulfate ore solution may be supplemented with a replenishing liquid or the like as needed by continuously performing electric forging of copper. The copper plating may be continuously performed. Further, when a soluble anode is used, the copper ions may be supplemented by the soluble anode. Further, when an insoluble anode is used, a tank capable of supplying copper ions may be additionally provided in addition to the ore tank 3, The groove is used to deposit copper ions in the tank. Next, the operation of the plating apparatus 本 of the present embodiment will be described. First, in the tank of the ore tank 13 during the construction of the bath The body 47 and the overflow tank 49, and the first space 17 and the second space 19 of the 201109478 tank 15 retain a quantitative liquid amount. Then, the driving pump 63 and the pump 64 are used to make the plating solution in the plating tank. 13 circulates with the tank 15. The level of the overflow tank 49 and the second space 19 can be adjusted by controlling the driving or stopping of the pump 63 and the pump. In this state, the cathode 57 of the object is impregnated. The plating bath in the tank body 4? is energized between the anode crucible and the yin wood. Thereby, the copper is bonded by the mineral. When the forged material is bonded, the other is exchanged for copper plating. When the pump 6 6 is driven, the plating solution is supplied to the tank body 47 through the return side dispenser 41. The plating solution is supplied to the tank body ', and the plating solution having the same amount as the supplied liquid passes over the tank. The upper edge portion 53 of the side wall 51 of the main body 47 flows into the overflow groove 4g. Further, when the pump 63 is driven, the shovel in the overflow groove 49 and the groove main body 47 passes through the delivery side pipe 29 to the space 17 of the groove 15 Supply. In the plating solution, 'causes are caused by, for example, the danger of k 7 1_ = pole 57 detachment or the residue generated at the soluble anode. The foreign matter floating in the space of the child, etc., in the second space of the groove 15, the density of the indium is larger than that of the plating solution; the face _ 叼 scraping particles will settle and precipitate at the bottom of the first space 丨7. The side pipe 29 supplies _ to the i-th space 17 and the same amount of liquid as supplied (4) flows into the second space 1 through the upper edge 2 3 of the i-th partition wall. The plating liquid which flows into the second space 19 into the cage 9 Bn After the second air flow in the second space, the liquid is left in the liquid level of the second space 19. The plating liquid is exposed to the air and is exposed to the air, and the plating is adjusted. liquid

Dissolved oxygen concentration. Specifically, when the soluble anode 55 is used as the A 1 hummer anode, oxygen in the air is taken in during plating, and the plating solution is taken in the milk to suppress the dissolution of the plating solution 14 201109478 The concentration is lowered. On the other hand, when an insoluble anode is used as the anode, oxygen is appropriately released from the plating solution into the air during plating, and an increase in the dissolved oxygen concentration of the plating solution can be suppressed. The dissolved oxygen concentration can be adjusted by changing the time in which the plating solution flows down the air, and the surface area of contact with the air when flowing in the air. The time during which the plating solution flows down the air and the surface area of contact with the air when flowing down the air can change the plating solution overflow by changing, for example, the distance between the upper edge portion 23 of the first partition wall 21 and the liquid level in the second space 19. The width of the upper edge portion 23 is adjusted. The concentration of dissolved oxygen in the plating solution of the tank body 47 of the plating tank 13 is preferably 4 to 2 mg/liter. When the dissolved oxygen concentration is less than 4 mg/liter or more than 2 〇mg/liter, the plating quality is deteriorated. Specifically, for example, the coating properties such as the elongation of the plating film and the tensile strength are lowered, or the uniformity (TP) of the through holes of the printed circuit board is lowered, and the hole filling property of the via hole is decreased (the amount of the depression is increased) The situation. In the present embodiment, since the plating solution overflows from the first space 17 and flows into the second space 179 as described above, air is entangled in the plating solution by the flow of the plating liquid thus overflowed. Thereby, the dissolved oxygen concentration in the plating solution can be made close to the saturated oxygen concentration. Air is mainly composed of oxygen (about 20%) and nitrogen (about 80%). Further, as a reference, for example, the saturated dissolved oxygen concentration of water of 25 t is about 8. The concentration of dissolved oxygen in the lmg/liter bismuth plating solution is smaller than the above preferred range (4 to 20 mg/liter). The oxygen in the air is dissolved in the plating solution by flowing down, so that the dissolved oxygen concentration in the plating solution is close to the saturated dissolved oxygen concentration. Thereby, the dissolved oxygen concentration in the plating solution can be easily adjusted to the above preferred range. On the other hand, when the concentration of dissolved oxygen in the plating solution is larger than the above-mentioned preferred range of 15 201109478, a part of the oxygen dissolved in the plating solution is caused by the overflow of the plating solution and is affected by the influence of nitrogen in the air. The ground release is in the air, so that the oxygen concentration in the plating solution is close to the saturated dissolved oxygen concentration. Thereby, the dissolved oxygen concentration in the clock solution can be adjusted to the above preferred range. The distance (difference) between the upper edge portion 23 of the first partition wall 21 and the plating liquid surface in the second space 19 is not particularly limited, and the point at which the dissolved oxygen concentration can be effectively adjusted is preferably 1 cm or more, and is 15 cm. The above is better. Further, in order to avoid an excessively large difference in the size of the groove 15 thereof, it is preferable that it is less than or equal to 0 cm. Further, in the present embodiment, a partition wall is provided in the other groove 15 and the plating solution is only once overflowed. However, as described later, by providing a plurality of partition walls in the tank body, the groove 15 is provided. The number of overflows is plural. The point at which the adjustment efficiency of the dissolved oxygen concentration can be increased is that the number of overflows of the tank 15 is preferably two or more. Further, in order to prevent the size of the groove 15 from becoming too large, the number of overflows is preferably 5 or less. As described above, in the first embodiment, the portion of the ore liquid that exceeds the predetermined height flows into the second space 19 from the first space 17, and the portion below the predetermined height stays in the first space I. Inside. Therefore, the metal particles remaining in the plating solution of the first space 17 can be settled below the i-th space 17. As long as the metal particles are settled and concentrated under the first space 17 in this manner, the metal particles can be periodically recovered by performing a recovery means to effectively remove the metal particles in the plating solution. Thereby, in the plating apparatus 11, the exchange frequency of the filter 65 can be lowered, and the filter 65 can be omitted even in the case. Further, a portion of the plating liquid in the first space 17 that exceeds the predetermined height flows into the second space 19 so that the second space 16 201109478 1 9 flows down in the air, that is, by flowing the mineral liquid. Exposure to air adjusts the dissolved oxygen concentration of the bath. Therefore, according to the first embodiment, the concentration of dissolved oxygen in the money liquid can be adjusted, and the cost due to the exchange filter can be reduced. Specifically, when a soluble anode is used as the anode, since oxygen in the air is taken into the plating solution during plating, the decrease in the dissolved oxygen concentration of the plating solution can be suppressed. On the other hand, when an insoluble anode is used as the anode, oxygen is released into the air by the plating solution during plating, so that an increase in the dissolved oxygen concentration of the plating solution can be suppressed. Further, in the first embodiment, the edge portion 23 is only laterally extended to the second space 19. Further, the tip end portion has a protruding piece 27 spaced apart from the side surface of the first partition wall 21. Therefore, by the first! The forging liquid that has flowed into the second space 19 in the space 17 is guided to the leading end portion along the protruding piece 27, and the front end portion of the leading end portion is opened and released into the air by the protruding piece 27. Therefore, in the first embodiment, it is possible to suppress the plating solution from flowing down along the side surface of the first partition wall 21. Thereby, since the contact surface # with air at the time of flowing the plating liquid can be increased, the dissolved oxygen concentration of the plating solution can be more effectively adjusted. <Second Embodiment> Fig. 4 is a view showing a configuration of a groove 15 of a plating apparatus according to a second embodiment of the present invention. In the second embodiment, the structure of the second chamber 17 of the groove 15 is The same components as those of the first embodiment are denoted by the same reference numerals, and the detailed description thereof will be omitted. As shown in Fig. 4, the groove 15 is provided with the groove body 20 and the first portion. The partition wall 21, 17 201109478 has a second partition wall 35. The second partition wall 35 has a substantially rectangular shape and is vertically erected from the bottom surface of the tank main body 20. The second partition wall 35 divides the inside of the first partition 17 into two spaces. The space on the side is provided by the transport side; the supply port 29a of 29 supplies the supply space 33 of the plating solution, and the space 'on the other side is located on the downstream side of the supply space 33, and the settling space 31 for sedimenting the metal particles 32 in the plating solution. The second partition wall 35 has a plurality of communication ports that communicate the settling space 31 and the supply space 33. The communication ports are provided at a predetermined height, that is, the height of the upper edge portion 23 of the first partition wall 21 is lower than that. In the space 17, the mineral liquid can be supplied through the plurality of communication ports The space 33 is moved to the settling space 31. As the second partition wall 35', for example, a metal plate or a resin plate in which a plurality of through holes are arranged at substantially regular intervals can be used. The communication port is adjusted to a size at which the metal particles can be transmitted. In the second embodiment, the first space 17 is divided into the sedimentation space 31 and the supply space 33 by the second partition wall 35, and the plating solution is supplied to the supply space 33 by the supply port 2 9 a of the transport-side pipe 2 9. Therefore, even in the supply The plating solution stored in the supply space 33 during the plating solution flows, and the flow is not easily transmitted to the sedimentation space 31. Therefore, the metal particles 32 can be made more effective than when the second partition 35 is not provided in the first space 17 In addition, in the second embodiment, the second partition wall 35 has a plurality of communication ports that are provided below the predetermined height and that communicate the settling space 31 and the supply space 33. Therefore, the plating liquid supplied to the supply space 33 is The plurality of communication ports of the second partition 35 can be dispersed and moved to the settling space 31. By dispersing the plating solution into the settling space 31 through the plurality of communication ports, the shovel of the storage space 31 can be suppressed. In addition, the other configurations, operations, and effects are omitted, but the same as the first embodiment described above. <Third Embodiment> FIG. 5 shows a tank 15 of the plating apparatus 11 according to the third embodiment of the present invention. In the third embodiment, the structure of the first space 17 of the groove 15 is different from that of the first embodiment and the second embodiment. Further, the same components as those of the first embodiment are given the same. The detailed description of the reference numerals is omitted. As shown in Fig. 5, the other groove body 15 and the first partition wall 21' further have a second partition wall 35. The second partition wall 35 has a substantially rectangular shape, and In the same manner as in the second embodiment, the bottom surface of the groove body 20 is erected upward. The second partition wall 3 5 ' divides the inside of the first space 17 into the supply space 33 and the settling space 3. The second partition wall 35 of the third embodiment is not provided with a plurality of communication ports. In the third embodiment, the upper edge portion 35a of the second partition wall 35 is located below the predetermined height. Therefore, the height of the upper edge portion 35a of the second partition wall 35 is located at a level higher than that of the plating liquid remaining in the settling space 31. Below the liquid level. Thereby, the plating liquid ' in the first space 17 can be moved from the supply space 33 to the sedimentation space 31 beyond the upper edge portion 35a of the second partition wall 35. Therefore, in the third embodiment, since the second barrier is provided, the flow of the money liquid supplied from the supply port 29a to the supply space 33 is less likely to be transmitted to the sedimentation space 31. Further, since the plating liquid flows into the sedimentation space 31 from the supply space 33 through the upper edge portion 35a of the second partition wall π, it is possible to suppress the volume of the metal particles 32 under the space of the settlement 19 201109478. In the case of the first embodiment, the configuration of the electric clock device 11 according to the fourth embodiment of the present invention is shown in Fig. 6 . In the fourth embodiment, the re-supply pipe 43 is different from the first embodiment. The same components as those in the third embodiment are denoted by the same reference numerals, and the detailed description thereof will be omitted. In the fourth embodiment, the plating apparatus π further includes a resupply device for returning the plating solution discharged from the tank 15 to the first space 17. The one end 43a of the resupply pipe 43 is connected to The second space 19 at the lower portion of the side portion of the tank body 20 communicates with each other. The other end 43b is disposed at the upper portion of the first space 17. The pump 66 and the filter 68 are provided in the resupply pipe 43. The embodiment will be in his slot 15 One of the two key liquids of the space can be supplied to the first space 17 again through the resupply pipe 43 before returning to the plating tank 13. The foreign matter in the plating solution can be further effectively removed. The fifth embodiment is the same as the above-described first embodiment. Fig. 7 is a view showing the configuration of the plating apparatus 11 according to the fifth embodiment of the present invention. The point where the underflow partition 45 is disposed in the space 19 is different from that of the first embodiment. Here, the same components as those of the first embodiment 20 201109478 are given the same effect as the same. The detailed description is omitted. As shown in Fig. 7, in the fifth sinus sinus, the second space 19 is located on the downstream side of the first space 177, and the burdock is improved by Jiy. a plate 45. The partition plate 45 is disposed in the second space 19, and a gap is formed between the lower end side of the partition plate 45 and the bottom side of the groove body 2〇, and the second space is formed above the slit. 19 is a plate-like body that is disposed in two regions of the upstream side region and the downstream side region. The money liquid that has flowed into the second space 19 from the i-th space 17 passes through the gap in the second space 19 when the upstream target 丨丨r5&quot; teaches the 7~ 恻&amp; field to move to the downstream side region. In the second space 19, the liquid can be stirred more uniformly. Further, other configurations, operations, and effects will be omitted, but the same as the above-described first embodiment. <Sixth embodiment> Figs. 8A and 8B FIG. 8A is a view showing a part of the plating tank 13 of the plating apparatus 11 according to the sixth embodiment of the present invention, and FIG. 8A is a view of a part of the plating tank 13 as viewed from the side, and FIG. 8B is viewed from above. Picture. In the sixth embodiment, the structure of the overflow groove 49 of the plating tank 3 is different from that of the first embodiment. The same components as those in the i-th embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. As shown in Fig. 8A and Fig. 8B, in the sixth embodiment, the overflow groove 49' of the plating tank 13 has an upstream side space 71 and a downstream side space 73 located on the downstream side of the upstream side space 71. The overflow tank 49 is composed of two grooves (the first groove 75 and the second groove 7 7). The upstream space 71 is a space surrounded by the first groove 75 and the side wall 51 of the groove body 47, and the downstream side space 21 201109478 is a space surrounded by the second groove 77 and the side wall 51 of the groove body 47. Among the upper edge portion 53 of the side wall 51 of the groove main body 47, the upper edge portion of the fifth portion, and the upper edge portion of the second groove 77, the second groove 7 is the highest, and the second is the lowest. As shown in Fig. 8B, a pair of overflow portions 81 are formed in the upper edge portion of the first groove 75. The overflow portion 8 is such that the plating solution overflows from the second groove 77' to be lower than the other portions. In the second slot? The bottom side of the seventh side is provided with a through port 79 that connects the piping side piping 29. As a result, the plating solution flows into the upstream side space 71 of the first groove 75 from the upper edge portion 53 of the side wall 51 of the overflow tank body 47, and further overflows the upper edge portion of the i-th groove 75 into the downstream side space 73 of the second groove 77. Through the through port? 9 Flows into the delivery side piping 29. As described above, in the sixth embodiment, the plating solution is in the air and has a structure of 2 persons. Therefore, not only in the tank 15, but also in the overflow tank 49 of the ore tank 13, the adjustment of the dissolved oxygen concentration in the plating solution can be performed. In particular, in the sixth embodiment, the shovel flows into the downstream side space 73 from the upstream side space 71 by making the drop of the liquid level of the upper edge portion of the first groove 75 to the second groove 77 larger than 1 〇 cii or more. The dissolved oxygen concentration is more effectively adjusted when flowing down in the air. Further, the upper edge portion 53 of the side wall 51 of the groove body 47 preferably has the same protruding piece as that of Fig. 2 . Similarly, the upper edge portion of the first groove 75 preferably has the same protruding piece as that shown in Fig. 2 . When the upper edge portion has the protruding piece, the plating liquid that has flowed into the first groove 75 from the groove main body 47 and the plating liquid that has flowed into the second groove 77 from the first groove 75 are guided to the tip end portion along the protruding piece, and the tip end is provided. The front end of the portion is separated from the air by the protruding piece 27. Therefore, it is possible to suppress the plating solution from flowing down along the side surface of the groove body or the side surface of the first groove 75. Borrowing 22 201109478, since the contact area with the air when the plating solution flows down can be increased, the concentration of the dissolved oxygen in the plating solution can be more effectively adjusted. Further, the other configurations, operations, and effects will be omitted, but are the same as those in the first embodiment. (Seventh Embodiment) Figs. 9A and 9B are views showing a configuration of a part of a plating tank 13 of a plating apparatus 11 according to a seventh embodiment of the present invention, and Fig. 9A shows a part of the plating tank 13 by a side. As seen from the figure, Fig. 9B is a view from the top. In the seventh embodiment, the structure of the overflow groove 49 of the plating tank 13 is different from that of the first embodiment. The structure of the first groove 75 is different from that of the sixth embodiment. The same components as those in the first embodiment and the sixth embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. As shown in Fig. 9A and Fig. 9B, in the seventh embodiment, the first groove 75 has a through hole 85 at its bottom surface, and the discharge pipe 83 is connected to each of the through holes 85. The plating solution in the upstream side space (71) passes through the discharge tubes (83), and flows into the downstream side space (73). The bottom of the first groove 753 is disposed above the bottom of the second groove 77. The discharge tube 83 can be omitted. The other configurations, operations, and effects are omitted, but are the same as those in the first embodiment. <Eighth Embodiment> Fig. 10 is a view showing the configuration of a plating apparatus J i according to an eighth embodiment of the present invention. In the eighth embodiment, the point that the number of overflows of the groove 15 is two - is different from that of the first embodiment. The same components as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. 23 201109478 As shown in Fig. 10, in the eighth embodiment, the groove 15 further has a third partition wall 91. Pick up the goods. * /, '^ The third partition wall 91' is slightly rectangular in shape, and the bottom surface of the body 20 is upwardly a &lt; square fork. The inside of the groove 15 is formed by the third partition 91 into a second space 19 and a third airtight portion 93 located on the downstream side of the second space 19. The burial ι·ι* ^ work is a more effective adjustment of the dissolved oxygen concentration of the plating solution. In the eighth embodiment, the second space 19 and the third space 93 on the downstream side of the first space 17 in which the metal particles have settled further include the underflow partition plate 45. Similarly to the fifth embodiment of Fig. 7, the partition plates 45 are provided in the second space 19 and the third space 93, and gaps are provided between the lower end sides of the partition plates c and the bottom surfaces of the groove bodies 2, respectively. At the same time, the second space 19 is partitioned into two regions of the upstream side and the downstream side, and the third space 93 is partitioned into the upstream side and the downstream side. Plates arranged regionally. Therefore, the plating solution that has flowed into the second space 19 from the first space 17 passes through the slit when it is moved from the upstream side region to the downstream side region in the second space 19. The plating solution that has flowed into the third space 93 from the second space 19 passes through the slit when moving from the upstream side region to the downstream side region in the third space 93, so that the second space 19 and the third space can be used. The recording liquid of 93 is more uniformly stirred. The upper edge portion 24' of the third partition wall 91 has the same structure as the upper edge portion 23 of the first partition wall 21. In other words, the upper edge portion 24 of the third partition wall 91 has the protruding piece 27 as the upper edge portion 23 of the first partition wall 21, so that the plating liquid flows into the third space 93 from the second space 19, along the protruding piece 27 It is guided to its tip end, and is separated from the protruding piece 27 by the front end of its tip end and placed in the air. Therefore, 24 201109478 can suppress the flow of the key liquid along the side of the third partition wall 91. Thereby, since the contact area with the air when the plating solution flows down can be increased, the dissolved oxygen concentration of the ore solution can be more effectively adjusted. Further, the other configurations, operations, and effects are omitted, but are the same as those in the first embodiment. <Ninth embodiment> Figs. 11A and 11B are views showing the first partition wall 21 of the other tank of the plating apparatus according to the ninth embodiment. In the ninth embodiment, instead of the upper edge portion 23 of the partition wall 21, the plating solution overflowing liquid of the embodiment is passed through the through hole 95 provided at the predetermined height of the first partition wall 21, and the first space 17 is provided. The structure that flows into the second space 19. In the ninth embodiment, when the plating solution flows into the second space 19 from the i-th space 17, it may flow down the side of the first 隔1 partition 21, but only along the first

Adjust the dissolved oxygen concentration of the plating solution.

The first embodiment is the same. &lt;Other Embodiments&gt; 25 201109478 The present invention is not limited to the above-described embodiments, and various modifications and improvements can be made without departing from the scope of the invention. For example, in the above embodiments, the case where the mineral is subjected to mineral ore is described as an example. The present invention may be applied to other electroplating such as electroless nickel or electric gold in addition to electroplating copper. In addition, in the above embodiment, the case where the other side of the tank 15 is divided into two or two spaces by the partition wall will be described as an example, but the tank 5 may be divided into four or more spaces. The form resupply pipe is provided in an electric clock device of another embodiment. The plating apparatus according to each of the above embodiments and the plating method using the same are suitable for use in forming a wiring pattern or the like on a mineral such as a printed circuit board or a wafer, but are not limited to such applications. The above embodiments are organized as follows. The electroplating device of the above-mentioned actual form includes: a plating tank for storing the plating solution; The black plated groove is a groove of the body and the plating solution is grooved between the plating tank and the plating tank. The above-mentioned tank ' has a first space in its interior; and is located at the same time! The space in which the space is the second space on the downstream side is the portion of the liquid recording in the first space, and the portion exceeding the intermediate level flows into the second space from the first space, and the key liquid is in the 兮笸9 The screaming, dying, and the production of the air in the space of the second space, the composition of the plating liquid exceeding the predetermined height will be entered into the second space by the first work space. The portion below the predetermined height stays in the first space, so that the metal particle sink 26 201109478 staying in the plating solution in the first space can be lowered below the first $. As long as the metal particles are deposited in the lower concentration 1 of the second space, the metal particles in the plating solution can be effectively removed by performing the recovery means to return the metal particles. Thereby, in the plating apparatus, the frequency of exchange of the filter can be reduced. Depending on the case, the filter can be omitted. Further, 'the portion of the key liquid in the first space that exceeds the predetermined height flows into the second space, and the air t in the second space flows, that is, the liquid state (4) is exposed to the air to adjust the dissolution of the ore solution. The oxygen concentration is 0 or more. According to the above (4), the dissolved oxygen of the ore solution can be adjusted, and the cost due to the exchange of the filter can be reduced. Specifically, as the above-described structure of the above-described groove, for example, the first i-space and the second space are spaced apart from each other in the vertical direction: a partition wall, and the ore liquid in the i-th space overflows in the partition wall The structure in which the edge of the predetermined height is above the edge and flows into the second space. In the above-described electric ore device, the upper edge portion of the partition wall has a protruding piece extending toward the second space side, and the protruding piece preferably has a tip end separated from a side surface of the partition wall. In this configuration, the plating solution that has flowed into the second space from the first space is guided to the air from the front end of the apex. In other words, when the protruding piece is not provided at the upper edge portion, the plating liquid "catched into the second space by the second space easily contacts the side surface of the partition wall and flows down along the side, but this configuration suppresses the mineral liquid along the side. The side of the next wall flows down. Since this can increase the contact area with the air when the ore liquid flows down, it is possible to effectively carry out the dissolved oxygen concentration of the liquid. Further, in the above-described plating apparatus, the protruding piece has a lateral portion extending in the lateral direction with respect to the second intermediate side and a longitudinal portion of the leading end of the lateral portion. The leading end of the vertical portion is separated from the side surface of the partition wall. With this configuration, the money flowing into the second space from the i-th space is guided to the tip end portion by the lateral portion, and the distance from the side surface of the partition wall is increased: : The vertical portion of the partition portion flows downward, so that the vertical portion flows downward. It can further inhibit the side of the partition wall from flowing down. In addition, in the above-described electric ore device, the above-described tank pair may have a structure in which the plating solution in the first space flows into the second space through a through port located at the predetermined height of the partition wall. Further, the plating apparatus further includes a transport-side pipe for transporting the money liquid from the mineral deposit tank to the tank, and the transport-side pipe has a supply port for supplying the plating solution in the 帛i space. Preferably, the supply port is located below the predetermined height. According to this configuration, when the supply port of the transport-side pipe is located below the predetermined height, that is, below the liquid level of the scooping liquid stored in the space of the crucible 1, the supply port is supplied with the mineral liquid in the i-th space. It can be directly supplied to the liquid stored in the ore liquid in the i-th space. In this way, the case where the plating solution is directly supplied to the plating solution in the i-th space can be reduced as compared with the case where the mineral liquid which is discharged into the air from the supply port falls into the liquid level of the mineral liquid stored in the first space. The impact on the bell of the first space. Thereby, the flow of the plating solution retained in the i-th space can be suppressed, and the metal particles τ can be effectively settled in the first space. In addition, in the case where the discharge direction of the plating solution of the supply port is directed toward the inner side surface of the other groove, for example, the flow of the plating liquid stored in the second space can be suppressed as compared with the case where the protruding direction is downward. Especially the flow of the bell liquid on the lower side. Thereby, since the metal particles whose precipitation in the i-th space is suppressed can be suppressed from being rolled up again, it is possible to suppress the sedimentation of the metal particles in the first space. Further, the electric iron device may further include a transport side pipe that transports the plating solution to the other tank by the key groove, and the partition wall first partition wall 'the other groove' has a second partition wall The inner π-knife of the first space is a settling space for causing the metal particles in the plating solution to settle, and the supply space for supplying the plating solution is supplied from the supply port of the transport-side pipe to the upstream side. The structure is extended in the up and down direction. 'W, rrv work buckle sighs &quot; U "bull - the king of the Han supply space 5 due to Dong Shi supply · private (Λ? pq丄,., eight ''Ό two supply by the supply side of the supply side of the mine Therefore, even if the liquid in the supply chain is deflated and the 镀β 艰 吟 吟 吟 吟 吟 吟 吟 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the case where the second partition wall is provided, it is possible to make the metal particles more effectively settle. Further, the second partition wall is provided below the predetermined height, and has a plurality of communication ports that communicate with the above-mentioned supply space. At the time, the liquid is supplied to the supply space. The liquid is dispersed and moved to the settling space through the plurality of communication ports of the second partition wall. Thus, ± 丄 丄 &amp; is dispersed into the settlement space by passing the ore through a plurality of communication ports It is possible to suppress the flow of the plating solution stored in the sedimentation space. Further, when the upper edge portion of the second 卩3 电 阳 阳! is located at the predetermined height or below the predetermined height, 卞 second The height of the upper edge of the next wall is presented with 29 201109478 The liquid level of the plating solution remaining in the settling space is the same or less. Therefore, since the liquid level of the plating solution in the settling space is substantially the same height as the liquid level of the key liquid in the supply space, the plating space flows into the settling space from the supply space. The liquid can alleviate the impact during the inflow. Since the metal particles in the settling space can be suppressed from being rolled up again, it is possible to suppress the sedimentation of the metal particles in the sedimentation space from being hindered. Further, the above plating apparatus includes: The groove feed back the return-side pipe of the plating solution, and when the plating solution discharged from the other tank is returned to the re-supply pipe of the second space, before a part of the plating solution in the groove is returned to the plating tank The first space can be re-supplied by the re-supply pipe. The τ can more effectively separate the foreign matter in the plating solution. Further, the step further includes a mechanical mixer that is disposed on the downstream side of the first space. When the metal particles are sedimented between the first and second sides, the ore liquid is supplied to the space on the downstream side by the above-mentioned mechanical money mixing machine, whereby the dissolved oxygen concentration of the plating solution can be made slightly. The whole of the ～ W W : 艰 艰 艰 艰 : : : 艰 艰 艰 艰 艰 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四The tank has an upstream side ♦ 〇Λ ^ under the inside, 1 and 2 and a downstream side space which is downstream of the upstream side space, and the plating side space flows into the lower second space in the second upstream space. The structure of the flow down. The π is called, not only the groove, but also the adjustment of the concentration of the oxygen θ overflow groove in the plating bath. The space λ L i 戮 由 由 上述 上述 上述 上述 二 二Adjustment between the time of the machine ^ 30 201109478 Further, the upper edge portion of the groove body has a protruding piece extending toward the overflow groove side, and the protruding piece has a front end of the groove body and a front end of the groove body The plating liquid flowing into the overflow tank of the groove body is guided to the tip end portion along the protruding piece, and is discharged from the protruding piece to the air by the front end of the tip end portion. Therefore, with this configuration, it is possible to suppress the plating solution from flowing down along the side surface of the groove body. Thereby, since the contact area with the air at the time of flowing the plating solution can be increased, the adjustment of the dissolved oxygen concentration in the plating solution can be performed more effectively. In the second space, the drop in the air flowing through the plating solution is preferably the above. By adjusting the above-described drop to 10 〇 cm or more, the concentration of dissolved oxygen in the plating solution in the other bath can be more effectively performed. In the plating method of the above embodiment, a plating bath including a plating bath is used, and an electroplating apparatus for circulating the plating solution between the plating tank and the plating tank is used. . The above-mentioned slot has a first space inside and is located at the same time! The space is the second space on the downstream side. In this method, the plating solution is stored in the first space to a predetermined height, and the metal particles in the plating solution are deposited below the ith $. Further, in the method of the present invention, the enthalpy exceeding the predetermined degree of the plating solution in the first space flows into the second space, and the dissolved oxygen concentration of the plating solution is adjusted in the second space. . Thereby, the concentration of dissolved oxygen in the plating solution can be adjusted, and the metal particles in the plating solution can be effectively removed. The electric ore device and the electroplating method according to the above embodiment are

It is used in copper plating, and it is particularly suitable to use a sulfur-containing compound as a pre-shell agent. Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples. <Example 1> Using a plating apparatus, the following .+, electric clock copper. The test piece is placed on the object to be pressed (sample material 8). In the plating apparatus 11, the plating plating apparatus is the same as the structure shown in Fig. 1. The groove 15 is in the groove body 20, and the first partition 21 and the third partition 91 are divided into the first partition 21 and the third partition 91. The structure of the three spaces of the 1st work room 17, the second space 19, and the younger work room 9 3 . The plating solution overflows the first partition 9 and the upper edge of the partition 21 flows into the second space 19 from the first space 17, overflowing the upper edge of the q@n, a brother 3 partition 91, and flows in from the second space 19 The third space 9 3. In the whistle 9 * Λ ? p 1 1 rv π second space 19 is provided with an underflow partition 45. Further, in the samples No 1 ς Q .. m , . , 5 8 ', the partition walls 21 and 91 were removed from the other grooves 15 of the plating apparatus 11 shown in Fig. 12 . The structure of the upper edge portion of the first partition wall 21 and the third partition wall 91 is as shown in Table 2, which will be described later, and the material N〇.4 is the structure a (the structure shown in Fig. 2D). 3 is a structure b (the structure shown in Fig. 2E). The difference between the upper edge of the first partition wall 21 and the third partition wall 91 to the liquid surface of the bell liquid is 5 cm, which is shown in Table 2, which will be described later. Three conditions of cm and 20 cm. The mineral (cathode), the stainless steel plate, and the substrate with the via hole (the printed circuit board with the blind via). The opening diameter of the via hole of the substrate is 100; / m, conduction The depth of the hole is 75 &quot; m. Other copper plating conditions are as follows. The bath amount of the plating tank 13 (total of the bath volume of the tank body 47 and the overflow tank 49): 4300 liters 32 201109478 The bath volume of the tank 15 (in The total amount of baths of the first space π, the second space 19, and the third space 93) _· 8 〇〇 liter bath amount: 51 0 0 liter plating bath: copper sulfate ore (containing copper sulfate pentahydrate and 200 g/ L, sulfuric acid 50 g/L 'and vaporization ion 5 〇mg/L) Additive added to the plating solution: "The cycle speed of THRU-CUP EVF-Tj mineral liquid manufactured by Shangcun Industrial Co., Ltd.: 860 liter / liter Pole: Soluble anode (in a titanium box containing phosphor bronze balls, this is placed in a polypropylene anode bag). The plated material is electroplated with copper under the above conditions, and the dissolved oxygen/initiality and the film properties are evaluated. The amount of depression of the via hole. The evaluation of the physical properties (elongation and tensile strength) of the film is applied to the above-mentioned stainless steel plate of the object to be plated with a bond copper of 5 〇 m. The evaluation of the amount of depression of the via hole is used. Applying a copper plate of 20 μm to the above-mentioned circuit board with the via hole of the object to be plated. In the first embodiment, the stainless steel plate is subjected to the prior treatment, electroplating copper treatment, and the following steps 1 to 8. Post-treatment. Step 1: Acid-washing detergent (MSc_3 a, manufactured by Uemura Kogyo Co., Ltd.) Step 2: Soup washing Step 3: Water washing Step 4: Pickling Step 5: Water washing step 6 • Electro-mineral copper Step 7: Washing 201109478 Step 8: Drying, 'For the substrate with the via hole, after the conventional degumming, enamel treatment and electroless copper plating (〇. 3 μ m), the previous treatment and plating are carried out in the same order as the above steps 1 to 8. Copper treatment and post-treatment. The conditions for electroplating copper of 1 are shown in Table 1. The treatment temperature of the copper (the temperature of the plating solution) was 25 ° C. Furthermore, the unit of the cathode current density in Table 1 was A/dm 2 . [Table 1] Plate cathode current density (ASD) 1.0 1.0 plating time (minutes) 226 90~ film thickness (//m) 50 20~ The results are shown in Table 2. In addition, Table 3 shows the contents of each sample. In the test procedure, after the plating treatment of the sample No. 1 was completed, the partition wall 2 shown in Fig. 12 was attached as a tank, and the dissolved oxygen concentration was electrolyzed for 30 minutes, 60 minutes, and 90 minutes. In addition, a portion of the plating liquid supplied to the tank main body 47 through the return-side piping 41 is supplied through the piping end portion 4ic by making the flow rate of the ore of the respective nozzles 6 to the object to be plated (the cathodes 5 7) substantially constant. The dissolved oxygen concentration is measured by the dissolved oxygen of the plating solution of the valve which is omitted from the piping attached to the pipe end portion 41c of Fig. 12 . The amount of depression of the via hole is the substrate 101 with the via hole shown in FIG. 5A, and after the copper plating 1〇3 shown in FIG. 15B is applied, the copper plating 103 formed in the via hole 101c is measured. The difference between the lowest portion of the surface and the height (the dimension in the thickness direction) of the surface of the steel 1〇3 formed at the peripheral portion of the via hole 101c is obtained (Fig. 15B). Further, the base 101 of the through-hole 34 201109478 is provided with a resin layer 101a and a copper layer 101b formed on the surface of the resin layer i〇ia, and a via hole i〇lc is formed therewith. Further, the elongation and the tensile strength were measured as follows using the test piece shown in Fig. 16. That is, 'first' the stainless steel plate was subjected to 5 〇 "±5" of copper plating, and then the wrought copper layer (copper hall) was carefully peeled off from the stainless steel plate by avoiding wrinkles or scratches. After the copper box was heat-treated at 120 t for 2 hours, a test piece of the shape shown in Fig. 16 was produced by punching. The thickness of the central portion of the test piece was measured by a fluorescent X-ray film thickness meter, and the measured value was defined as the film thickness d (nm) of the test piece. Next, the distance between the chucks of the tensile tester was set to 4 〇 _, and the inner round portion of the test piece was exposed by the chuck, and the test piece was fixed with a cool head, and the test was performed at a tensile speed W. Next, 'read from the chart obtained by the test 2 pull: stress F (kgf)', the value is F (kgf) in the cross-sectional area of the test piece I:: Table, 6, 9 shows the tensile strength (kg&quot;&quot;10 The test piece is made up of a width of 1 〇mm and a film at the center of the 5th piece. The elongation, total, and dmm are measured by S. The test piece is stretched to the length of the test piece. ΛΤγ, 破破·断Μ·0, and this Δ was calculated by dividing the size (2 〇mm) of the straight portion of the center 4 of the test piece of the stretched money. 35 201109478 [Table 2] Sample No. The specification of the tank is the circulating amount of dissolved oxygen concentration mg / liter of the membrane physical permeability hole depression amount β \ Ά the partition wall elongation elongation % tensile strength kgf / mm2 1 - 10 turns 2.4 25.6 35.6 28.5 2 Yes (8) 5cm 10 turns 3.7 31.2 32.4 19.2 3 Yes (B) 20cm 10 turns 7.7 32 33.1 15.2 4 Yes (A) 10cm 10 turns 7.4 31.5 32.8 14.5 5 No 10 turns 6 32 33 15.2 6 Benefit 1 »»&gt; 10 turns 4.3 30.7 32.2 16.3 7 益#»*, 10 3.4 3.4 31.1 33.3 18.1 8 益»«»\10 2.6 31 33.3 24.4 [Table 3: Sample No. 1 Using a tank without partition (separator) to cathodic current Density 1. 〇ASD electrolysis for 3 hours. Then, the number of the steel sheets and the substrate with the via holes are recorded. 2 Electrolyze at 1.0 ASD for 24 hours using the tank shown in Fig. 14. The rust steel plate and the substrate with the via holes are subjected to chain number. 3 Electrolyze at 1.0 ASD for 24 hours using the tank shown in Fig. 14. The rust steel plate and the substrate with the via holes are subjected to chain number. 4, using the tank shown in Figure 14, electrolysis at 1.0 ASD for 24 hours. The number of clocks is given to the rust steel plate and the substrate with the via holes. 5, sample Ν〇· 4 ‘Use the tank without partition (separator) to circulate the ore liquid for 8 hours. The number of shovel is performed on the rust steel plate and the substrate with the through holes. 6 Salty, Ν〇·5 continuous 'Use the tank without partition (separator) to circulate the ore liquid for 8 hours. The 5^-' rust steel plate and the substrate with the via holes are bonded. 7 决, No. 6 continuous 'Using a tank without a partition (separator), the key liquid was electrolyzed for 8 hours. The rust steel plate and the substrate with the via holes are plated. 8 test, Μ〇·7 continuous 'Use the tank without partition (separator) to circulate the ore liquid for 8 hours. The rust steel plate and the substrate with the via holes are plated. Dissolved oxygen concentration (mg/liter) ^9 7^6 Electrolysis (minutes) 30^ 90~^ 36 201109478 From the results of sample No. 1 of Table 2, it can be seen that plating is performed using a groove in which the partition walls 21 and 91 are not provided. The low dissolved oxygen concentration of the liquid has a tendency to increase the amount of depression of the via hole. As a result of the samples No. 2 to 4, it is understood that the dissolved oxygen concentration can be extracted by overflowing the ore liquid by providing the partition walls 21 and 91 in the groove 15. Further, if the sample N〇, 3, and 4 have a drop of the plating solution of 1 〇cm or more at the time of overflow, the dissolved oxygen concentration can be remarkably increased. In the samples No. 3 and 4, even if electrolysis is performed for a long period of time, the dissolved oxygen is dissolved. The concentration did not decrease. After the plating treatment of the sample No. 4, the results of the samples ν〇·5 to 8 which were successively carried out were determined, and it was found that the partition walls 21 and 91 were removed from the other grooves 15, and the dissolved oxygen concentration decreased as the electrolysis time became longer. Increase the tendency of the via hole to be recessed. Further, as shown in Table 4, after the plating treatment of the sample Νο.丨, the partition walls 21 and 91 were electrolyzed in the other tank, and the dissolved oxygen concentration was increased over time. <Example 2> Using the plating apparatus shown in Fig. 13A and Fig. 13A, the object to be plated (sample No. 9 to 14) was subjected to electroplating copper under the following conditions. For the sample Ν〇. 12 to 14, as the other groove 15, a groove having the same partition walls 21, 9 ι as the device of Fig. 12 was used. Further, the plating tank 13 includes a tank body 47 as shown in Figs. 13A and 13β, and an overflow tank 49, and the plating liquid overflowing from the tank body 4 flows into the overflow tank 49. In the tank body 47, the plate-like objects of the cathode 57 are arranged in a horizontally arranged manner, and a plurality of anodes 55 are arranged on the upper and lower sides of the cathode 57, respectively. Further, nozzles 61 are disposed above and below the cathode 57, respectively. Each of the nozzles 61 is provided with a plurality of discharge ports (not shown) for discharging the ore liquid conveyed from the other tanks 15 through the return-side piping 41 toward the cathode 57 37 201109478 side. Further, in the "type material Νο·9 to 11', the partition walls 21 and 91 are removed from the other tank a. The difference between the upper edge portion of the first partition wall 21 and the third partition wall 91 to the plating liquid level is as follows. Three conditions of 5 cm' 1 〇 cm and - shown in Table 6 to be described later. As the object to be plated (cathode), a stainless steel plate and a substrate having a through hole are used. The inner diameter of the through hole of the substrate is 〇3. The thickness of the substrate is 1.6 mm. The conditions of other electroplated copper are as follows. The amount of bath of the plating tank 13 (total of the bath volume of the tank body 47 and the overflow tank 49): 1 000 liters of bath of the tank 15 ( The total amount of baths in the second space 17, the second space 19 and the third space 9 3): 14 〇〇 liter bath: 2400 liters of mineral liquid: copper sulfate plating solution (including copper sulfate pentahydrate and substance l〇〇) g/L, sulfuric acid · 200g / L, and vapor ion 5〇mg / L) Additive added to the mineral liquid: "THRU_CUp ETN" made by Shangcun Industrial Co., Ltd. The circulation speed of the plating solution: 3000 liters / min. Anode: Insoluble anode ( Coating the ruthenium oxide on Ti-Pt) In the second embodiment, the stainless steel plate was treated in the same manner as in the first step 1 to 8 of the first embodiment. Copper treatment and post-treatment. Further, the substrate having the through holes was subjected to conventional desmear treatment and electroless copper plating (〇. 3 #m) treatment in the same manner as in Example 1, and the same procedure as in Example 1 was carried out at 38 201109478. ~8 order of 丨, 7 &amp; accounted for 刖 刖 treatment, electroplating copper treatment and post-treatment. Further, the electroplated copper conditions of Example 2 are shown in Table 5. The electroplating copper treatment temperature (temperature of the plating solution) is 25 ° C 〇 * go * - a 〇 test the cathode current density in Table 5 is the A/dm2. [Table 5] Stainless steel plate cathode current density (ASD) 5.0 _ plating time (minutes) 45 ' film thickness (Am) 50 _ , 曲 The above conditions were used to conduct copper ore plating, and the dissolved oxygen concentration at this time was evaluated. , the physical properties of the membrane, the uniformity of the through holes (ΤΗ_τρ). The results are shown in Table 6. Further, Test (4) of each sample is shown in Table 7. The dissolved oxygen concentration is measured by the dissolved oxygen in the plating solution of the valve which is omitted from the return side pipe η installed on the downstream side of the transition gas 65 of Fig. 13 . Uniformity, which is defined as the ratio of the thickness of the ore-plated copper plated in the center of the through-hole to the thickness of the copper plated on the surface of the substrate near the through-hole. #,均性(ΤΗ-ΤΡ)' is as shown in Fig. 17, and after applying the ore copper m to the substrate 〇5 or more of the formation of the friend hole i〇5a, the key is measured in the depth direction of the through hole. The thicknesses e and f of the ore in the center portion and the thickness a to d' of the copper plating surface on the surface of the substrate in the vicinity of the through hole are obtained by substituting each value into the following formula (5). TH-TP(%)=2(e+f)/(a+b+c+d)xi〇〇(5) 39 201109478 [Table 6] Sample No. The specification of the tank is the circulating amount of dissolved oxygen concentration mg/ Liters of the physical properties TP TP % rise rate of the next drop ° / 〇 resistance tension kgf / mm2 9 no - 75 7.4 7.4 30.4 33.6 75.7 10 benefits - 75 to 23.4 23.5 37.8 70.7 11 no - 75 to 38.5 15.4 43.4 65.6 12 with (8) 5 Cm 75 to 21.5 24.5 37.5 72.5 13 Yes (8) 20cm 75 rpm 15.6 30.3 31.2 76.2 14 Yes (A) 10cm 75 rpm 18.5 30.1 32.2 75.6 [Table 7] Sample No. 9 Using grooved side plating without partition (separator) The liquid is plated on a stainless steel plate and a circuit board. 10 Continued sample No. 9, electrolysis for 3 hours. After that, the stainless steel plate and the circuit board are plated. 11 Continue the sample No. 10 and electrolyze for 3 hours. After that, the stainless steel plate and the circuit board are plated. 12 Electrolysis was carried out for 24 hours at a cathode current density of 5.0 ASD using a tank having a partition. After that, the stainless steel plate and the circuit board are plated. 13 Electrolyse for 24 hours at 5.0 ASD using a tank with a partition. After that, the stainless steel plate and the circuit board are plated. 14 Electrolyse for 24 hours at 5.0 ASD using a tank with a partition. After that, the stainless steel plate and the circuit board are plated. As a result of the sample No. 9 of Table 6, the dissolved oxygen concentration at the start of plating was 7.4 mg / liter, so that the physical property of the film was good. However, as a result of the sample Nos. 10 and 11, it was found that as the electrolysis time became longer and the dissolved oxygen concentration increased, the physical properties of the sample No. 10 after 3 hours deteriorated, and the TH-TP became relatively low. The sample No. 11 after 6 hours showed that the physical properties of the film became worse, and the TH-TP decreased to 65.6%. On the other hand, Sample Nos. 12 to 14 can suppress the increase in the concentration of dissolved oxygen by providing the partition walls 21 and 91 in the other grooves 15 to overflow the plating solution. In particular, 40 201109478 1 Ocm or more, below the above-mentioned samples, the effect of suppressing the increase in the dissolved oxygen concentration can be remarkably improved by the difference in the case where the plating solution is overflowed by the samples Νο·ΐ3, 14. No. 13, 14 ' can reduce the dissolved oxygen concentration to 2 〇 mg / liter. The film properties are also good ΤΗ TP-TP is also 75% or more. <Example 3 &gt; Electroplating of the object to be plated (Sample No. 15 to 18) was carried out under the following conditions using a plating apparatus as shown in Fig. 14 . For the samples N 〇 17 and 18, as the other grooves 15, the same grooves 21 and 9 ι as those of the device of Fig. 12 were used. Further, the plating tank 13, as shown in Fig. 14, includes a tank body 47, and an overflow tank 49, and the plating liquid overflowed from the tank body 47 flows into the overflow tank 49. Inside the groove body 47, the diaphragm 99 is divided into two spaces. As the intestinal film 99, an anode 55 is disposed in a space of "Y-9205T, a space-arranged cathode of the grid 5' of the space of the grid", and a nozzle 61 ^ nozzle 61 is disposed in the vicinity of the cathode 57. A discharge port (not shown) that ejects the plating liquid transported from the other side of the pipe through the return-side pipe 41 toward the cathode 57 is provided. Further, in the sample No. 15, 16, the partition wall 15 is used to remove the partition wall. 21, 91. The difference between the upper edge portion of the first partition wall 21 and the third partition wall 91 to the plating liquid surface is two conditions of 1 〇cm and 2 〇cin as shown in Table 9 to be described later. For the plating (cathode), a wafer having a stainless steel plate and a blind via is used. The opening diameter of the via hole in the substrate is 丨5 μm, and the depth of the via hole is 2 5 // m. The conditions are as follows: 41 201109478 The amount of bath in the plating tank 13 (total of the bath volume of the tank body 47 and the overflow tank 49): 50 liters of the bath volume of the tank 15 (in the second space 17, the second space 19 and the 3 The total amount of bath in space 93): 1 50 liter bath: 200 liters of key solution. Copper sulphate ore (containing copper sulfate and water) Material 2 QQ g / L, sulfuric acid 50g / L, and vaporization ion 50mg / L) Additive added to the menstrual fluid: "thru-cup ESA-21" plating solution manufactured by Shangcun Industrial Co., Ltd. Cycle speed: 100 liter / minute anode : Soluble anode (in the case of a titanium-containing phosphor-containing copper ball) In the third embodiment, the "stainless steel plate" was subjected to the prior treatment, the electroplating copper treatment, and the post-treatment in the same manner as in the first step of the first embodiment. Further, after the barrier layer and the seed layer were applied to the wafer by a conventional method, the prior treatment, the electroplating copper treatment, and the post treatment were carried out in the same manner as in the first embodiment. Further, the conditions for electroplating copper in Example 3 are shown in Table 8. The temperature of the electroplated steel treatment (temperature of the plating solution) was 25 °C. Further, the unit of the cathode current density in Table 8 is A/dm2.

The object to be plated was subjected to electroplating copper under the above conditions, and the concentration of dissolved oxygen 42 201109478, the physical properties of the film, and the amount of depression of the via holes were evaluated. The results are shown in Table 9. Further, the test procedure of each sample is shown in Table 10. The dissolved oxygen concentration is measured by the dissolved oxygen of the ore of the valve which is omitted from the return-side pipe 41 installed on the downstream side of the filtered gas 65 of Fig. 14 . Further, in Sample No. 15, the first space 17 of the other tank 15 was plated by air agitation using air agitation means 94 while supplying air to the plating solution. [Table 9 5 type material No. The specification of the tank dissolved oxygen concentration mg / liter of the membrane physical permeability hole recessed / / m filter partition drop air stirring elongation % tensile strength kgf / ram2 15 no - there are 3.8 30.5 33.4 7.4 m 16 None - Benefit 7.1 31.3 33.1 3.5 New product 17 Yes (8) 20cm No 7.7 30.7 32.6 2.7 White 18 Yes (A) 10cm No 7.5 31.4 32.3 3.3 White [Table 10] Sample No. 15 Use the groove without partition (separator) Electrolyzed at a cathode current density of 1.0 ASD for 24 hours. Thereafter, the stainless steel plate and the substrate are plated. 16 After the plating of sample No. 15, the stainless steel plate and the substrate were plated immediately after the filter was exchanged. 17 Electrolyze at 1.0 ASD for 24 hours using a tank with a partition. Thereafter, the stainless steel plate and the substrate are plated. 18 Electrolyze at 1.0 ASD for 24 hours using a tank with a partition. Thereafter, the stainless steel plate and the substrate are plated. The sample No. 15 of Table 9 was electrolyzed by air agitation in the first space 17 of the tank 1 5, and the dissolved oxygen concentration of the plating tank 13 was 3.8 mg/liter as shown in Table 9, and at this time, the tank was The dissolved oxygen concentration of 15 is 7.2 mg / liter. By performing the air agitation in this manner, the dissolved oxygen concentration in the other tank can be maintained in an appropriate range. However, the air agitation hinders the sedimentation of the copper particles in the space of 43 201109478, and the majority of the copper particles are confirmed in the filter 65. Since the steel particles adhering to the filter 65 are depleted of dissolved oxygen, the concentration of dissolved oxygen in the ore-growing tank is lowered, and the amount of recessed in the via hole tends to increase. As a result of the sample No. 16, the copper particles immediately after the exchange of the crucible 65 were hardly adhered, so that the dissolved oxygen concentration in the plating tank was also good, and the amount of recessed in the via hole was also small. In Sample Nos. 17, and 18, the copper particles hardly adhered to the filter 65 (in the first white state of the new product), and it was found that the copper particles effectively settled in the i-th space 17. Thus, the copper particles can be effectively separated from the plating solution while the plating solution is overflowed by the partition wall in the other tank to increase the dissolved oxygen concentration. Thereby, the dissolved oxygen concentration in the plating tank can be maintained in an appropriate range, and the amount of recessed in the via hole becomes small. &lt;Reference Example&gt; The relationship between the dissolved oxygen concentration in the plating solution, the concentration of the brightener, and the Ar value was investigated using a cyclic volt stripping method (CVS) measurement method. The method of CVS measurement is as follows. 1) Method for measuring Ar value A rotating platinum electrode as a working electrode is used as a copper rod of a counter electrode as a silver/vaporized silver double salt of a reference electrode. The bridge electrode is immersed in the plating solution to change the potential applied to the rotating platinum electrode, and the re-plating step, the stripping step, and the cleaning step are used to create a potential-current curve (Voltammogram), and the potential-current curve is used to determine the stripping step. The area is 44 201109478 (Ar value). The results shown in Tables 11 and 12 below are the results obtained by applying the above CVS measurement method by the repeated measurement of the Ar value by the above-described measurement method. 2) Measuring equipment and measuring conditions for measuring Ar value Measuring equipment: "QL-5" manufactured by ECI Corporation

Measurement conditions: Rotational platinum electrode rotation number 2500 rpm, potential pumping speed 100 mV/sec, temperature 25 ° C 3) Measurement liquid The measurement liquid was prepared as follows. A VMS 30 mL, which will be described later, was placed in a container, and a mixed solution of 30 mL of a plating solution to be measured was used as a measuring liquid. , VMS and measurement target plating solution 1. The plating solution of the test object No. 19 to 23 is as shown in Table η = as shown in Table 12 for the sample Νο. 24 to 28. In other words, in the sample Μ, the ore-like coating liquid, the shovel taken between the illustrations of the piping of the sample No. 1 of the first embodiment, which is attached to the vicinity of the pipe end portion 41c of Fig. 12, is omitted.尬X liquid 'sample N 〇. 20 measurement object plating solution, tied to

The crude M plating solution of Example 1 was applied. D — N〇. 3 In the plating process, what is the case with the same position? The plating solution of the measurement target No. 24 is carried out after the implementation of 65. The U-packing process of the U-packing process on the downstream side of the filter attached to Fig. 13 is omitted. The measurement of the plating material No. 25 taken by the valve is shown. Further, the plating solution of the object was the plating solution taken from the same position in the plating treatment of the test of Example 2. 45 201109478 In addition, the plating solution for the measurement of the sample No. 21 to 23 and the sample No. 26 to 28 is prepared in a beaker so that the dissolved oxygen concentration and the brightener concentration of the prepared measurement liquid are shown in Table 11 and Table 2. The value of each sample. The additive of the plating solution to be measured by the sample No. 19 to 23 is used as "THRU-CUP EVF-T" manufactured by Uemura Industrial Co., Ltd., and the additives of the plating solution to be measured by the sample Νο· 24~28 are used. "THRU-CUP ΕΤΝ" made by Uemura Industrial Co., Ltd. As VMS (mineral solution without added additive) 'About sample No. 19 to 23' of Table 11, copper sulfate plating solution (containing copper sulfate pentahydrate and 2 g/L, sulfuric acid 50 g/L, and chloride) Ion 5〇mg/L), regarding the sample No. 24~28 of Table 12, the use of copper sulfate ore (including copper sulfate pentahydrate and substance g/L, sulfuric acid 20 g/L, and vaporization ion 5 〇mg/L). 5) Measurement results The measurement results are shown in Table 11 and Table 12. Table 11 Sample No. Determination of plating solution additive dissolved oxygen concentration (mg/L) Brightener concentration (%) Ar value (me) 0 15 minutes 30 minutes 45 minutes after 60 minutes after the clock 75 minutes 90 minutes after the clock After 105 minutes and 120 minutes later, 19 sample No. 1 plating solution EVF-T 2.4 100 1.249 1.2 1.176 1.166 1.163 1.16 1.157 1.152 1.155 20 Sample No. 3 plating solution 7.7 100 1.142 1.143 1.144 1.145 1.144 1.144 1.144 1.142 1.142 21 Beaker Bath 8 100 1.155 1 158 1.16 1.162 1.157 1.158 1.157 1.16 1.157 22 Beaker Bath 8 200 1.211 1 ?,1?, 1.214 1.209 1.207 1.21 1.214] 1.218 1.213 23 Beaker Bath 8 20 1.11 1.104 1.111 1.Π3 1.114 1.111 1.104 1.1 Π02] Table 12 Sample No. Measurement of plating solution additive dissolved oxygen concentration (mg/L) Brightener concentration (%) Ar value (me) 0 After 15 minutes, 30 minutes, 45 minutes, and 60 minutes after the clock After 75 minutes, 90 minutes, after the clock, 105 minutes, 12 U minutes, after the clock, 24 sample No. 11 plating solution ETN 38.5 100 1.907 1.918 1.923 1.935 1.95 1.955 1.959 1.963 1.964 25 Sample No. 13 plating solution 15.6 100 1.967 1.965 1.963 1.963 1.963 1.96 5 1.966 1.964 1.967 27 Beaker Bath 8 100 1.97 1.973 1.973 1.974 1.972 1.969 1.972 1.973 1.975 Beaker Bath 8 200 2.01 2 009 2.012 2.013 2.011 2.008 2.007 2.008 2.009 2« Beaker Bath 8 20 1.899 1.89 1.892 1.892 1.892 1.9 1.9 1.898 1.893 46 201109478 The value of Ar measured, reflecting the concentration of brightener. From Table 11, for example, when the sample N 〇 2 0, 21 w, the state λαp k s bath oxygen concentration and the brightener concentration, the A value is about 1.16. For example, if the concentration of the brightener is ^ and the concentration of the second (4) is insufficient, the initial Ar value is approximately the same as the brightener concentration: clear: (sample n〇.22) is "left and right." The Ar of the sample No. 19 was reduced to approximately the same as the sample &·5. *, the quotient is shown in Table 12' as sample N. · 25, 26 ‘ dissolved oxygen concentration and light timing, k is about W. For example, even if the concentration of the light is excessively dissolved, the concentration of the brightener is insufficient. When the concentration of the brightener is insufficient, the initial AM is approximately 1,91, which is approximately the same as the sample Νο. The same 1: left: the time of the _ again 'such as the above sample N 〇 H ... not close to the sample I": / with ^ ie 'If the scanning is repeated continuously, the liquid, so as shown in Table 11, 12 - The 虱 虱 冷 冷 。 。 。 。 。 。 。 。 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气 空气

The dissolved oxygen concentration is close to that of the gold-transferred electrode, and the saturation concentration of the VMS &lt; BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the configuration of the present invention. Fig. 2A to Fig. 2F are eight ± _ ', and the knife is shown on the other side of the above-mentioned money money device. 47 201109478 A modification of the structure of the edge portion. 3A to 3E show a modification of the shape and arrangement state of the conveying-side piping, respectively. Fig. 4 is a view showing the configuration of a groove of a plating apparatus according to a second embodiment of the present invention. Fig. 5 is a view showing the configuration of a groove of a plating apparatus according to a third embodiment of the present invention. Fig. 6 is a view showing the configuration of a plating apparatus according to a fourth embodiment of the present invention. Fig. 7 is a view showing the configuration of a plating apparatus according to a fifth embodiment of the present invention. Figs. 8A and 8B are views showing the configuration of a money application tank of the plating apparatus according to the sixth embodiment of the present invention. Fig. 9A and Fig. 9B are views showing the configuration of a plating tank of a plating apparatus according to a seventh embodiment of the present invention. Fig. 10 is a view showing the configuration of a plating apparatus according to an eighth embodiment of the present invention. Fig. 11A is a view showing a first partition wall of another tank of the plating apparatus according to the ninth embodiment of the present invention, and Fig. 11B is a sectional view taken along line XIB-XIB of Fig. 11A. Fig. 12 is a view showing the configuration of a plating apparatus used in the first embodiment. Fig. 13A is a view showing a configuration of a plating apparatus used in the second embodiment, and Fig. 13B is a cross-sectional view taken along line ΧΙΙΙΒ-ΧΙΠΒ of Fig. 13A. Fig. 14 is a view showing the configuration of a plating apparatus used in the third embodiment. 48 201109478 Fig. 1A and Fig. 15B are cross-sectional views for explaining a method of measuring the amount of depression of the via hole in the embodiment 3. Fig. 16 is a plan view showing the shapes of the test pieces for measuring the elongation and the tensile strength in Examples 1 to 3. Figure 17 (throwing is a cross-sectional view for explaining the evaluation method of the uniformity of the via hole of the second embodiment). Main component symbol description] 11 ~ plating device; 15 ~ his groove; 19 ~ 2nd space; 2 Bu 1st partition; 2 4 ~ upper edge; 27 ~ protruding piece; 27b ~ vertical part; 2 9 a~ supply port ; 3 2 ~ metal particles; 35 ~ second partition; 4 b return side piping; 4 lb ~ end; 4 3 ~ re-supply pipe; 43b ~ supply pipe 43 another 45 ~ baffle; 4 9 ~ overflow trough ; 13 ~ key groove; 17 ~ first space; 20 ~ his groove body; 23 ~ upper edge; 25 ~ partition body; 27a ~ horizontal; 2 9 ~ wheel side piping; 3 pad settlement space; 3 3 ~ supply space; 35a ~ upper edge portion; 41 a ~ end portion; 41 c ~ end portion; 43a ~ one end of one end of the supply pipe 43; 47 ~ groove body; 51 ~ side wall; 49 201109478 53 ~ upper edge portion; 55 ~ anode; 5 7 ~ cathode; 59 ~ anode bag; 61 ~ nozzle; 63 ~ pump; 64 - pump; 6 5 ~ filter; 66 ~ pump; 6 8 ~ filter, 71 ~ upstream side Space; 73~ downstream side space 75~1st slot; 77~2nd slot; 7 9~through port; 8 3 ~ spout pipe; 85~through port; 9b third partition wall; 93~3rd space; 95a~ protruding piece. 95~through port; 50

Claims (1)

201109478 VII. Patent application scope: 1. An electroplating device comprising: a forging groove for storing a plating solution; and a groove thereof, which is a groove corresponding to the chain groove, and the chain liquid is in the plating groove Circulating, the other groove having a first space therein and a second space located downstream of the first space, and having a predetermined height of the mineral liquid in the second space The portion flows into the second space by the fi space. The plating solution is formed by flowing the second space in the air. 2. The plating apparatus according to the above aspect of the invention, wherein the other tank has a partition wall extending in the vertical direction so as to partition the first space from the second space, and has the first one and two The plating solution overflows in a structure in which the partition wall is located at an upper edge of the predetermined height and flows into the second space. 3. The application device of the above-mentioned (4) (4), wherein the above-mentioned other tanks are spaced apart from the first space The partition wall extending in the vertical direction from the second space has a structure in which the ore liquid having the i-th office has flowed into the second space through a member opening of the partition wall at the predetermined height. The plating apparatus according to Item 2, wherein the upper edge portion of the wall has a protruding piece extending toward the second space side. The protruding piece has a tip end separated from a side surface of the partition wall. The electroplating apparatus according to claim 4, wherein the above-mentioned 51 201109478 protruding piece has a horizontal direction extending transversely to the second space side. And the longitudinal portion extending from the ridge of the rafter in the downward direction, the side of the wall is separated from the side. The apex of the D. is separated from the above. 6. The scope of the patent application is 5-1 to 5, wherein the The plating step has a transfer side pipe to the other liquid by the plating tank, and the groove is transported to the transfer side pipe, and the supply port for the liquid is supplied to the supply port, and the supply port is provided at the predetermined height. 7. The plating solution of the electroplating apparatus according to item 6 of the patent application is provided by the above-mentioned mountain supply, the above-mentioned...: the outward direction toward the inner side of the above-mentioned groove. &amp; And wherein the step further comprises: the electric ore tube according to the item, wherein the transporting side of the money tank is transported by the bell jar to the other tank, and the first side wall is separated by And the first and second working chambers of the second space and the second partition wall of the second space are formed by η in the plating solution (the inside of the first working chamber is divided into the above, and the sedimentation of the particles is sedimentation). Space, and located in the settlement space The side 'the space is supplied from the supply port of the above-mentioned transport side pipe, and is extended in the up-and-down direction. (7) The supply of the sputum ore is the electric recording device described in Item 8 of the patent application, and the second partition wall of the sputum has And the above-mentioned second aspect of the present invention is provided in the above-mentioned second aspect, and the above-mentioned second aspect is connected to the plurality of communication ports of the above-mentioned supply space. The upper edge of the partition wall is located at the above-mentioned predetermined height or is lower than the above-mentioned predetermined high-production. The electroplating apparatus according to the above aspect of the invention, further comprising: returning the plating solution to the plating by the above-mentioned other tank a returning side piping of the groove; and a resupply pipe for returning the plating solution discharged from the other tank to the first door. 12. The electroplating device of claim 2, wherein the electroplating device further comprises: a mechanical agitator disposed on a downstream side of the i-th space. 13. The electroplating device according to claim 2, wherein the plating tank has: a tank body for storing the ore liquid; and the tank body is disposed, the plating solution of the tank body overflowing the above An overflow groove into which the upper edge of the side wall of the groove body flows, ' 一 π , the downstream side space of the downstream side of the upstream side space, and the above-mentioned ore liquid flows into the downstream side space from the upstream side space The structure of the air flowing down. 14. The electric material according to Item 13, wherein the upper edge portion of the groove body has a protruding piece extending toward the overflow groove side, and the protruding piece has a tip end spaced apart from a side surface of the groove body. 15. The electric ore device according to claim 1, wherein the ore solution has a drop in the air in the second space. The electroplating apparatus according to claim 1, wherein the plating solution is used for copper plating, and comprises a sulfur-containing organic compound in which the solvent is used as a buffer. 53 201109478 I7. The electroplating method and the electroplating device of the groove in which the plating tank is a groove of the other body, using a plating tank comprising: a plating bath, the plating solution being between the plating tank and the plating tank According to the above-mentioned trough, the second to the second is the space that is downstream of the gan~ space! There is a space in the first place; and there is space in the second dynasty, in the second place, the above plating solution is stored. In the predetermined plating solution, the gold particles are placed under the first space, and the upper portion of the plating solution in the first + 2 and the second θ flows into the above-mentioned first space. The second method is to adjust the plating solution by flowing the above plating solution into the air; the second empty method. The electric plating of the tie/morning. 18. If the scope of the application is used, the plating solution is used for copper plating. The electroplating apparatus according to item 17, wherein the upper portion comprises a cut organic compound as a brightener.