US20070062816A1 - Method of electroplating printed circuit board using magnetic field having periodic directionality - Google Patents

Method of electroplating printed circuit board using magnetic field having periodic directionality Download PDF

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Publication number
US20070062816A1
US20070062816A1 US11/516,772 US51677206A US2007062816A1 US 20070062816 A1 US20070062816 A1 US 20070062816A1 US 51677206 A US51677206 A US 51677206A US 2007062816 A1 US2007062816 A1 US 2007062816A1
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Prior art keywords
magnetic field
plating
periodic
directionality
electroplating
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Abandoned
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US11/516,772
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English (en)
Inventor
Tae Chung
Young Ko
Young Park
Ji Park
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Samsung Electro Mechanics Co Ltd
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Samsung Electro Mechanics Co Ltd
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Assigned to SAMSUNG ELECTRO-MECHANICS CO., LTD. reassignment SAMSUNG ELECTRO-MECHANICS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHUNG, TAE JOON, KO, YOUNG GWAN, PARK, JI YEON, PARK, YOUNG GEUN
Publication of US20070062816A1 publication Critical patent/US20070062816A1/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/007—Electroplating using magnetic fields, e.g. magnets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/104—Using magnetic force, e.g. to align particles or for a temporary connection during processing

Definitions

  • the present invention relates to a method of electroplating a printed circuit board (PCB) using a magnetic field having periodic directionality. More particularly, the present invention relates to a method of electroplating a PCB, capable of realizing uniform plating while preventing the aging of a plating solution without the need for an additional external liquid flow device, using a magnetic field which is generated substantially perpendicular to the current direction and which has periodic directionality between a forward wave and a reverse wave.
  • PCB printed circuit board
  • PCBs for use in the operation of electronic products are produced through numerous fabrication processes comprising complicated process steps.
  • a plating process that is, a metallization process
  • slim, short and small PCBs since the sizes of via holes used in the connection of metal wires and electronic devices are further decreased, a more uniform plating process is required.
  • a technique of forming a seed layer using an electroless chemical plating process and then forming a metal layer through electroplating is typically employed.
  • Such a technique is advantageous because it is relatively inexpensive and also because a uniform plating layer may be formed in the case where the distance between the metal wire and the insulating layer is 60 ⁇ m or less and the via hole has a large diameter of 100 ⁇ m or more.
  • FIG. 1 schematically illustrates the plating device used in the method of electroplating the PCB, according to a conventional technique.
  • a plating bath 1 filled with an electrolyte solution 3
  • voltage is applied from a power source 6 to an anode 2 for transferring a plating ion and a substrate 4 (cathode) on which a wire is formed, according to Faraday's law, such that current may flow to conduct a plating process .
  • Japanese Patent Laid-open Publication Nos. Hei. 7-169714 and 5-78885 disclose an electroplating method using a magnetic field, aging of the plating solution and non-uniform ionic concentration thereof are caused by the application of a magnetic field having a fixed flow direction, undesirably resulting in non-uniform plating.
  • FIG. 2 illustrates the plating device used in the electroplating method using a magnetic field according to the conventional technique.
  • the conventional electroplating method using a magnetic field when voltage is applied using a power source 6 , the plating ion is detached from the anode 2 and then deposited on the substrate 4 through the electrolyte solution 3 in the plating bath 1 .
  • a magnetic field is applied perpendicular to a current direction using a magnetic field generator 5 (electromagnets or permanent magnets)
  • the flow of the plating ion is activated by Lorentz force.
  • the device of FIG. 2 is equal to the plating device shown in FIG. 1 .
  • one aspect of the present invention is to provide a method for electroplating on a PCB using a magnetic field having periodic directionality, which can prevent aging of a plating solution and can make the ionic concentration of the plating solution uniform without the use of an additional external liquid flow device.
  • Another aspect of the present invention is to provide a method of electroplating a PCB using a magnetic field having periodic directionality, which can form a uniform plating layer on the PCB.
  • the present invention provides a method of electroplating a PCB using a magnetic field having periodic directionality, comprising (a) bringing an electrolyte solution into contact with the surface of a PCB; and (b) simultaneously applying a magnetic field to the electrolyte solution and applying voltage between the PCB and the electrolyte solution, wherein the magnetic field is generated substantially perpendicular to the current direction and has periodic directionality between a forward wave and a reverse wave.
  • the magnetic field may be supplied using permanent magnets, and the magnetic field having the periodic directionality is preferably supplied through the rotation of a pair of permanent magnets.
  • the magnetic field may be supplied using electromagnets.
  • the magnetic field having the periodic directionality may be supplied through change in a current waveform using a pair of electromagnets and a pulse modulator/demodulator connected thereto.
  • the magnetic field having the periodic directionality may be supplied through change in a current waveform using a pair of electromagnets and a reverse pulse rectifier connected thereto.
  • the electrolyte solution may include a copper ion.
  • FIG. 1 is a schematic view showing the plating device used in a method of electroplating a PCB according to a conventional technique
  • FIG. 2 is a schematic view showing the plating device used in a method of electroplating a PCB according to another conventional technique
  • FIG. 3 is a view showing the direction of Lorentz force with respect to the directions of current and magnetic field in the plating device of FIG. 2 ;
  • FIG. 4 is a schematic view showing the plating device used in a method of electroplating a PCB, according to a first embodiment of the present invention
  • FIG. 5 is a schematic view showing the plating device used in a method of electroplating a PCB, according to a second embodiment of the present invention.
  • FIG. 6 is a schematic view showing the plating device used in a method of electroplating a PCB, according to a third embodiment of the present invention.
  • FIGS. 7A to 7 D are schematic views showing the current waveforms resulting from the electroplating method using the plating devices of FIGS. 4 and 5 ;
  • FIGS. 8A and 8B are views showing the direction of Lorentz force, varying depending on the direction of a magnetic field, in the plating method of the present invention.
  • FIGS. 9A to 9 C are electron micrographs ( ⁇ 500) showing the cross-sections of the plated substrates in the example and comparative examples of the present invention.
  • FIGS. 10A to 10 C are SEM photographs ( ⁇ 30,000) showing the surfaces of the plated substrates in the example and comparative examples of the present invention.
  • the method of the present invention is characterized in that a magnetic field is applied to a plating solution so as to control the flow direction and density of the ion in the plating solution.
  • a magnetic field is applied to a plating solution so as to control the flow direction and density of the ion in the plating solution.
  • an electric field and a magnetic field induce large convection flow through Lorentz force, and thus small MHD (Magneto Hydrodynamics) flow is generated near the cathode on which the plating process is conducted so as to make the plating process uniform.
  • the applied magnetic field functions to enlarge the mean free path of the ion near the plating surface so as to increase the quantity of charge. Thereby, the current amount is increased, leading to an increased plating rate.
  • the method of the present invention is characterized in that the direction of the magnetic field is periodically changed, thus increasing the flow of the electrolyte solution and decreasing the variation in plating. Accordingly, through the method of the present invention, excellent plating may be conducted on the PCB.
  • FIGS. 4 to 6 illustrate the plating devices used in the method of electroplating the PCB, according to the preferred embodiments of the present invention.
  • a plating bath 101 is filled with an electrolyte solution.
  • a magnetic field is applied to the electrolyte solution 103 using a magnetic field generator 105 a , that is, electromagnets 105 a
  • voltage is applied between the substrate 104 and the electrolyte solution 103 using a power source 107 such that current flows.
  • ions in the plating solution are detached from the anode 102 and then deposited on the substrate 104 through the electrolyte solution 103 , thus forming a plating layer.
  • the magnetic field is applied substantially perpendicular to the current direction using the electromagnets 105 a , and therefore the flow of the plating ion is activated by Lorentz force.
  • the phase of current may be varied over time, as shown in FIGS. 7A to 7 D. Accordingly, the direction of the magnetic field is periodically changed between the forward wave and the reverse wave, thereby varying the direction of Lorentz force.
  • FIG. 7A is suitable for use in plating a substrate that has a via hole having a large diameter of 100 ⁇ m or more and requires large liquid flow due to the simple phase change of current waveform.
  • FIG. 7B since a pause time of current is present, the thickness of a hydraulic boundary layer may be adjusted through the control of such a pause time, thus realizing the plating of a substrate having a complicated pattern.
  • FIG. 7C the small flow of the magnetic field may be generated due to the fine change in current and thus the throwing power of the plating may be increased with respect to a substrate having both a via hole and a pattern. Therefore, such a waveform is suitable for plating a substrate having a pattern and a via hole. Since the case of FIG. 7D helps greatly increase the small throwing power through application of the same fine waveforms having a short period, it is suitable for use in plating a substrate having a small via hole having a diameter of 50 ⁇ m.
  • the concentration of the plating ion capable of being deposited near the substrate becomes 0.
  • the current applied to the substrate is referred to as a threshold current density.
  • an external flow device for example, an air blower or an E-ductor, may be used, it may negatively affect the formation of a uniform plating layer.
  • the control of such flow is regarded as important in the fabrication of a fine metal wire substrate, such as a PCB.
  • the current direction may be changed as in FIGS. 7A to 7 D, such that the N pole and S pole of the electromagnet are alternately changed as in FIGS. 8A and 8B .
  • periodic change in Lorentz force is caused which therefore contributes to making the concentration gradient of the plating solution uniform.
  • MHD convection flow is induced near the substrate to realize the formation of a uniform plating layer without the use of an additional device, such as an air blower or an E-ductor, functioning to negatively affect the uniform plating process.
  • FIGS. 7A to 7 D the period and interval of the magnetic field are depicted in FIGS. 7A to 7 D.
  • the magnetic field increases in proportion to the magnitude of current inducing the magnetic field depending on the law of Lorentz force.
  • B is the magnitude of a magnetic field
  • ⁇ right arrow over (l) ⁇ is the extension distance of a magnetic field
  • I is a current
  • r the radius of a conductor for inducing a magnetic field
  • ⁇ right arrow over (Y) ⁇ is a unit vector in a current flow direction
  • ⁇ 0 is a dielectric constant related to magnetism
  • ⁇ is a ratio of a circumference of a circle to its diameter.
  • the extent of liquid flow in the plating bath may be adjusted by controlling the magnitude of current inducing the magnetic field.
  • the magnitude of the magnetic field suitable for plating the substrate preferably falls in the range of 0.1 T to 10 T. If the magnitude of the magnetic field is beyond the above range, there is no effect thereof, or an effect impeding the movement of the ion may result.
  • the plating time and the current density are proportional to the plating thickness according to Faraday's law.
  • d M w ⁇ I ⁇ ⁇ ⁇ ⁇ ⁇ t n ⁇ ⁇ F ⁇ ⁇ A ⁇ ⁇ D
  • d is the plating thickness
  • n is the number of charges
  • F is the Faraday constant
  • A is the area of the plating surface
  • D is the metal density
  • M w is the atomic weight of metal
  • I is the current density
  • ⁇ t is the plating time. That is, when the plating time and the current density are increased, the plating thickness may be increased.
  • a method of increasing the current density for plating within the same time using a magnetic field to improve the plating rate is proposed.
  • FIG. 5 illustrates the plating device using a reverse pulse rectifier 106 b , in which the pulse modulator/demodulator 106 and the power source 107 of FIG. 4 are combined. Even with the use of such a device, the current waveforms of FIGS. 7A to 7 D may also be formed, and thus the direction of the magnetic field of FIGS. 8A and 8B is periodically changed, leading to uniform plating.
  • FIG. 6 is a view showing the plating device for periodic application of the magnetic field through the rotation of permanent magnets 105 b .
  • the means for rotating the permanent magnets 105 b is not particularly limited so long as it is known in the art. For example, while a fan belt 109 connected to a rotation motor 108 is moved, the permanent magnets 105 b provided to both ends thereof are rotated, but the present invention is not limited thereto. Thereby, the periodic change in the direction of the magnetic field is caused as in FIGS. 8A and 8B , consequently forming a uniform plating layer.
  • the substrate actually used in the plating process has a size of about 40.5 cm (width) ⁇ 51 cm (length).
  • the plating bath should have a volume capable of accommodating one to four substrates.
  • Such a substrate may have a via hole of 50 ⁇ 120 ⁇ m and a pattern having a size of 100 ⁇ m.
  • the trajectory of the metal ion is made more precise through the MHD convection flow than in a conventional unidirectional magnetic plating device.
  • a via hole having an aspect ratio about 1 ⁇ 2 times higher than conventional via holes may be plated, or a fine pattern having a via hole diameter of about 20 ⁇ 60 ⁇ m may be uniformly plated.
  • the current waveforms may be changed using the pulse modulator/demodulator or the reverse pulse rectifier, or various magnetic waveforms may be formed through the rotation of the permanent magnets, thus preventing the aging of the plating solution and making the ionic concentration in the plating solution uniform.
  • a copper plating solution comprising 50 g/l sulfuric acid, 200 g/l copper sulfate, 50 ppm chlorine, and various additives, that is, 100 mg of a carrier, 2.5 mg of a brightener, and 7.5 mg of a leveller, was used as an electrolyte solution, and conditions shown in Table 1 below were applied, thus forming an electroplating layer on a PCB.
  • a 6 cm (width) ⁇ 6 cm (length) sized test sheet having a via hole having a diameter of 50 ⁇ m and a pattern of 40 ⁇ m was used as the PCB.
  • the test sheet was sonicated for 5 min to remove organic material from the substrate and then washed with 0.1 N sulfuric acid for 30 sec and subsequently with distilled water to increase affinity with the plating solution, before copper electroplating.
  • the above pretreatment procedure was the same as a plating pretreatment process typically known in the art.
  • An electroplating layer was formed on the PCB in the same manner as in Example 1, with the exception that the electroplating process was conducted using the conventional electroplating device of FIG. 1 without the application of a magnetic field.
  • the electroplating conditions are given in Table 1 below.
  • An electroplating layer was formed on the PCB in the same manner as in Example 1, with the exception that the electroplating process was conducted using the conventional electroplating device of FIG. 2 through the application of a unidirectional magnetic field.
  • the electroplating conditions are given in Table 1 below. TABLE 1 Conditions Ex. 1 C. Ex. 1 C. Ex.
  • FIGS. 9A to 9 C and FIGS. 10A to 10 C The SEM photographs of the cross-sections and surfaces of the PCB samples having the electroplating layer formed under the conditions shown in Table 1 are shown in FIGS. 9A to 9 C and FIGS. 10A to 10 C.
  • the plating layer of Example 1 ( FIG. 9A ) had a maximum thickness of 26 ⁇ m, and the plating layers of Comparative Examples 1 and 2 ( FIGS. 9B and 9C ) were 21 ⁇ m and 15 ⁇ m thick, respectively.
  • the reason why the plating layer of Comparative Example 2 ( FIG. 9C ) was the thinnest despite the application of the magnetic field is believed to be because the concentration of the plating solution was non-uniform due to the application of the unidirectional magnetic field and because heat was emitted from the electromagnet and thus the temperature of the plating solution increased, thus facilitating the aging of the plating solution.
  • the plating layer of Example 1 ( FIG. 10A ) had the finest texture, whereas the plating layers of Comparative Examples 1 and 2 had coarse textures, in which the texture of the plating layer of Comparative Example 2 ( FIG. 10C ) was coarser than that of the plating layer of Comparative Example 1 ( FIG. 10B ).
  • the current applied to the electrolyte solution in the absence of the external liquid flow, the copper ion is deposited on the substrate (cathode) with time. After a certain time period, the concentration of the copper ion capable of being deposited near the substrate becomes 0. At this point, the current applied to the substrate is referred to as a threshold current. In this way, when the current reaches a threshold current, the plating process does not proceed any further.
  • Example 1 As is apparent from the results in Table 1, the plating process in Example 1 was seen to be conducted for a period of time increased by about 60% compared to the plating process of Comparative Example 1 without the application of the magnetic field, and by about 25% compared to the plating process of Comparative Example 2 through the application of the unidirectional magnetic field. As such, that the plating process is conducted for a longer period of time without the external liquid flow indicates the realization of a uniform plating process on the metal wire substrate having various thicknesses.
  • the plating rate may be increased. Further, by changing the magnetic waveform, the liquid flow is increased, therefore preventing the non-uniform copper ion that has occurred in a conventional electromagnetic plating process.
  • the plating solution may be easily aged due to the non-uniform solution concentration and the generation of heat.
  • the liquid flow can be activated through various current waveforms or using permanent magnets.
  • the electromagnetic magnets less heat is generated and thus the aging of the solution may be slowed. Therefore, a uniform plating process is realized, leading to the formation of the fine circuit of the substrate.
  • the present invention provides a method of electroplating a PCB using a magnetic field having periodic directionality.
  • a periodically changeable magnetic field is applied, such that the trajectory of a metal ion is made more precise through MHD convection flow, compared to the use of a conventional unidirectional magnetic plating device.
  • it is possible to realize a process of plating a via hole having a high aspect ratio or of uniformly plating a fine pattern, even without the use of an external liquid flow device.
  • the use of a conventional plating device continuously applying the unidirectional magnetic field results in fast aging of the plating solution or in the ionic concentration of the plating solution inclined in only one direction through unidirectional Lorentz force
  • the aging of the plating solution can be prevented and the ionic concentration thereof can be made uniform thanks to the change of current waveforms using a pulse modulator/demodulator or a reverse pulse rectifier or thanks to the formation of various magnetic waveforms through the rotation of permanent magnets.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
US11/516,772 2005-09-16 2006-09-07 Method of electroplating printed circuit board using magnetic field having periodic directionality Abandoned US20070062816A1 (en)

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KR1020050086812A KR100645630B1 (ko) 2005-09-16 2005-09-16 주기적 방향성을 갖는 자기장을 이용한 인쇄회로기판의전해 도금방법

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090050486A1 (en) * 2007-08-24 2009-02-26 International Business Machines Corporation Enhanced Magnetic Plating Method and Apparatus
US20110042223A1 (en) * 2009-08-24 2011-02-24 Ezekiel Kruglick Magnetic Electro-Plating
US10526719B2 (en) * 2013-08-21 2020-01-07 Taiwan Semiconductor Manufacturing Company Limited Magnetic structure for metal plating control
CN112695351A (zh) * 2020-12-18 2021-04-23 苏州天承化工有限公司 一种印刷电路板的通孔电镀方法
US12054846B2 (en) 2021-09-15 2024-08-06 Samsung Electronics Co., Ltd. Electroplating apparatus and electroplating method

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Publication number Priority date Publication date Assignee Title
KR20090022877A (ko) * 2007-08-31 2009-03-04 주식회사 탑 엔지니어링 박막 금속 전도선의 제조 방법
TWI410531B (zh) * 2010-05-07 2013-10-01 Taiwan Semiconductor Mfg 直立式電鍍設備及其電鍍方法

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US5883762A (en) * 1997-03-13 1999-03-16 Calhoun; Robert B. Electroplating apparatus and process for reducing oxidation of oxidizable plating anions and cations
US20050258044A1 (en) * 2004-05-21 2005-11-24 Berman Michael J Magnetic focus rings for improved copper plating

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JPH02135795A (ja) * 1988-11-17 1990-05-24 Mitsubishi Electric Corp プリント回路用基板のレジスト塗布装置
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US4904362A (en) * 1987-07-24 1990-02-27 Miba Gleitlager Aktiengesellschaft Bar-shaped magnetron or sputter cathode arrangement
US5883762A (en) * 1997-03-13 1999-03-16 Calhoun; Robert B. Electroplating apparatus and process for reducing oxidation of oxidizable plating anions and cations
US20050258044A1 (en) * 2004-05-21 2005-11-24 Berman Michael J Magnetic focus rings for improved copper plating

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090050486A1 (en) * 2007-08-24 2009-02-26 International Business Machines Corporation Enhanced Magnetic Plating Method and Apparatus
US7964081B2 (en) * 2007-08-24 2011-06-21 International Business Machines Corporation Enhanced magnetic plating method
US20110220020A1 (en) * 2007-08-24 2011-09-15 International Business Machines Corporation Enhanced magnetic plating method
US8168045B2 (en) * 2007-08-24 2012-05-01 International Business Corporation Apparatus for an enhanced magnetic plating method
US20110042223A1 (en) * 2009-08-24 2011-02-24 Ezekiel Kruglick Magnetic Electro-Plating
CN102482791A (zh) * 2009-08-24 2012-05-30 英派尔科技开发有限公司 磁电镀
US9797057B2 (en) * 2009-08-24 2017-10-24 Empire Technology Development Llc Magnetic electro-plating
US10526719B2 (en) * 2013-08-21 2020-01-07 Taiwan Semiconductor Manufacturing Company Limited Magnetic structure for metal plating control
US11230791B2 (en) 2013-08-21 2022-01-25 Taiwan Semiconductor Manufacturing Company Limited Magnetic structure for metal plating control
CN112695351A (zh) * 2020-12-18 2021-04-23 苏州天承化工有限公司 一种印刷电路板的通孔电镀方法
US12054846B2 (en) 2021-09-15 2024-08-06 Samsung Electronics Co., Ltd. Electroplating apparatus and electroplating method

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