TW201247946A - Electroplating method - Google Patents

Abstract

An electroplating method is capable of reliably embedding via holes with a plated metal such as copper or the like when a substrate with a seed layer of a metal having a greater ionization tendency than hydrogen is electroplated using an acidic plating solution such as a copper sulfate plating solution. The electroplating method including preparing a substrate having via holes covered with a first metal, which has a greater ionization tendency than hydrogen, in a surface thereof, pretreating the substrate by immersing the substrate in a pretreatment solution in which a second metal that is more noble than the first metal or a salt thereof is dissolved, and then electroplating the surface of the substrate to embed the second metal or a third metal in the via holes.

Description

201247946 VI. DESCRIPTION OF THE INVENTION: [Spraying of the genus of the genus: 彳 $ 贝 贝 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 Loading such a metal such as copper into the vias in the fabrication of the substrate, such as a semiconductor substrate or the like, the substrate having a plurality of vertically penetrating via posts (hole plugs) therein, and It can be used in a three-dimensional package of so-called semiconductor wafers. [Prior Art 3] Background of the Invention The formation of a metal via post such as copper, which vertically penetrates a semiconductor substrate, is known as a method of electrically connecting the layers of a multilayer stack of semiconductor substrates. Figures 1A through 1C show an exemplary method for fabricating a substrate having a copper via post therein. First, as shown in FIG. 1A, a substrate W is prepared by forming a plurality of upwardly open vias in a substrate, such as a germanium wafer, for example by using the lithography/etching. a technique; on the surface of the substrate 10, including a sidewall of the via 12, forming a dielectric film (not shown), such as by PVD; on the entire surface of the substrate 10, including the inner surface of the via 12, A metal barrier layer 14 such as Ti (titanium) is formed, and then a copper seed layer 16 is formed on the surface of the barrier layer 14. The diameter of the through hole 12, d" is, for example, 2 to 50 μm, especially 1 〇 to 2 〇 μηι, and the depth "h" of the through hole 12 is, for example, 20 to 150 μm The copper electroplating system uses the copper seed layer 16 as a cathode on the surface of the substrate 201247946, so as to fill a plating metal (copper) 18 into the through hole, and deposit the plating metal 18 to The surface of the copper seed layer 16 is as shown in FIG. 1B. In the case of embedding copper into the via hole 12 by copper plating, a copper sulfate plating solution is widely used as a plating solution. The person is relatively inexpensive and relatively easy to control, including its waste treatment, thereafter, as shown in Figure 1C, additional bond metal 18, copper seed layer 16 and barrier layer on the substrate 10. The 14-series is removed, for example, by chemical mechanical polishing (CMP). Further, the surface side of the substrate 10 is polished off, for example, to the position indicated by the two-dot chain line in Figure 1C, thereby exposing a bottom surface of the plating metal 18 embedded in the through hole 12. W having a copper (electroplated metal 18) via post therein, vertically penetrating through the substrate W, can be fabricated in this manner. The via 12 generally has a high aspect ratio, that is, a depth to diameter ratio And has a large depth. In order to thoroughly fill the copper (electroplated metal) into the through hole 12, it has a high aspect ratio and a large depth, and is not manufactured by an electric key such as in the embedded metal. The defect of the void, which is usually necessary to perform the electroplating in a bottom-up manner to allow the electroplated metal to preferentially grow from the bottom of the via 12. This bottom-up electrowinning is generally performed by using a sulfuric acid. It is carried out by a copper plating solution containing various additives such as sps (bissulfide (disulfide)) (bis (3-sulf〇pr〇pyi) disulfide) as an electric ore accelerator, PEG (poly(10) Ethylene glycol) acts as a homogenizer—(iv) and pm (polyethyleneimine). These additives exert their effects on 201247946 after they are absorbed onto a substrate surface. PVD generally has a low ladder. Cover coverage. So 'if that The continuous copper seed layer 16 is formed on the surface of the barrier layer 14 by PVD. Then the continuous copper seed layer 16 needs to have a considerable thickness, for example, in the range from 800 nm to 1000 nm. Inevitably, there is a need for a smaller thickness seed layer. As shown in Figure 2, it is already understood that a conformal CVD process is performed on the entire surface of the substrate 10, including such The surface of the through hole 12 forms a cobalt film 20 as a sublayer, which serves as a barrier layer. Then a 'copper plating process is performed on the cobalt film 20 as a cathode to electroplate metal. That is, copper is embedded in the through hole 12. C SUMMARY OF THE INVENTION 3 SUMMARY OF THE INVENTION However, it is difficult to completely fill the through holes 12 in accordance with an electroplating process with a metal such as copper or the like without generating an unfilled land. The cobalt film 20 covers the surface and has a high south width ratio and a large depth. For example, as shown in Fig. 3, the surface of a substrate prepared by a substrate w is covered by a cobalt film and has a plurality of through holes 12a having a depth of 1 ^ ^ 彳 岳 。 。 。 。 。 When the surface of the substrate is plated using a copper sulfate plating solution containing various additives, and an electroplated metal crucible is incorporated into the through holes 12a, the unfilled strip 22a has a rather rough surface. A large bottom portion of the hole 12a is formed. Cobalt thin coating Fig. 4 shows another substrate W which is covered with 201247946 and has a plurality of through holes 12b having a diameter of 20 μm and a depth of about 120 μm. When the substrate Wq surface ❹ contains one of various additives, a copper sulphate plating solution, the galvanic metal 18 copper is embedded in the through holes l2b, and the unfilled strip 22b has a rather rough surface. The large bottom portion 7 is formed into a blade and the copper filled in the through holes 12b is easily different in length. Fig. 5 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12c having a diameter of 3 μm and a depth of about 130 μm. The surface of the substrate W is plated with copper sulfate containing one of various additives. When the liquid ore is embedded in the through holes 12c with the electric ore metal 18, the copper metal is only in the through hole 12. It grows on the upper inner surface. The grown electric ore metal 18 does not close the open end of the through holes 12c, and the through holes 12 are not completely embedded in the plating metal 18. As described above, a copper plating metal is completely embedded in the through hole according to one of the electroplating processes using copper sulfate plating solution, and the unfilled land is non-volatile, and the surface of the through holes is a cobalt film. Covered and has a high aspect ratio and a large depth. For the reason that the through holes are not completely provided, it is believed that the thin film is dissolved in the copper copper ore solution, which is stored with the acidic copper sulfate electric ore solution. Directly. Specifically, if the difficult-to-like metal is less inert (four) gold; | 'such as Μ' means that if the metal of the seed layer has a larger ionization tendency than hydrogen' then the seed layer is dissolved in the "acidic ore solution" . a ruthenium cobalt ruthenium film, that is, the seed layer, which is dissolved in a plating solution, the 201247946 problem, '4 roads themselves', especially in the contact area of the outer surface of the substrate (four), the area contact-seal member prevents it Or sealing the outer surrounding surface 'with its adjacent zone from the money solution. Specifically, the contact area of the 4 film with the surrounding surface of the 4 substrate and its adjacent zone - a higher rate of dissolution 'because - the film of the ore film is less likely to deposit on these local areas' due to the local area The electric field is blocked. The substrate is generally supplied with current from the surface of the outer egg of the tablet 2G which is protected from the electroplating solution by the sealing member. If the film is dissolved in the contact zone of the outer substrate with the outer surface of the adjacent substrate, the current is prevented from flowing in the absence of the seed layer. The substrate. 『: The test pyrotechnic electro-key solution will be a usable solution. However, the solution is more expensive than the sulfur-electric ship (four) and makes the management of the plating solution more complicated, including waste disposal. The problem that the shell seed layer is transferred to the acidic f lin liquid (4) #—gu film <surface system, appearing in copper Wei, and when the metal surface having a tendency to ionize with hydrogen is electroplated with another metal appear. L In the above case, the present invention has been made. Therefore, the present invention is directed to providing a plating material which is provided with a substrate having a metal seed layer which is relatively large in hydrogen and which is electroplated with a copper sulfate electroplating solution, such as a copper sulfate electroplating solution. The present invention provides an electrical inclusion preparation substrate having a first metal cladding on its surface; = 201247946 hole, the first The metal has a tendency to ionize more hydrogen, pretreating the substrate by immersing the substrate in a pretreatment solution, and in the pretreatment solution, one of the second metals is more inert than the first metal or The salt is dissolved, and then the surface of the substrate is plated to embed the second metal or a third metal in the through hole. Since the substrate has a tendency to have a larger hydrogen ionization degree on the surface thereof The first metal-covered through hole is pretreated by immersing the substrate in a pretreatment solution, and the second metal or its salt which is more inert than the first metal in the pretreatment solution Is dissolved, compared to the first a metal film of a second metal which is more inert is formed on the surface of the first metal by substitution. When the surface of the substrate is plated, the first metal is prevented from directly contacting an acidic plating solution. Contacting and being dissolved in the acidic plating solution to positively embed the plating metal in the through holes. The pretreatment solution is preferably in a range from a slightly acidic degree to a slightly alkaline degree, thereby Preventing the first film, such as a cobalt film, from being dissolved therein upon contact with the pretreatment solution. Preferably, the substrate is prior to pretreatment of the substrate by immersing the substrate in the pretreatment solution. Pretreating by immersing the substrate in the deaerated water, wherein the second metal or a salt thereof is dissolved in the pretreatment solution. This can enhance the hydrophilicity of the surface of the substrate, and in the permeation After the deaerated water enters the through hole, the permeated deaerated water in the through holes may be replaced by the pretreatment solution, and the person thus surely enters the through holes. The first metal may be For example, and the second metal which is more inert than cobalt 201247946 may be copper. In the case of a recirculation towel, the pretreatment solution should preferably have a copper concentration ranging from 1 to 70 g/L. - the copper metal film is formed on the surface of the cobalt film by means of substitution, and the neotite film is prevented from being dissolved in the (iv) solution. The pretreatment containing copper The solution can be prepared by dissolving sulphur in pure water, for example, and the concentration of copper in the pretreatment solution (four) is set to a desired value depending on the size of the through hole. _ The second metal may be 1 bar, gold, turn or silver, and the third gold may be copper. In this case, an acidic copper sulfate plating solution is preferably used as the plating solution. According to the present invention, when the first metal, For example, it has a tendency to ionize more than hydrogen 1, the system is used as a seed layer, and the substrate is made of an acid electric wire, such as a copper sulfate surface, the first metal is made of a metal of the second metal. Thin (four) is damaged by the electric lining liquid, and the second metal is more than the first More metal ship, and the thin-film material in fine assist substitution - are formed on the metal surface. (4) The through-holes covered by the first metal are surely carried in due to the fine metal. Circular Simple Description 1A to 1C® is a cross-sectional view showing a method of fabricating a substrate having a plurality of steel through-hole posts extending vertically through the substrate, and FIG. 2 is a cross-sectional view showing surface coverage a substrate having a thin film and having a through hole; Fig. 3 is a cross-sectional view showing a substrate, the surface of which is covered with a cobalt film of 201247946, and having a plurality of through holes having one of ΙΟμπι a diameter and a depth of ΙΟΟμίΉ, when the substrate is plated with a copper sulfate plating solution, the through holes are embedded with copper plating metal; FIG. 4 is a cross-sectional view showing a substrate, the surface of which is covered with a cobalt film having a plurality of through holes having a diameter of one of 20 μm and a depth of 120 μm. When the substrate is electroplated using a copper sulfate plating solution, the through holes are embedded in the copper plating metal; FIG. 5 is a The cross-sectional view shows a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 30 μm and a depth of 130 μm, which is electroplated using a copper sulfate plating solution. In the case of a plate, the through holes are embedded in a copper plated metal; Fig. 6 is a schematic plan view showing the overall arrangement of an electroplating facility for performing one of the electroplating methods of the present invention; Fig. 7 is in Fig. 6. A schematic elevational view of one of the transport robots used in the electroplating facility is shown; Fig. 8 is a schematic cross-sectional view of one of the electroplating devices employed in the electroplating facility shown in Fig. 6; a plan view of a stirring paddle (stirring tool) of one of the plating apparatuses shown in Fig. 8; Fig. 10 is a cross-sectional view taken along line Α-Α of Fig. 9;

Figure 11 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηη and a depth of about ΙΟΟμηη, using a copper sulfate plating When the solution is electroplated, the through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L 10 201247946; and FIG. 12 is a cross-sectional view showing a substrate The surface of the person is covered with a cobalt film and has a plurality of through holes having a diameter of one of 20 μm and a depth of about 120 μm. When the substrate is electroplated using a copper sulfate plating solution, the copper plating metal is embedded therein. a through hole after the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L; FIG. 13 is a cross-sectional view showing a substrate covered with a cobalt film and having a number The through holes have a diameter of one of 30 μm and a depth of about 130 μm. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and the substrate is used. After treatment with a pretreatment solution of 10 g/L copper concentration; Fig. 14 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of ΙΟμηι And plating the substrate with a copper sulfate plating solution at a depth of about 之一μιη, the copper plating metal is embedded in the through holes, and the substrate is treated with a pretreatment solution having a copper concentration of 30 g/L; Is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 20 μm and a depth of about 120 μm, which is electroplated using a copper sulfate plating solution. In the case of a substrate, the through holes are embedded in a copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 30 g/L; and FIG. 16 is a cross-sectional view showing a substrate, the surface of the substrate Covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηη and a depth of about ΙΟΟμηη, when the substrate 11 201247946 is electroplated using a copper sulfate plating solution, The metal plating is embedded in the through holes after the substrate is treated with a pretreatment solution having a copper concentration of 60 g/L; and FIG. 17 is a cross-sectional view showing a substrate covered with a cobalt film. And having a plurality of through holes having a diameter of one of 20 μm and a depth of about 120 μm. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and the substrate is used with 60 g/ One of the L copper concentrations is treated with the pretreatment solution; and the 18th is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 30 μm At a depth of about 130 μm, when the substrate was plated with a copper sulfate plating solution, the through holes were embedded with copper plating metal after the substrate was treated with a pretreatment solution having a copper concentration of 60 g/L. I. Embodiment 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. The following description exemplifies an exemplary case in which, as shown in FIG. 2, a substrate W is provided, the substrate is formed by a homomorphic CVD process, formed on the entire surface thereof, and includes a via hole 12 The surface, as a cobalt film of the seed layer, doubles as a barrier layer. Then, a copper plating process is performed on the surface of the substrate W using a copper sulfate plating solution, so that a plating metal, that is, copper, is embedded in the through holes 12, thereby forming a copper via hole in the substrate W. . Fig. 6 is a plan view showing the overall layout of an electroplating facility used in the electroplating method of the present invention. This electro-mineral facility is designed to automatically perform all electroplating processes in a phase 12 201247946, including pre-substrate processing, electroplating, and post-plating processing. The interior of the equipment frame 110 having one of the mounting panels attached thereto is divided by a partitioning plate 112 into a plating space 116' for performing an electric forging process of a substrate and being attached to the electric clock solution. The processing of the substrate, and the cleaning space 114 used to perform one of the other processes, that is, the process that is not directly involved in a plating solution. Two substrate adjusters 160 (see FIG. 7) are arranged in parallel, and a substrate attaching/separating stage 162 to which a substrate is attached to each substrate support 160 and a substrate is separated from each substrate support 160 is One of the partitions separated by the partition plate 112 is provided as a substrate delivery section, wherein the partition plate 1丨2 divides the electric ore space 116 from the cleaning space 114. The loading/unloading port 12 is attached to the cleaning space 114 on the substrate on which the substrate is stored. Further, the equipment frame 110 has a manipulation panel 121 provided thereon. In the   cleaning space 114, it is configured to align one of the directional plates of a substrate or - the aligner 122 of the pre-determined direction, two for cleaning - electric "plate and rotate at high speed" The substrate is spin-dried to the cleaning/drying device 124 of the substrate. The step-by-step-transport robotic arm 128 is substantially disposed in the center of the guarding device, that is, the aligner a] and the center of the cleaning/drying county 124, and thus in the processing device 122 124. The substrate attachment/detachment stage 162 and a substrate mounted and transported between the loading/unloading cassettes. The aligner m disposed in the cleaning space i 14 and the cleaning/drying device 12 are designed to support the substrate in a horizontal state and process a substrate in which the front surface of the substrate faces upward. The first conveyor 13 201247946 arm 128 is designed to transport and deliver the substrate in a horizontal manner, in which state the front surface of the substrate faces upward. In the key space 116, in the order from the partition plate m, it is provided with a stocker 164 for storing or temporarily storing the substrate holder (10); for performing-pre-wetting processing ( The first pre-treatment of the first-pretreatment) is 126 to enhance the hydrophilicity of the surface of the substrate by wetting with the deaerated water, such as pure water (_); one for performing the substitution process (second before a second pretreatment device 166 for treating the cobalt on the surface of the ruthenium film by immersing the substrate in a slightly acidic or slightly alkaline pretreatment solution, wherein The solution contains copper which is more inert than cobalt; a first water cleaning device 168a for cleaning the surface of the substrate with pure water; - a plating device for performing electroplating 17: a second water cleaning device 168b, and a The air blowing device 172 for dehydrating the electric boat substrate. Two second conveyor arms 174a, 174b are disposed beside these devices for movement along a track 176. One of the second transport robots 17 transports the substrate baffle 160 between the substrate attachment/detachment stage 162 and the reservoir 164. The other one of the second transfer robots 174b is in the storage 164, the first pre-processing device 126, the second pre-processing device 166, the first water cleaning device 168a, the plating device 17A, the second The substrate holder 16 is transported between the water cleaning device 168b and the air blowing device 172. As shown in Fig. 7, the second conveyor robots 174a, 174b each have a body 178 extending in a vertical direction and are vertically movable along the body 178 and rotatable about its axis - the arm 18 Hey. The arm 18 has two substrate holder fixing portions 182 provided in parallel for detachably fixing the substrate holder 160 such as the 2012 201247946. The substrate holder 160 is designed to support the substrate W in a state in which the front surface of the substrate is exposed and a peripheral portion of the substrate is sealed, and is designed to adhere the substrate W to the substrate holder 160. The substrate W is separated from the substrate holder 160. The storage 164, the first pretreatment device 126, the second pretreatment device 166, the water cleaning devices 168a, 168b, and the plating device 170 are designed to be disposed at both ends of each substrate supporter 160. The outwardly projecting portion engages 'and thus supports the substrate holder 160 in such a state that the substrate holder 160 is suspended in a vertical direction. The first pretreatment device 126 has two pretreatment tanks 127 for holding a deaerated water therein, such as pure water (degassed DIW) having, for example, a dissolved oxygen concentration of no more than 2 mg/L or Class. As shown in FIG. 7, the arm 180 of the second conveyor arm 174b supporting the substrate support 160 is lowered for engagement with the upper end of the first pretreatment tank 127 to support the suspension in a suspension manner. The substrate holder 160 is mounted, wherein the substrate holders 160 are loaded in a vertical state. Therefore, the first pre-processing device 126 is designed such that the substrate holders 16 are immersed in the degassed water in the pre-treatment tank 127 together with the substrates w to perform the surface of the substrate. A pre-wetting treatment (first pre-treatment). The second pretreatment unit 166 has two pretreatment tanks 183 for holding therein a slightly acidic or slightly alkaline pretreatment solution containing relatively more inert copper. As shown in FIG. 7, the arms 180 of the second conveyor arm 174b supporting the substrate holders 160 are lowered for engagement with the upper ends of the pretreatment tanks 183 to support the bases in a suspension manner. 15 201247946 A plate holder 160, wherein the substrate holders 160 are loaded with the substrates W in a vertical state. Therefore, the second pre-processing device 166 is designed such that the substrate holder 160 is immersed in the pre-treatment liquid in the pre-treatment tank 183 with the substrate W to perform a cobalt film surface. One of the substitution processes (second pre-processing). a pretreatment solution in which the copper system is dissolved and the person is in a range from a slightly acidic degree to a slightly alkaline degree, that is, having a pH from the range of 2 to 9 by Copper sulfate is dissolved in pure water, for example, prepared. The copper concentration of the pretreatment solution may be in the range of from 1 to 70 g/L, and is set to a desired value depending on the size or the like of the through hole. A buffer for pH adjustment, such as phosphate, titanate, citric acid, succinic acid or boric acid, may be added to the pretreatment solution to inhibit pH fluctuation of the pretreatment solution. Similarly, the water washing devices 168a, 168b have two water washing tanks 184a and two water washing tanks i84b, respectively, which hold pure water therein, and the plating apparatus 170 has a plurality of holdings therein. Electroplating bath 186 for the plating solution. The water cleaning devices 16A, 168b and the plating device 170 are designed such that the substrate holder 160 is immersed in the water cleaning tanks 184a, 184b with the substrate W. In the plating solution in the plating bath 186, water washing or plating is performed in the same manner as described above. The arm 180 of the second transfer robot arm 174b supporting the substrate supporter 160 is lowered, and air or inert gas is injected toward the substrates w mounted on the substrate supporters 160 to blow away the substrates attached thereto. The support 160 and the liquid on the substrates w and the substrates W are removed from the 20124794646 water, wherein the substrate holders are loaded with the substrate w in a vertical state. Therefore, the air blowing device i 7 2 is configured to perform a blowing process. As shown in Fig. 8, each of the electrowinning tanks 186 provided in the electroplating apparatus 17 is designed to hold a predetermined number of electric-key solutions Q in its napkin. The substrates W are maintained in the _ state, whereby the front surface (the surface to be plated) is exposed, and the peripheral portion of the substrate is sealed by the substrate holder _ watertight, in the vertical direction In this case, the acid sulfur solution is used as the electric shovel solution Q, which contains various additives in addition to copper ions, supporting electrolysis f and halogen ions. 'such as SPS (disulfide (double handle base)) as - electroplating accelerator, PEG (polyethylene glycol) as an inhibitor, and PEI (polyethyleneimine) as - (4), for example Words. Preferably, the sulfuric acid is used as the supporting electricity (4), and the ion system is preferably used as the halogen ion. An overflow tank 200 for receiving the electric ore solution q from which the party has overflowed the edge of the key slot 186 has been disposed around the upper end of the plating tank 186. a end of a circulation line 2〇4, the line is provided with a pump 202 connected to the bottom of the overflow tank 2〇〇, and the other end of the circulation line 204 is connected to the plating The plating solution supply port 186a is one of the grooves 186 bottom #. Therefore, the plating solution in the overflow tank 2 is returned to the key slot 186 by the driving of the pump 2〇2. Downstream of the pump 202, a temperature unit 206 for controlling the temperature of the electromineral solution Q and a filter 208 for filtering foreign matter contained in the electromineral solution are interposed in the middle of the circulation line 2〇4. of. bottom. The seesaw 210, which has a large number of plating solution through holes therein, 17 201247946 is disposed in the bottom of the plating bath 186. The interior of the plating bath 186 is thus divided by the bottom plate 210 into an upper substrate processing chamber 214 and a lower clock solution distributed to 212. Further, a shielding plate 216 extending vertically downward is mounted on the lower surface of the bottom plate 210. According to the plating apparatus 170, the plating solution Q is introduced into the plating solution distribution chamber 212 of the plating tank 186 by the driving of the pump 2〇2, and flows through the plating solution through the bottom plate 210. The substrate processing chamber 214' vertical flow is approximately parallel to the surface of the substrate W supported by the substrate holder 16A, and then flows into the overflow groove 2''. An anode 22 having an annular shape corresponding to the shape of the substrate w is supported by an anode holder 222 and vertically disposed in the plating tank ι86. When the plating solution Q is loaded in the plating tank 186, the anode 220 supported by the anode holder 222 becomes immersed in the plating solution Q' in the electric recording tank 186 and faces the substrate holder The substrate W supported and disposed in the plating bath 186. Further, in the key slot 186, an adjustment plate 224 for adjusting the potential distribution in the plating bath 186 is disposed between the anode 220 and the substrate w disposed at a predetermined position in the plating bath 186. Between configurations. In this embodiment, the adjustment plate 224 includes a cylindrical portion 226 and a rectangular flange portion 228 and is made of a dielectric material of polyethylene. The cylindrical portion 226 has such an opening size and shaft length as to substantially limit electrical expansion. The lower end of one of the flange portions 228 of the adjusting plate 224 hits the bottom plate 210. Further, in the plating tank 186, an adjusting plate 224 is used for adjustment.

18 201247946 This potential distribution in the money slot 186 is disposed between the anode 22 and the substrate w disposed in the keyway 186 at a predetermined position. In this yoke case, the adjustment plate 224 includes a cylindrical portion 226 and a rectangular = edge portion 228' and is made of a dielectric material polyvinyl chloride. The columnar portion: 226 has such a (four) size and shaft length in order to sufficiently limit the electric field expansion. The bottom plate 210 is formed by the flange portion 228 of the (four) plate 224. Between the adjusting plate 224 and a predetermined position of the plating plate 186, a vertically extending mixing wood 232 is disposed as a dialing tool, which is used to reciprocate the surface of the wire r The plating solution Q between the substrate W and the conditioning plate 224 is stirred. A sufficient amount of copper ions can be uniformly supplied to the surface of the substrate W by the stirring violet 232 (stirring tool) during the electric key. As shown in Figures 9 and 1 , the agitating paddle 232 is composed of a rectangular, plate-like member having a uniform thickness &quot;t&quot; of ^ to ^ mm, and having a plurality of parallel slits 232a defined The vertically extending strip portions 23 are formed by, for example, a resin such as pvc, pp, and pTFE, and a sus or a layer having a weave coating. At least part (4) mixed with purple m, contact with the key solution, is electrically isolated. The vertical length L1 of the search purple 232 and the vertical length L2 of the slit coffee are sufficiently larger than the vertical size of the substrate W. Further, the stirring paddle 232 is designed such that the sum η of its lateral lengths and its reciprocating distance (stroke) are sufficiently larger than the lateral dimension of the substrate W. Preferably, the slit is The width and number of 232a are determined by 201247946 by the fact that each strip portion 232b is narrower as far as possible to the extent that it has the necessary rigidity such that the strip portions between the narrow strips 232a 232b can effectively mix the key solution, and the plating solution can be The plating device 170 is provided with a plating power source 250. The positive electrode of the device is connected to the anode 220 via a wire during plating, and the negative electrode is connected to the substrate W via a wire. The plating power source 250 is coupled to a control section 252' and the plating apparatus 170 is controlled based on signals originating from the control section 252. The series of plating processes will be described below, which is by the sixth The electroplating apparatus shown in the figure is used for plating the surface of the substrate W. The substrate is provided with a cobalt film 2〇 formed on the entire surface thereof, including the surface of the through holes 12, as shown in FIG. It is shown that a copper sulphate plating solution is used, so that a plated metal 'meaning copper' is embedded in the through holes 12. First, the substrate W is placed in a substrate , with its front surface (the surface to be plated) Face up, and the substrate is mounted on the loading/unloading cassette 120. One of the substrates W is taken out from the substrate mounted on the loading/unloading cassette 12Q by the first conveying robot arm 128. And placed in The aligner 12 2 is aligned with one of the substrates w to align the flat plate or the notch in a pre-determined direction. Another aspect is 'two substrate supports (10) which are stored in a vertical state in the reservoir (6) By taking out the 'rotation' by the second transfer robot arm (10), whereby the substrate supports (four) 16 处于 in a - horizontal state ' and then placed in parallel on the substrate attachment/separation table 162 0 20 201247946 in a predetermined The substrates W that are aligned with their alignment plates or notches are transported and loaded into the substrate holder 160 placed on the substrate attachment/detachment stage 162, which is in a state by which the substrates are The peripheral part is sealed. The two substrate holders 160, which have been loaded with the substrates w, are simultaneously fixed, lifted, and then transported to the reservoir 164 by the second transfer robot arm 74a. The substrate support 160 is rotated 90. The vertical state is lowered and lowered, whereby the two substrate holders 16 are held in the suspension 164 in a hanging manner (temporary storage). The above operations are repeated in a sequential manner whereby the substrate is successively loaded into the substrate holder 16 存放 stored in the reservoir 164 and successively in a suspension mode The predetermined position is maintained in the storage 164 (temporary storage). On the other hand, the two substrate supporters 160, which have been loaded with the substrates and temporarily stored in the storage 164, are simultaneously fixed, lifted, and then transported to the first by the first conveyor arm 174b. The pre-processing device 126 is in the first pre-processing device 126, and the substrates w supported by the substrate holders 16 are immersed in degassed water in the pre-treatment tank 127, such as pure water (DIW). ) to thereby perform a pre-wetting treatment (first pre-treatment) on the surface of the substrate. The pure water used as the deaerated water is preferably adjusted to a dissolved oxygen concentration of 2 mg/L or less by a vacuum deaerator, and therefore, by performing pre-wetting treatment on the surface of the substrate W (the first) The pre-treatment), the hydrophilicity of the surface of the substrate W can be increased, allowing the highly permeable degassed water to enter the through holes 12 in the substrate W. After the first pre-processing, the two substrate holders 16 are each loaded with a substrate, which is transported to the 21st 201247946 pre-processing H166 in the same manner as described above, in which , the substrate substrate is in the treatment tank 183 - the former Lu persimmon j treatment "cold liquid, the pretreatment solution contains copper in the system ^ ° micro acidity to a slight degree of inspection, so as to «Mysterious cobalt: 4 membrane 2 〇 on the surface - generation domain (second pretreatment). In this substitution process (= two pre-treatments), the job water, the person performing the pre-wet treatment (the W-th treatment) has entered the through-holes 12 in the substrate w, by the pre-treatment solution Change, and the side of the hole 12 is still filled with a simple solution. This replacement process will be described in detail below. When reducing the film 2〇 covering the surface of the riding substrate ~ every __, when immersed in the treatment solution containing copper, 'cobalt on the surface of the (four) lion, which is less inert than the copper system, The pretreatment solution towel was changed, and the surface of the cobalt film 20 was woven from (4). The surface of the #2G film, covered with copper, will be protected from a money solution. When copper covers the entire surface of the cobalt film 2, the substitution reaction is stopped, and a very thin copper film is deposited on the surface of the cobalt film. The thickness of the cobalt ruthenium film 20 is not substantially affected by the copper film, whereby the function of the cobalt ruthenium film 20 as a barrier layer is still effective or not. The pretreatment solution is preferably in a range from a slightly acidic degree to a slightly alkaline degree to prevent the cobalt film 2 from being dissolved therein upon contact with the pretreatment solution. The pretreatment solution may have a dissolved oxygen concentration adjusted to 2 mg/L or less, such as the deaerated water. After the second pre-treatment, the substrate holders 160, each carrying the substrates W, are transported to 22 201247946, the first water cleaning device 168a, in the same manner as described above. The surface of the substrate w is cleaned with pure water held in the first water washing tank 184a. After the water cleaning, the two substrate holders 16 are loaded with the substrates W and transported to the plating bath 186 of the plating apparatus 170 in the same manner as described above. The plating bath 186 has been filled with a predetermined amount of plating solution Q having a predetermined composition which is carried by the sinusoidal system. The substrate board 16 is then lowered to immerse the substrates W supported by the substrate holders 160 in the electroplating solution Q in the plating bath 186. Each of the substrates w is disposed at one of the positions of the electric ore solution q facing the anode 220 of the building supported by the anode baffle 222. Each substrate W is immersed in the plating solution Q for a predetermined time, and the plating solution Q is substituted for the pre-treatment solution in the through holes 12 during the predetermined time period, at the anode 220 and the No voltage is applied between the cobalt films, wherein the drill film is attached to the surface of each substrate W and covered with a copper film. Thereafter, a voltage is applied between the anode 22 and the surface of each substrate w between the cobalt thin films covered with a copper film, and an electroplating process is performed to coat the cobalt film covered by the copper film. A copper plating film is deposited on the surface of the film 20, and the plating film of the steel is embedded in the through holes 12. The plating solution q used in the electroplating process is an acidic sulfuric acid bond solution. The management of the person is relatively easy to carry out. If the cobalt film 2 is in direct contact with the acidic copper sulfate plating solution, then the cobalt film 20 is dissolved in the plating solution. In this embodiment, however, since the surface of the cobalt film 20 is covered with a very thin copper film, the cobalt film 2 23 23 201247946 remains in direct contact with the acidic copper sulphate plating solution, and thereby prevents Dissolved in the plating solution Q. The plating process is terminated after the voltage between the anode 22 and the surface of the substrate w has been applied for a predetermined period of time. After the 5 well substrate W has been immersed in the key solution Q, and until the plating gyro system is terminated, the agitating paddles 232 are moved back and forth parallel to the substrate w to agitate between the adjusting plate 224 and the The plating solution Q between the substrates W. The embedding of the vias 12 continues until the aspect ratio of the vias 12 is reduced until the plating solution Q can easily reach the limit of the surface of the metal plated on the sides of the vias 12. If the plating solution Q is still vigorously stirred by the stirring paddles 232 at this time, then the growth of the plating metal may be slowed down, requiring an extra time until the through holes 12 are completely embedded. In order to avoid this disadvantage, it is desirable that the plating solution Q is less agitated when the plating process has been carried out to some extent. After the termination of the electroplating process, the voltage applied between the anode 220 and the surface of each substrate, the cobalt film 20 covered with a copper film, is closed. Thereafter, the two substrate holders 160, each loaded with the substrate W', are again supported by the second transfer robot arm 174b and withdrawn from the keyway 186. The two substrate holders 16 0 are then routed to the second water cleaning device 168b in the same manner as described above, where the surfaces of the substrates are immersed in the water by immersing the substrates It is cleaned by 5 liters of pure water held in the tank 184b. Thereafter, the substrate holders 160, each loaded with the substrate, are transported to the blow 24 201247946 gas device 172' at the same location as described above, the electromineral solution and the water droplet system The substrate holder 16 is removed from the substrate holder 16 by blowing air or inert gas onto the substrate support n16(). Thereafter, the substrate branches (4) (10) are loaded into the reservoir 164 in the same manner as described above, and each of the substrates is held in the storage. Library (6). The second transport robot arm 174b sequentially repeats the above operations to sequentially support the substrate to the H16G, and each of the substrates is loaded with a substrate to return to the library 164. The substrate holder 160 is suspended and suspended in the reservoir 164. On the other hand, 'two substrate holders 160 loaded with the plated substrate' have been returned to the reservoir 164, simultaneously grasped by the second conveyor robot 174a in the same manner as described above. It is taken and placed on the substrate attachment/detachment stage 162. The first transfer robot arm 128 is disposed in the cleaning space 114, and takes out a substrate from a substrate holder 160 placed on the substrate attachment/detachment table 162 and transports the substrate to the cleaning/drying device. One of the 24s. In the cleaning/drying devices 124, the substrates are maintained in a horizontal position with the front surface facing up, cleaned, for example, with pure water, and then spin dried by rotation at a high speed. Thereafter, the substrates are returned to the substrate on the loading cassette 120 by the material-conveyor arm 128 to complete the plating operation. - The experiment is performed on the surface of the substrate, and the entire surface of the substrate is covered with a cobalt film, including surfaces of different sizes of through holes. The pre-treatment (first-pre-treatment) is performed by immersing the base = immersed in deaerated water followed by the substitution process (second pre-treatment), which makes 25 201247946 use a number of different copper concentrations A type of pretreatment solution for substituting the film. Thereafter, the substrates are plated to embed the vias with copper plating metal. The embedding of these through holes in the experiment will be explained below. Figure 11 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12a. The through holes na are plated on the substrate W using a copper sulfate plating solution, embedded in a copper plated metal 18 The through holes i2a are performed in a pre-wet treatment (first pre-treatment) to immerse the substrate W in deaerated water for 10 minutes and then a one-generation process (second pre-treatment) is carried out to use 10 g. One of the /L copper concentrations of the pretreatment solution is substituted for the surface of the cobalt film for 1 minute after it has a diameter of 1 〇μηι and a depth of about ΙΟΟμπι. Figure 12 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12b which are plated with a copper sulfate plating solution on the substrate W. In the case of the through holes 12b, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in the U-th image, it has a diameter of one of 20 μm and a depth of about 120 μm. Figure 13 shows a substrate W which is covered with a cobalt film and has a plurality of through holes 12c. The through holes 12c are plated on the substrate W using a copper sulfate electroplating solution to electroplate a metal 18 When the through holes 12c are embedded, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in Fig. 12, they have a diameter of one of 30 μm and a depth of about 130 μm. It can be seen from the 11th to 13th that when the substitution treatment (second pretreatment) is performed by using one of the 10 g/L copper concentration pretreatment solutions to replace the surface of the ruthenium film for 1 minute, One of the diameters of the ΙΟμηι and the depth of the hole 12a, as shown in Fig. 11, is embedded in different deep production, 26 201247946 having a depth of one of 30 μπι and a depth of 13 〇 μη The through holes 12c, as shown in Fig. 13, are embedded in the depth of the through holes 12c to form an unfilled land, and have such a through hole 12b having a diameter of 20 μm and a depth of 12 μm. As shown in Fig. 12, it is well embedded. The pretreatment solution having a steel concentration of 1 Og/L is prepared by dissolving copper sulfate in pure water. The pretreatment solution having a concentration of 3 〇g/L copper And a pretreatment solution having a copper concentration of 60 g/L, as described below, is also prepared by dissolving copper sulfate in pure water. Figure 14 shows a substrate W which is covered with a cobalt. The film has a plurality of through holes 12a, and the through holes 12a use a sulfuric acid on the substrate The copper plating solution is electroplated, and when a copper plating metal 18 is embedded in the through holes 12a, a pre-wetting treatment (first pre-treatment) is performed to immerse the substrate w in the deaerated water for 10 minutes and then to replace the treatment ( The second pretreatment was carried out to replace the surface of the cobalt film with a pretreatment solution having a copper concentration of 30 g/L for 1 minute, which had a diameter of 1 μm and a depth of about 1 μm. Figure 15 shows a substrate W which is covered with a cobalt film and has a plurality of through holes 12b which are plated on the substrate using a sulfuric acid steel plating solution and embedded in a copper plating metal 18 In the case of the through holes 12b, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in FIG. 4, it has a diameter of one of 20 μm and a depth of about 120 μm. From the 14th to the 15th. It can be seen that when the substitution treatment (second pretreatment) is carried out by using a pretreatment solution of 30 g/L copper concentration to replace the surface of the cobalt film for 1 minute, it has a diameter of ΙΟμιη and 1 〇〇μιη—the depth of these The hole 12a, as shown in Fig. 14, is uniformly embedded to a depth of 27 201247946 and at the same time produces a small unfilled zone at the depth of the through holes 12a and has a diameter of one 及μηι and one depth The through hole 12b, as shown in Fig. 15, is substantially completely embedded. Fig. 16 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12a' such through holes 12a. The substrate W is plated with a copper sulfate plating solution, and a copper plating metal 18 is embedded in the through holes 12a, and is subjected to a pre-wetting treatment (first pretreatment) to immerse the substrate W in the deaerated water up to 10 Minutes and then one-generation treatment (second pre-treatment) is carried out to replace the surface of the cobalt film with one of the pretreatment solutions having a copper concentration of 60 g/L for one minute, which has one diameter of ΙΟμιη and one of about ΙΟΟμιη depth. Figure 17 shows a substrate w which is covered with a cobalt film and has a plurality of through holes 12b which are plated with a copper sulfate plating solution on the substrate W. In the case of the through holes 12b, after the pre-wetting treatment and the substitution processing are carried out in the same manner as in Fig. 16, it has a diameter of one of 20 μm and a depth of about 120 μm. Figure 18 shows a substrate W which is covered with a cobalt film and has a plurality of through holes 12c. The through holes 12c are plated on the substrate W using a copper sulfate electroless solution, embedded in a copper plated metal 18 The through holes 12c have a diameter of one of 30 μm and a depth of about 130 μm after the pre-wet lake treatment and the replacement process are carried out in the same manner as in Fig. 16. It can be seen from Figures 16 to 18 that 'when this substitution process (second pretreatment) is performed using one of the 60 g/L copper concentrations to pretreat the surface of the drill film for 1 minute' The through holes 12a of one of the diameters of ΙΟμηι and one of the depths of ι〇〇μηη, as shown in Fig. 16, are embedded in the small unfilled zone at the depth 28 201247946 of the through holes 12a, and have a 20 μηι The through holes 12b' having a diameter and a depth of 12 〇μη as shown in FIG. 17, and having the diameter of one of 3 μm and one of the depths of 130 μm, as shown in FIG. 18, The system is well embedded. In the above embodiment, the copper (second metal) is embedded in the through hole according to an electroplating process, and the cobalt is used as a first metal, which has a larger ionization tendency than hydrogen, and the copper system is used. As a second metal, this is more inert than cobalt. A copper-containing pretreatment solution is prepared by dissolving copper sulfate contained in a plating solution in pure water. Since the pretreatment solution is prepared using one of the components in the plating solution, it is not necessary to take care of entraining the undesired material to the subsequent process. Palladium, gold, platinum or silver may be used as a metal (second metal) which is more inert than cobalt (metal), and vias may be embedded in copper (third metal) according to an electroplating process. In the above embodiment, the pre-wetting treatment (the first pre-treatment) is for immersing a substrate in degassed water such as pure water (DIW) to enhance the hydrophilicity of the surface of the substrate, and the substitution is performed. The treatment (second pretreatment) is carried out by immersing the plate in a copper-containing slightly slightly or slightly lining (four) pretreatment solution, wherein the copper is replaced by a cobalt thief, and the copper is substituted for the surface of the film. The two pre-treatments are implemented separately from each other. However, the pre-wetting treatment (first pre-treatment) and the substitution treatment (second pre-treatment) may be performed by immersing the substrate in the pre-degassing treatment solution from a slight acidity to a slightity. To the extent that it has the copper dissolved therein: the same as: 29 201247946. In the above embodiment, the steel system is deposited by means of substitution on the surface of a drilled film. It is a barrier layer and a sub-layer, and the through-hole is embedded with human copper by a plating process. However, the present invention can also be applied to the surface of a metal having a tendency to be more hydrogen-larger ionization according to the -Wei process. Herein, the copper system deposits 'and' by using a pretreatment solution having copper dissolved therein on the surface of the metal, and then the surface is electroplated (4) to act as a barrier layer. '-_ Membrane may be used as a barrier layer. The metal (metal), which covers the vias such as 6 hai, may not necessarily act as a barrier layer. The fortune can be used to form a further barrier process in which a metal (metal) is deposited on the barrier layer, which has a larger ionization tendency than hydrogen, and the money is electrically charged on the deposited metal. The metal material deposited by the substitution is limited to the copper 'domain (4). The person is not limited to copper 0. The metal (first metal) example has a larger ionization tendency than hydrogen according to the present invention. , including nickel, for example, in addition to cobalt. An example of the metal (second metal) deposited by substituting the first metal surface includes, in addition to copper, gold, silver, and silver. In the above embodiment, a metal system is embedded in the through hole. However, the principles of the present invention can also be applied to the embedding or through hole of a metal in trench interconnects. Although the present invention has been described with reference to the preferred embodiments thereof, it is to be understood that the invention is not limited to the embodiments, but various modifications can be made in the general inventive concept described herein. BRIEF DESCRIPTION OF THE DRAWINGS 201247946 Sections 1A to 1C are cross-sectional views showing a method of fabricating a substrate having a plurality of copper via posts extending vertically through the substrate; FIG. 2 is a cross-sectional view showing the same The surface is covered with a cobalt film and has a substrate of a through hole; FIG. 3 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having one of ΙΟμιη a diameter of one of 1 ΟΟμιη, when the substrate is electroplated with a copper sulfate plating solution, the through holes are embedded with copper plating metal; FIG. 4 is a cross-sectional view showing a substrate, the surface of which is covered a cobalt film having a plurality of through holes having a diameter of one of 20 μm and a depth of 120 μm. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded with copper plating metal; A cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of 30 μm and a depth of 130 μm, using a copper sulfate plating solution In the case of the substrate, the through holes are embedded in the copper plating metal; FIG. 6 is a schematic plan view showing the overall arrangement of the electroplating facility used in the electroplating method of the present invention; FIG. 7 is in the sixth The figure shows a schematic elevational view of one of the transport robots used in the electroplating facility; Fig. 8 is a schematic cross-sectional view of one of the electroplating devices used in the electroplating facility shown in Fig. 6; A plan view of a stirring paddle (stirring tool) of the plating apparatus shown in Fig. 8; 31 201247946 Fig. 10 is a cross-sectional view taken along line AA of Fig. 9; Fig. 11 is a A cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηι and a depth of about ΙΟΟμηη, when the substrate is plated using a copper sulfate plating solution The through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L; FIG. 12 is a cross-sectional view showing a substrate, the surface of which is covered with One cobalt film And having a plurality of through holes having a diameter of one of 20 μm and a depth of about 120 μm, and when the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and the substrate is used with 10 g/ After the pretreatment solution is treated as one of the L copper concentrations; Fig. 13 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of about 30 μm and about At a depth of 130 μm, when the substrate is electroplated using a copper sulfate plating solution, the through holes are embedded in a copper plating metal, and the substrate is treated with a pretreatment solution having a copper concentration of 10 g/L; A cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of one of ΙΟμηη and a depth of about ΙΟΟμπι, when the substrate is plated using a copper sulfate plating solution Inserting the through holes with copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 30 g/L; FIG. 15 is a cross-sectional view showing a substrate, The surface of the person is covered with a cobalt film and has a plurality of through holes having a diameter of 20 μm and a depth of about 120 μm. When the substrate 32 201247946 is electroplated using a copper sulfate plating solution, the copper plating metal is embedded therein. The through hole is processed after the substrate is treated with a pretreatment solution having a steel concentration of 30 g/L; and FIG. 16 is a cross-sectional view showing a substrate covered with a cobalt film and having a number The through hole has a diameter of one of ΙΟμίΉ and a depth of about ΙΟΟμιη. When the substrate is plated with a copper sulfate plating solution, the through holes are embedded in the copper plating metal, and one of the copper concentrations of 60 g/L is used in the substrate. After the treatment of the pretreatment solution; Fig. 17 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 20 μm and a depth of about 120 μm. When the substrate is electroplated using a copper sulfate plating solution, the through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 60 g/L; And Figure 18 is a cross-sectional view showing a substrate covered with a cobalt film and having a plurality of through holes having a diameter of 30 μm and a depth of about 130 μm, using copper sulfate When the plating solution is plated with the substrate, the through holes are embedded in the copper plating metal after the substrate is treated with a pretreatment solution having a copper concentration of 60 g/L. [Description of main component symbols] Via 110.·· 10... Substrate 12, 12a, 12b, 12c, ... 14... barrier layer 16... seed layer 18... electro-mineral metal. 20... drilled film 22a, 22b... unfilled zone Equipment frame 112··· partition plate 114...cleaning space 116···plating space 120···loading/unloading埠33 201247946 121···manipulation panel 122···aligner 124···cleaning/drying device 126···First pretreatment device 127, 183... pretreatment tank 128···first transport robot arm 160···substrate support 162...substrate attachment/separation table 164...storage 166··· Two pre-processing devices 168a...first water washing device 168b...second water washing device 170···plating device 172···air blowing device 174a, 174b...second conveying robot arm 176...track 178··· body , 180...arm 182···substrate holder fixing portion 184a, 184b...water cleaning tank 186···plating tank 186a...electroplating solution supply inlet 200···overflow tank 202...helper 204···circulation line 206···Thermal unit 208···Filter 210···Bottom plate 212···The lower plating solution distribution room 214··· Upper substrate processing chamber 216&quot;·shield plate 220...anode 222···anode support 224...adjustment plate 226···column portion 228···rectangular flange portion 232...stirring paddle 232a...slit 232b... strip portion 250···plating power supply 252... control section W... substrate Q... plating solution 34

Claims (1)

201247946 VII. Patent application scope: 1. A plating method comprising: preparing a substrate having a through hole covered with a first metal on a surface thereof, the first metal having a hydrogen ionization tendency; Pre-treating the substrate by immersing the substrate in a pre-treatment solution, wherein in the pre-treatment solution, one of the second metal or a salt thereof is more inert than the first metal; and then electroplating a surface of the substrate to embed the second metal or a third metal in the through hole. 2. The electroplating method of claim 1, wherein the pretreatment solution is in a range from slightly acidic to slightly alkaline. 3. The electroplating method according to claim 1, further comprising: pre-treating by immersing the substrate in deaerated water before pretreating the substrate by immersing the substrate in the pretreatment solution The substrate, wherein the second metal or a salt thereof is dissolved in the pretreatment solution. 4. The electroplating method of claim 1, wherein the first metal is a drill. 5. The electroplating method of claim 1, wherein the second metal is copper and the pretreatment solution has a copper concentration ranging from 1 to 70 g/L. 6. The electroplating method of claim 1, wherein the second metal is a handle, gold, turn or silver, and the third metal is copper. 7. The electroplating method according to claim 4, wherein the second metal 35 201247946 is copper, and the pretreatment solution has a copper concentration in the range of 1 to 70 g/L. 8. The electroplating method according to any one of claims 4, wherein the second metal is palladium, gold, platinum or silver, and the third metal is copper. 36