WO2023013987A1 - A leveling agent and an electroplating composition including the same - Google Patents

A leveling agent and an electroplating composition including the same Download PDF

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Publication number
WO2023013987A1
WO2023013987A1 PCT/KR2022/011179 KR2022011179W WO2023013987A1 WO 2023013987 A1 WO2023013987 A1 WO 2023013987A1 KR 2022011179 W KR2022011179 W KR 2022011179W WO 2023013987 A1 WO2023013987 A1 WO 2023013987A1
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Prior art keywords
group
leveling agent
via hole
electroplating composition
independently selected
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PCT/KR2022/011179
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French (fr)
Inventor
Sungwook CHUN
Bomook CHUNG
Deageun KIM
Nakeun Ko
Juyong SIM
Seongho Seok
Joosok Kim
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Corning Precision Materials Co., Ltd
Ymt Co., Ltd.
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Publication of WO2023013987A1 publication Critical patent/WO2023013987A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • C25D5/02—Electroplating of selected surface areas
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/486—Via connections through the substrate with or without pins
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49827—Via connections through the substrates, e.g. pins going through the substrate, coaxial cables
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/426—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in substrates without metal

Definitions

  • the present invention relates to a leveling agent that may allow the inside of a via hole (or through hole) formed in a glass via hole substrate (TGV substrate) to be efficiently plated and an electroplating composition including the same.
  • Glass via hole substrates are attracting attention as a component material for various electronic devices due to characteristics of high thermal stability and low surface roughness.
  • an electrode formation technique by via metallization acts as an important factor.
  • a side seed metal layer is formed by electroless plating, and a plating method of filling a via hole by electrolytic plating is applied.
  • voids or seams are formed in via holes due to the influence of a via hole aspect ratio, a hole diameter, an additive to a plating solution, resulting in a deterioration in electrical characteristics of a glass via hole substrate or reliability of a device package.
  • Patent document 0001 Korean Patent Publication No. 2019-0003050
  • the present invention provides a leveling agent that allows the inside of a via hole (or through hole) formed in a glass via hole substrate to be efficiently and uniformly plated.
  • the present invention provides an electroplating composition including the leveling agent.
  • the present invention provides a method of plating a via hole of a glass via hole substrate by using the electroplating composition.
  • the present invention provides a leveling agent which is a compound represented by Formulae 1 to 3 below.
  • R 1 and R 6 are each independently selected from the group consisting of a sulfonic acid group (-SO 3 H), a hydroxyl group (-OH), a C 1 -C 10 alkyl group, a C 6 -C 20 aryl group, and a C 2 -C 20 heteroaryl group,
  • R 2 to R 5 are each independently selected from the group consisting of a hydroxyl group (-OH), a C 2 -C 20 heteroaryl group, -NR 7 R 8 , and -NR 9 -L 3 -R 10 ,
  • L 1 and L 2 are each independently selected from the group consisting of oxygen (O) and a C 2 -C 20 heteroarylene group,
  • a and b are each independently an integer from 1 to 5
  • n is an integer from 1 to 10
  • R 7 to R 10 are each independently selected from the group consisting of hydrogen (H), a hydroxyl group (-OH), a C 6 -C 20 aryl group, and a C 2 -C 20 heteroaryl group,
  • L 3 is a C 1 -C 5 alkylene group
  • an alkyl group, an aryl group, and a heteroaryl group of each of R 1 and R 6 and a heteroarylene group of each of L 1 and L 2 are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of a hydroxyl group (-OH), an amino group (-NH 2 ), a halogen group, and a C 1 -C 10 alkyl group.
  • the present invention provides an electroplating composition including a metal ion source and the leveling agent.
  • the present invention provides a method of plating a via hole of a glass via hole substrate, the method including: forming a via hole in a glass substrate; forming an electroless plating layer by performing electroless plating on the glass substrate in which the via hole is formed; and forming an electrolytic plating layer by performing electrolytic plating on the glass substrate on which the electroless plating layer is formed, and the electrolytic plating is performed by using the electroplating composition.
  • a leveling agent according to the present invention can allow a decomposition rate and concentration of an additive (e.g., brighteners, carriers, and accelerating agents) included in an electroplating composition to be maintained constant during a plating process. Therefore, when plating (filling) of a via hole (or through hole) formed in a glass via hole substrate is performed by using an electroplating composition including the leveling agent according to the present invention, the occurrence of voids or seams can be minimized, thereby improving the reliability and stability of the glass via hole substrate or a device package.
  • an additive e.g., brighteners, carriers, and accelerating agents
  • FIG. 1 schematically shows a process of plating a via hole of a glass via hole substrate, according to an embodiment of the present invention.
  • FIG. 2 shows a waveform of a current density applied during electrolytic plating in a process of plating a via hole of a glass via hole substrate, according to an embodiment of the present invention.
  • FIG. 3 shows experiment results according to Experiment Example 1 of the present invention.
  • the present invention relates to a leveling agent that allows the inside of a via hole (through hole) formed in a glass substrate to be efficiently plated (filled), and an electroplating composition including the same, which will be described in detail as follows.
  • the leveling agent according to the present invention may be a compound represented by Formulae 1 to 3.
  • R 1 and R 6 are identical to or different from each other, and are each independently selected from the group consisting of a sulfonic acid group (-SO 3 H), a hydroxyl group (-OH), a C 1 -C 10 alkyl group (e.g., a C 1 -C 5 alkyl group), a C 6 -C 20 aryl group (e.g., a C 6 -C 10 aryl group), and a C 2 -C 20 heteroaryl group (e.g., a C 3 -C 10 heteroaryl group),
  • R 2 to R 5 are identical to or different from each other, and are each independently selected from the group consisting of a hydroxyl group (-OH), a C 2 -C 20 heteroaryl group (e.g., a C 3 -C 10 heteroaryl group), -NR 7 R 8 , and -NR 9 -L 3 -R 10 ,
  • L 1 and L 2 are identical to or different from each other, and are each independently selected from the group consisting of oxygen (O) and a C 2 -C 20 heteroarylene group (e.g., a C 3 -C 10 heteroarylene group),
  • a and b are each independently an integer from 1 to 5, and n is an integer from 1 to 10,
  • R 7 to R 10 are identical to or different from each other, and are each independently selected from the group consisting of hydrogen (H), a hydroxyl group (-OH), a C 6 -C 20 aryl group (e.g., a C 6 -C 10 aryl group), and a C 2 -C 20 heteroaryl group (e.g., a C 3 -C 10 heteroaryl group),
  • L 3 is a C 1 -C 5 alkylene group (e.g., a C 1 -C 3 alkylene group), and
  • an alkyl group, an aryl group, and a heteroaryl group of R 1 , an alkyl group, an aryl group, and a heteroaryl group of R 6 , a heteroarylene group of L 1 , and a heteroarylene group of L 2 are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of a hydroxyl group (-OH), an amino group (-NH 2 ), a halogen group, and a C 1 -C 10 alkyl group.
  • R 1 and R 6 may each independently be selected from the group consisting of a sulfonic acid group (-SO 3 H), a hydroxyl group (-OH), , , , and .
  • R 2 to R 5 may each independently be selected from the group consisting of a hydroxyl group (-OH), , , , , and .
  • L 1 and L 2 may each independently be selected from the group consisting of oxygen (O) and .
  • a and b may each independently be an integer from 1 to 3, and n may be an integer of 1.
  • the leveling agent according to the present invention may be embodied as compounds represented by C-1 to C-4 below, but is not limited thereto.
  • the heteroaryl group in the present invention may indicate a monovalent aromatic ring group including at least one hetero atom such as N, O, S, F, etc.
  • the halogen group in the present invention may indicate a fluorine group, a bromine group, a chlorine group, an iodine group, and the like.
  • a method of synthesizing a leveling agent according to the present invention is not particularly limited, but a method of reacting an alkylation agent compound with an amine-based compound in the presence of a solvent may be employed to increase synthesis efficiency. Specifically, after a first alkylation agent compound and an amine-based compound are added to a solvent and reacted, a second alkylation agent compound is added thereto and reacted, to thereby synthesize a leveling agent according to the present invention.
  • the first alkylation agent compound is not particularly limited, but may be at least one selected from the group consisting of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,2-bis(2-chloroethoxy)ethane.
  • the second alkylation agent compound is not particularly limited, but may be at least one selected from the group consisting of 1,3-propanesultone, epichlorohydrin, benzyl chloride, aniline, 3-(chloromethyl)pyridine, propylene oxide, benzoic anhydride, 2-methyl aziridine, pyridine, tetramethylthiourea, and benzimidazole.
  • the amine-based compound is not particularly limited, but may be at least one selected from the group consisting of imidazole, 4-amino pyridine, piperazine, mono ethanol amine, aniline, 2-nitro imidazole, urea, pyrazine, and pyrimidine.
  • Reaction conditions of the first alkylation agent compound and the amine-based compound are not particularly limited, but their reaction may be performed at 50 oC to 170 oC for 6 hours to 24 hours. Also, reaction conditions after addition of the second alkylation agent compound are not particularly limited, but the reaction after the addition of the second alkylation agent compound may be performed at 50 oC to 100 oC for 3 hours to 12 hours.
  • Each reaction ratio of the first alkylation agent compound, the second alkylation agent compound, and the amine-based compound is not particularly limited, but a reaction ratio of the first alkylation agent compound and the amine-based compound may be a weight ratio of 1:1 to 3:1, and a reaction ratio of the first alkylation agent compound and the second alkylation agent compound may be a weight ratio of 1:1 to 4:1.
  • a solvent used for the reaction of the first alkylation agent compound, the second alkylation agent compound, and the amine-based compound is not particularly limited as long as the solvent is a commonly known solvent, but considering solubility and synthesis efficiency, at least one selected from the group consisting of an aqueous solvent (water, purified water, deionized water, etc.), an alcoholic solvent (ethanol, methanol, etc.), and an organic solvent (dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide, etc.) may be used.
  • the present invention provides an electroplating composition including the leveling agent.
  • the electroplating composition according to the present invention includes the leveling agent and a metal ion source.
  • the leveling agent included in the electroplating composition according to the present invention is the same as described above, and thus will be omitted.
  • a concentration (content) of the leveling agent is not particularly limited, but considering uniformity of a circuit pattern and plating efficiency, may be in a range of 3 ml/l to 50 ml/l, for example, 5 ml/l to 20 ml/l.
  • the metal ion source included in the electroplating composition according to the present invention supplies a metal ion in the composition, and a commonly known material may be used.
  • the metal ion source may be a copper ion source.
  • a concentration (content) of the metal ion source is not particularly limited, but considering uniformity and density of a circuit pattern, may be in a range of 100 g/L to 300 g/L, for example, 200 g/L to 250 g/L.
  • the electroplating composition according to the present invention may further include at least one selected from the group consisting of a strong acid, a halogen ion source, a brighteners, and a carrier (inhibitor) to increase physical properties thereof.
  • the strong acid included in the electroplating composition according to the present invention controls pH and serves as an electrolyte, and a commonly known material may be used.
  • the strong acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, sulfonic acid, hydrobromic acid, and fluoroboric acid.
  • a concentration (content) of the strong acid is not particularly limited, but considering pH of the electroplating composition, may be in a range of 50 g/L to 150 g/L, for example, 90 g/L to 110 g/L.
  • the halogen ion source included in the electroplating composition according to the present invention supplies a halogen ion in the composition, and a commonly known material may be used.
  • the halogen ion source may be a chlorine ion source.
  • a concentration (content) of the halogen ion source is not particularly limited, but considering uniformity and density of a circuit pattern, may be in a range of 30 mg/L to 60 mg/L, for example, 40 mg/L to 50 mg/L.
  • the brightener included in the electroplating composition according to the present invention promotes plating by increasing the reduction rate of metal ions, and a commonly known material may be used.
  • the brightener may be at least one selected from the group consisting of bis-(3-sulfopropyl)disulfide (sodium salt), 3-mercapto-1-propanesulfonic acid (sodium salt), 3-amino-1-propanesulfonic acid, O-ethyl-S-(3-sulphopropyl) dithiocarbonate (sodium salt), 3-(2-benzthiazoly-1-thio)-1-propanesulfonic acid (sodium salt), and N,N-dimethyldithiocarbamic acid-(3-sulfopropyl)ester (sodium salt).
  • a concentration (content) of the brightener is not particularly limited, but considering a plating rate, may be in a range of 0.5 ml/L to 5 ml/L
  • the carrier included in the electroplating composition according to the present invention is for increasing the surface flatness of a circuit pattern, and a commonly known material may be used.
  • a concentration (content) of the carrier is not particularly limited, but considering uniformity of a circuit pattern and plating efficiency, may be in a range of 5 ml/l to 15 ml/l, for example, 8 ml/l to 12 ml/l.
  • the present invention provides a method of plating a via hole of a glass via hole substrate by using the electroplating composition.
  • a method of plating a via hole of a glass via hole substrate according to the present invention includes: forming a via hole in a glass substrate; forming an electroless plating layer by performing electroless plating on the glass substrate in which the via hole is formed; and forming an electrolytic plating layer by performing electrolytic plating on the glass substrate on which the electroless plating layer is formed.
  • a via hole H is formed in a glass substrate 201.
  • the via hole H may be formed by a commonly known method, and may be formed to have a tapered shape as shown in FIG. 1.
  • electroless plating is performed on the glass substrate 201 in which the via hole H is formed, to form an electroless plating layer 202 on the inside of the via hole H and a surface of the glass substrate 201.
  • a plating solution composition for performing the electroless plating a commonly known composition may be used.
  • a plating solution composition including copper ions, a copper ion complexing agent, a copper ion reducing agent, a pH adjuster, and an additive may be used.
  • electroless plating conditions are not particularly limited, but may be set to form the electroless plating layer 202 having a thickness of 1 ⁇ m or less in a temperature range of 20-40 oC.
  • electrolytic plating is performed on the glass substrate 201 on which the electroless plating layer 202 is formed, to form an electrolytic plating layer 203, thereby completing the plating (filling) of the via hole H.
  • the electroplating composition described above may be used as a plating solution composition for performing the electrolytic plating.
  • a current density applied during the electrolytic plating by using the electroplating composition may be applied in a specific waveform. That is, referring to FIG. 2, a current density of a stepwise pulse (+current applied)-reverse (-current applied) waveform having an interval of t 1 +t 2 +t 3 +t 4 +t 5 +t 6 and a current density of a direct current waveform (+current applied) having an interval of t 7 may be sequentially applied.
  • a waveform in which a positive current I 1 is maintained for a time t 1 , a positive current I 2 is maintained for a time t 2 , the positive current I 1 is maintained for a time t 3 , a negative current I 3 is maintained for a time t 4 , a negative current I 4 is maintained for a time t 5 , and a negative current I 6 is maintained for a time t 6 , is periodically applied for a predetermined time, and then a positive current I 7 (direct current) is applied for a time t 7 to perform electrolytic plating.
  • a positive current I 7 direct current
  • I 1 may be in a range of 0.5 ASD to 3 ASD
  • I 2 may be in a range of 0.75 ASD to 4.5 ASD
  • I 3 may be in a range of -0.1 ASD to -1 ASD
  • I 4 may be in a range of -1 ASD to -9 ASD
  • I 5 may be in a range of 1 ASD to 6 ASD.
  • t 1 , t 2 , and t 3 may each be in a range of 10 ms to 300 ms
  • t 4 , t 5 , and t 6 may each be in a range of 2 ms to 20 ms
  • t 7 may be in a range of 10 min to 60 min.
  • a current density is applied to a stepwise pulse-reverse waveform (PR) representing an interval of t 1 +t 2 +t 3 +t 4 +t 5 +t 6
  • a current density is applied to a direct current waveform (DC) representing an interval of t 7 , thereby minimizing the formation of dimples and voids and allowing a via hole to be efficiently plated.
  • PR pulse-reverse waveform
  • DC direct current waveform
  • 1,4-butanediol diglycidyl ether and 4-aminopyridine were put into dimethylformamide (DMF), dissolved at 120- 150 °C, and then reacted for 10 hours to 15 hours. Next, benzyl chloride was added thereto, followed by a process of reaction for 5 hours to 8 hours, thereby synthesizing a leveling agent compound.
  • a use ratio of 1,4-butanediol diglycidyl ether and 4-aminopyridine was a weight ratio of 2:1
  • a use ratio of 1,4-butanediol diglycidyl ether and benzyl chloride was a weight ratio of 2:1.
  • Leveling agents were synthesized in the same manner as in Example 1, except that reaction raw materials shown in Table 1 below were used instead of 1,4-butanediol diglycidyl ether, 4-aminopyridine, and benzyl chloride.
  • Example 1 1,4-butanediol diglycidyl ether 4-aminopyridine benzyl chloride
  • Example 2 1,4-butanediol diglycidyl ether piperazine aniline
  • Example 3 1,4-butanediol diglycidyl ether monoethanolamine 3-(chloromethyl)pyridine
  • Example 4 neopentyl glycol diglycidyl ether aniline propylene oxide
  • Example 5 neopentyl glycol diglycidyl ether 2-nitroimidazole benzoic anhydride
  • Example 6 neopentyl glycol diglycidyl ether urea 2-methylaziridine
  • Example 7 1,2-bis(2-chloroethoxy)ethane urea pyridine
  • Example 8 1,2-bis(2-chloroethoxy)ethane pyrazine tetramethylthiourea
  • Example 9 1,2-bis(2-chloroethoxy)ethane
  • an electroplating composition including 230 g/L of copper sulfate pentahydrate, 100 g/L of sulfuric acid, 40-50 mg/L of hydrochloric acid, 1-3.5 ml/L of bis-(sodium sulfopropyl)-disulfide, 10 ml/L of carrier, and 10 ml/L of the leveling agent of Example 1.
  • An electroplating composition was prepared in the same manner as in Preparation Example 1, except that the leveling agent of Example 2 was used instead of the leveling agent of Example 1.
  • An electroplating composition was prepared in the same manner as in Preparation Example 1, except that a known leveling agent (KDY2, available from Dicolloy) of the related art was used instead of the leveling agent of Example 1.
  • KDY2 available from Dicolloy
  • a tapered via hole having a top width of 150 ⁇ m and a bottom width of 20 ⁇ m was formed in a glass substrate having a thickness of 400 ⁇ m.
  • cleaning was performed by immersing the glass substrate in 25 % NaOH for 5 minutes.
  • the glass substrate in which the via hole was formed was put into a plating solution composition including copper ions, a copper ion complexing agent, a copper ion reducing agent, a pH adjuster, and an additive, followed by electroless plating at 34 °C, thereby forming an electroless plating layer having a thickness of about 0.5-0.8 ⁇ m.
  • the inside of the via hole was plated with the electroplating compositions prepared in Preparation Examples 1 and 2 and Comparative Preparation Example 1.
  • plating conditions were set as follows.
  • FIG. 3 it was confirmed that when electrolytic plating was performed using the electroplating compositions of Preparation Examples 1 and 2 according to the present invention, the formation of voids was minimized while plating was performed in stages from a base surface of a substrate. In contrast, it was confirmed that when electrolytic plating was performed using the electroplating composition of Comparative Preparation Example 1, a large void was formed in the central portion.
  • Condition 1 Non-occurrence (plating is well performed in stages from a base surface)
  • Condition 2 Non-occurrence (plating is well performed in stages from a base surface)
  • Condition 3 Occurrence in the central portion

Abstract

The present invention relates to a leveling agent and an electroplating composition including the same, and when a via hole of a glass substrate is plated with the electroplating composition according to the present invention, the inside of the via hole may be plated while the formation of dimples or voids is minimized.

Description

A LEVELING AGENT AND AN ELECTROPLATING COMPOSITION INCLUDING THE SAME
The present invention relates to a leveling agent that may allow the inside of a via hole (or through hole) formed in a glass via hole substrate (TGV substrate) to be efficiently plated and an electroplating composition including the same.
Glass via hole substrates (TGV substrates) are attracting attention as a component material for various electronic devices due to characteristics of high thermal stability and low surface roughness. In order to bond a semiconductor chip to a glass via hole substrate or to form a circuit wiring on a glass via hole substrate, an electrode formation technique by via metallization acts as an important factor.
In the related art, for via metallization of a glass via hole substrate, a side seed metal layer is formed by electroless plating, and a plating method of filling a via hole by electrolytic plating is applied.
However, in the plating method, voids or seams are formed in via holes due to the influence of a via hole aspect ratio, a hole diameter, an additive to a plating solution, resulting in a deterioration in electrical characteristics of a glass via hole substrate or reliability of a device package.
Therefore, there is a need to develop a technology capable of controlling the occurrence of voids or seams during a plating process for via metallization of a glass via hole substrate.
RELATED ART DOCUMENT
Patent Document
(Patent document 0001) Korean Patent Publication No. 2019-0003050
The present invention provides a leveling agent that allows the inside of a via hole (or through hole) formed in a glass via hole substrate to be efficiently and uniformly plated.
Also, the present invention provides an electroplating composition including the leveling agent.
Also, the present invention provides a method of plating a via hole of a glass via hole substrate by using the electroplating composition.
In order to solve the problem, the present invention provides a leveling agent which is a compound represented by Formulae 1 to 3 below.
[Formula 1]
Figure PCTKR2022011179-appb-img-000001
[Formula 2]
Figure PCTKR2022011179-appb-img-000002
[Formula 3]
Figure PCTKR2022011179-appb-img-000003
In Formulae 1 to 3,
R1 and R6 are each independently selected from the group consisting of a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a C1-C10 alkyl group, a C6-C20 aryl group, and a C2-C20 heteroaryl group,
R2 to R5 are each independently selected from the group consisting of a hydroxyl group (-OH), a C2-C20 heteroaryl group, -NR7R8, and -NR9-L3-R10,
L1 and L2 are each independently selected from the group consisting of oxygen (O) and a C2-C20 heteroarylene group,
a and b are each independently an integer from 1 to 5,
n is an integer from 1 to 10,
R7 to R10 are each independently selected from the group consisting of hydrogen (H), a hydroxyl group (-OH), a C6-C20 aryl group, and a C2-C20 heteroaryl group,
L3 is a C1-C5 alkylene group, and
an alkyl group, an aryl group, and a heteroaryl group of each of R1 and R6 and a heteroarylene group of each of L1 and L2 are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of a hydroxyl group (-OH), an amino group (-NH2), a halogen group, and a C1-C10 alkyl group.
The present invention provides an electroplating composition including a metal ion source and the leveling agent.
Also, the present invention provides a method of plating a via hole of a glass via hole substrate, the method including: forming a via hole in a glass substrate; forming an electroless plating layer by performing electroless plating on the glass substrate in which the via hole is formed; and forming an electrolytic plating layer by performing electrolytic plating on the glass substrate on which the electroless plating layer is formed, and the electrolytic plating is performed by using the electroplating composition.
A leveling agent according to the present invention can allow a decomposition rate and concentration of an additive (e.g., brighteners, carriers, and accelerating agents) included in an electroplating composition to be maintained constant during a plating process. Therefore, when plating (filling) of a via hole (or through hole) formed in a glass via hole substrate is performed by using an electroplating composition including the leveling agent according to the present invention, the occurrence of voids or seams can be minimized, thereby improving the reliability and stability of the glass via hole substrate or a device package.
FIG. 1 schematically shows a process of plating a via hole of a glass via hole substrate, according to an embodiment of the present invention.
FIG. 2 shows a waveform of a current density applied during electrolytic plating in a process of plating a via hole of a glass via hole substrate, according to an embodiment of the present invention.
FIG. 3 shows experiment results according to Experiment Example 1 of the present invention.
The terms or words used in the description of the present invention and claims shall not be interpreted as being limited to ordinary or dictionary meanings and the terms or words should be interpreted as meanings and concepts consistent with the technical idea of the present invention, based on the principle that an inventor may properly define the concept of a term to explain his own invention in the best way.
The present invention relates to a leveling agent that allows the inside of a via hole (through hole) formed in a glass substrate to be efficiently plated (filled), and an electroplating composition including the same, which will be described in detail as follows.
The leveling agent according to the present invention may be a compound represented by Formulae 1 to 3.
[Formula 1]
Figure PCTKR2022011179-appb-img-000004
[Formula 2]
Figure PCTKR2022011179-appb-img-000005
[Formula 3]
Figure PCTKR2022011179-appb-img-000006
In Formulae 1 to 3,
R1 and R6 are identical to or different from each other, and are each independently selected from the group consisting of a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a C1-C10 alkyl group (e.g., a C1-C5 alkyl group), a C6-C20 aryl group (e.g., a C6-C10 aryl group), and a C2-C20 heteroaryl group (e.g., a C3-C10 heteroaryl group),
R2 to R5 are identical to or different from each other, and are each independently selected from the group consisting of a hydroxyl group (-OH), a C2-C20 heteroaryl group (e.g., a C3-C10 heteroaryl group), -NR7R8, and -NR9-L3-R10,
L1 and L2 are identical to or different from each other, and are each independently selected from the group consisting of oxygen (O) and a C2-C20 heteroarylene group (e.g., a C3-C10 heteroarylene group),
a and b are each independently an integer from 1 to 5, and n is an integer from 1 to 10,
R7 to R10 are identical to or different from each other, and are each independently selected from the group consisting of hydrogen (H), a hydroxyl group (-OH), a C6-C20 aryl group (e.g., a C6-C10 aryl group), and a C2-C20 heteroaryl group (e.g., a C3-C10 heteroaryl group),
L3 is a C1-C5 alkylene group (e.g., a C1-C3 alkylene group), and
an alkyl group, an aryl group, and a heteroaryl group of R1, an alkyl group, an aryl group, and a heteroaryl group of R6, a heteroarylene group of L1, and a heteroarylene group of L2 are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of a hydroxyl group (-OH), an amino group (-NH2), a halogen group, and a C1-C10 alkyl group.
Specifically, considering the interaction between the leveling agent and an additive (e.g., brighteners, carriers, and accelerating agents) added to the electroplating composition, R1　and R6 may each independently be selected from the group consisting of a sulfonic acid group (-SO3H), a hydroxyl group (-OH),
Figure PCTKR2022011179-appb-img-000007
,　
Figure PCTKR2022011179-appb-img-000008
,　
Figure PCTKR2022011179-appb-img-000009
, and　
Figure PCTKR2022011179-appb-img-000010
.
Also, R2　to R5 may each independently be selected from the group consisting of a hydroxyl group (-OH),
Figure PCTKR2022011179-appb-img-000011
,　
Figure PCTKR2022011179-appb-img-000012
,　
Figure PCTKR2022011179-appb-img-000013
,　
Figure PCTKR2022011179-appb-img-000014
, and　
Figure PCTKR2022011179-appb-img-000015
.
Also, L1 and L2 may each independently be selected from the group consisting of oxygen (O) and
Figure PCTKR2022011179-appb-img-000016
.
Also, a and b may each independently be an integer from 1 to 3, and n may be an integer of 1.
Specifically, the leveling agent according to the present invention may be embodied as compounds represented by C-1 to C-4 below, but is not limited thereto.
Figure PCTKR2022011179-appb-img-000017
Figure PCTKR2022011179-appb-img-000018
Figure PCTKR2022011179-appb-img-000019
Figure PCTKR2022011179-appb-img-000020
The heteroaryl group in the present invention may indicate a monovalent aromatic ring group including at least one hetero atom such as N, O, S, F, etc.
The halogen group in the present invention may indicate a fluorine group, a bromine group, a chlorine group, an iodine group, and the like.
A method of synthesizing a leveling agent according to the present invention is not particularly limited, but a method of reacting an alkylation agent compound with an amine-based compound in the presence of a solvent may be employed to increase synthesis efficiency. Specifically, after a first alkylation agent compound and an amine-based compound are added to a solvent and reacted, a second alkylation agent compound is added thereto and reacted, to thereby synthesize a leveling agent according to the present invention.
The first alkylation agent compound is not particularly limited, but may be at least one selected from the group consisting of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,2-bis(2-chloroethoxy)ethane.
The second alkylation agent compound is not particularly limited, but may be at least one selected from the group consisting of 1,3-propanesultone, epichlorohydrin, benzyl chloride, aniline, 3-(chloromethyl)pyridine, propylene oxide, benzoic anhydride, 2-methyl aziridine, pyridine, tetramethylthiourea, and benzimidazole.
The amine-based compound is not particularly limited, but may be at least one selected from the group consisting of imidazole, 4-amino pyridine, piperazine, mono ethanol amine, aniline, 2-nitro imidazole, urea, pyrazine, and pyrimidine.
Reaction conditions of the first alkylation agent compound and the amine-based compound are not particularly limited, but their reaction may be performed at 50 ºC to 170 ºC for 6 hours to 24 hours. Also, reaction conditions after addition of the second alkylation agent compound are not particularly limited, but the reaction after the addition of the second alkylation agent compound may be performed at 50 ºC to 100 ºC for 3 hours to 12 hours.
Each reaction ratio of the first alkylation agent compound, the second alkylation agent compound, and the amine-based compound is not particularly limited, but a reaction ratio of the first alkylation agent compound and the amine-based compound may be a weight ratio of 1:1 to 3:1, and a reaction ratio of the first alkylation agent compound and the second alkylation agent compound may be a weight ratio of 1:1 to 4:1.
A solvent used for the reaction of the first alkylation agent compound, the second alkylation agent compound, and the amine-based compound is not particularly limited as long as the solvent is a commonly known solvent, but considering solubility and synthesis efficiency, at least one selected from the group consisting of an aqueous solvent (water, purified water, deionized water, etc.), an alcoholic solvent (ethanol, methanol, etc.), and an organic solvent (dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide, etc.) may be used.
The leveling agent according to the present invention may be a monomer (n=1) itself obtained through the above synthesis method, or a polymer (n=2 to 10) obtained by performing a polymerization reaction of the related art by using the obtained monomer.
The present invention provides an electroplating composition including the leveling agent. Specifically, the electroplating composition according to the present invention includes the leveling agent and a metal ion source.
The leveling agent included in the electroplating composition according to the present invention is the same as described above, and thus will be omitted. A concentration (content) of the leveling agent is not particularly limited, but considering uniformity of a circuit pattern and plating efficiency, may be in a range of 3 ml/l to 50 ml/l, for example, 5 ml/l to 20 ml/l.
The metal ion source included in the electroplating composition according to the present invention supplies a metal ion in the composition, and a commonly known material may be used. Specifically, the metal ion source may be a copper ion source. A concentration (content) of the metal ion source is not particularly limited, but considering uniformity and density of a circuit pattern, may be in a range of 100 g/L to 300 g/L, for example, 200 g/L to 250 g/L.
The electroplating composition according to the present invention may further include at least one selected from the group consisting of a strong acid, a halogen ion source, a brighteners, and a carrier (inhibitor) to increase physical properties thereof.
The strong acid included in the electroplating composition according to the present invention controls pH and serves as an electrolyte, and a commonly known material may be used. Specifically, the strong acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, sulfonic acid, hydrobromic acid, and fluoroboric acid. A concentration (content) of the strong acid is not particularly limited, but considering pH of the electroplating composition, may be in a range of 50 g/L to 150 g/L, for example, 90 g/L to 110 g/L.
The halogen ion source included in the electroplating composition according to the present invention supplies a halogen ion in the composition, and a commonly known material may be used. Specifically, the halogen ion source may be a chlorine ion source. A concentration (content) of the halogen ion source is not particularly limited, but considering uniformity and density of a circuit pattern, may be in a range of 30 mg/L to 60 mg/L, for example, 40 mg/L to 50 mg/L.
The brightener included in the electroplating composition according to the present invention promotes plating by increasing the reduction rate of metal ions, and a commonly known material may be used. Specifically, the brightener may be at least one selected from the group consisting of bis-(3-sulfopropyl)disulfide (sodium salt), 3-mercapto-1-propanesulfonic acid (sodium salt), 3-amino-1-propanesulfonic acid, O-ethyl-S-(3-sulphopropyl) dithiocarbonate (sodium salt), 3-(2-benzthiazoly-1-thio)-1-propanesulfonic acid (sodium salt), and N,N-dimethyldithiocarbamic acid-(3-sulfopropyl)ester (sodium salt). A concentration (content) of the brightener is not particularly limited, but considering a plating rate, may be in a range of 0.5 ml/L to 5 ml/L, for example, 1 ml/L to 3.5 ml/L.
The carrier included in the electroplating composition according to the present invention is for increasing the surface flatness of a circuit pattern, and a commonly known material may be used. A concentration (content) of the carrier is not particularly limited, but considering uniformity of a circuit pattern and plating efficiency, may be in a range of 5 ml/l to 15 ml/l, for example, 8 ml/l to 12 ml/l.
The present invention provides a method of plating a via hole of a glass via hole substrate by using the electroplating composition. Specifically, a method of plating a via hole of a glass via hole substrate according to the present invention includes: forming a via hole in a glass substrate; forming an electroless plating layer by performing electroless plating on the glass substrate in which the via hole is formed; and forming an electrolytic plating layer by performing electrolytic plating on the glass substrate on which the electroless plating layer is formed.
First, a via hole H is formed in a glass substrate 201. The via hole H may be formed by a commonly known method, and may be formed to have a tapered shape as shown in FIG. 1.
Next, electroless plating is performed on the glass substrate 201 in which the via hole H is formed, to form an electroless plating layer 202 on the inside of the via hole H and a surface of the glass substrate 201. As a plating solution composition for performing the electroless plating, a commonly known composition may be used. For example, a plating solution composition including copper ions, a copper ion complexing agent, a copper ion reducing agent, a pH adjuster, and an additive may be used. Also, electroless plating conditions are not particularly limited, but may be set to form the electroless plating layer 202 having a thickness of 1 μm or less in a temperature range of 20-40 ºC.
Next, electrolytic plating is performed on the glass substrate 201 on which the electroless plating layer 202 is formed, to form an electrolytic plating layer 203, thereby completing the plating (filling) of the via hole H. As a plating solution composition for performing the electrolytic plating, the electroplating composition described above may be used.
In this regard, a current density applied during the electrolytic plating by using the electroplating composition may be applied in a specific waveform. That is, referring to FIG. 2, a current density of a stepwise pulse (+current applied)-reverse (-current applied) waveform having an interval of t1+t2+t3+t4+t5+t6 and a current density of a direct current waveform (+current applied) having an interval of t7 may be sequentially applied. Specifically, a waveform, in which a positive current I1 is maintained for a time t1, a positive current I2 is maintained for a time t2, the positive current I1 is maintained for a time t3, a negative current I3 is maintained for a time t4, a negative current I4 is maintained for a time t5, and a negative current I6 is maintained for a time t6, is periodically applied for a predetermined time, and then a positive current I7 (direct current) is applied for a time t7 to perform electrolytic plating.
In this regard, in plating the inside of the via hole H, in order to minimize the formation of dimples and voids, I1 may be in a range of 0.5 ASD to 3 ASD, I2 may be in a range of 0.75 ASD to 4.5 ASD, I3 may be in a range of -0.1 ASD to -1 ASD, I4 may be in a range of -1 ASD to -9 ASD, and I5 may be in a range of 1 ASD to 6 ASD. Also, t1, t2, and t3 may each be in a range of 10 ms to 300 ms, t4, t5, and t6 may each be in a range of 2 ms to 20 ms, and t7 may be in a range of 10 min to 60 min.
As such, during electrolytic plating, after a current density is applied to a stepwise pulse-reverse waveform (PR) representing an interval of t1+t2+t3+t4+t5+t6, a current density is applied to a direct current waveform (DC) representing an interval of t7, thereby minimizing the formation of dimples and voids and allowing a via hole to be efficiently plated.
Hereinafter, the present invention will be described in more detail according to Examples. However, the following Examples are provided for illustrating the present invention. It is apparent to a person skilled in the art that various modifications and alterations may be made without departing from the scope and spirit of the present invention, and the scope of the present invention is not limited thereto.
[Example 1]
1,4-butanediol diglycidyl ether and 4-aminopyridine were put into dimethylformamide (DMF), dissolved at 120- 150 ℃, and then reacted for 10 hours to 15 hours. Next, benzyl chloride was added thereto, followed by a process of reaction for 5 hours to 8 hours, thereby synthesizing a leveling agent compound. In this regard, a use ratio of 1,4-butanediol diglycidyl ether and 4-aminopyridine was a weight ratio of 2:1, and a use ratio of 1,4-butanediol diglycidyl ether and benzyl chloride was a weight ratio of 2:1.
[Examples 2 to 9]
Leveling agents were synthesized in the same manner as in Example 1, except that reaction raw materials shown in Table 1 below were used instead of 1,4-butanediol diglycidyl ether, 4-aminopyridine, and benzyl chloride.
Category First compound Second compound Third compound
Example 1 1,4-butanediol diglycidyl ether 4-aminopyridine benzyl chloride
Example 2 1,4-butanediol diglycidyl ether piperazine aniline
Example 3 1,4-butanediol diglycidyl ether monoethanolamine 3-(chloromethyl)pyridine
Example 4 neopentyl glycol diglycidyl ether aniline propylene oxide
Example 5 neopentyl glycol diglycidyl ether 2-nitroimidazole benzoic anhydride
Example 6 neopentyl glycol diglycidyl ether urea 2-methylaziridine
Example 7 1,2-bis(2-chloroethoxy)ethane urea pyridine
Example 8 1,2-bis(2-chloroethoxy)ethane pyrazine tetramethylthiourea
Example 9 1,2-bis(2-chloroethoxy)ethane pyrimidine benzimidazole
[Preparation Example 1]
Prepared was an electroplating composition including 230 g/L of copper sulfate pentahydrate, 100 g/L of sulfuric acid, 40-50 mg/L of hydrochloric acid, 1-3.5 ml/L of bis-(sodium sulfopropyl)-disulfide, 10 ml/L of carrier, and 10 ml/L of the leveling agent of Example 1.
[Preparation Example 2]
An electroplating composition was prepared in the same manner as in Preparation Example 1, except that the leveling agent of Example 2 was used instead of the leveling agent of Example 1.
[Comparative Preparation Example 1]
An electroplating composition was prepared in the same manner as in Preparation Example 1, except that a known leveling agent (KDY2, available from Dicolloy) of the related art was used instead of the leveling agent of Example 1.
[Experimental Example 1]
A tapered via hole having a top width of 150 μm and a bottom width of 20 μm was formed in a glass substrate having a thickness of 400 μm. Next, cleaning was performed by immersing the glass substrate in 25 % NaOH for 5 minutes. Afterwards, the glass substrate in which the via hole was formed was put into a plating solution composition including copper ions, a copper ion complexing agent, a copper ion reducing agent, a pH adjuster, and an additive, followed by electroless plating at 34 °C, thereby forming an electroless plating layer having a thickness of about 0.5-0.8 μm. Next, the inside of the via hole was plated with the electroplating compositions prepared in Preparation Examples 1 and 2 and Comparative Preparation Example 1. When the plating was performed by using the electroplating compositions, plating conditions were set as follows.
- Temperature of electroplating composition: 21-24 °C
- Stirring: 0.5-1.5 LPM/con.
- Electrode: Insoluble electrode
- Current density: Apply a direct current (DC) waveform after applying a stepwise pulse-reverse waveform under the conditions of Table 2 below
Current density (ASD) Application time (ms) of each pulse
 Application time (ms) of each reverse
 Total application time (min.) of pulse-reverse
 Total application time (min.) of DC
I1 I2 I3 I4 I5 10-300 2-20 45 30
1 3 -0.5 -3 2
After the plating of the inside of the via hole was completed, a cross-section of the glass substrate was checked with an optical microscope, and the result is shown in FIG. 3. Referring to FIG. 3, it was confirmed that when electrolytic plating was performed using the electroplating compositions of Preparation Examples 1 and 2 according to the present invention, the formation of voids was minimized while plating was performed in stages from a base surface of a substrate. In contrast, it was confirmed that when electrolytic plating was performed using the electroplating composition of Comparative Preparation Example 1, a large void was formed in the central portion.
[Experimental Example 2]
When electrolytic plating was performed using the electroplating composition of Preparation Example 1 as in Experimental Example 1, a condition for applying current density was adjusted as shown in Table 3 below to plate the inside of a via hole. After the plating was completed, whether voids were formed in a cross-section of a glass substrate was evaluated, and the result is shown in Table 4 below.
Category Current density (ASD) Application time (ms) of each pulse Application time (ms) of each reverse Total application time (min.) of pulse-reverse Total application time (min.) of DC
I1 I2 I3 I4 I5
Condition 1
(PR->DC)		 1 3 -0.5 -3 2 10-300 2-20 45 30
Condition 2 (PR->DC) 1 3 -0.5 -3 2 10-300 2-20 60 30
Condition 3 (DC->PR->DC) 1 3 -0.5 -3 2 10-300 2-20 60 40
(First DC: 10
Second DC: 30)
Category Occurrence of voids
Condition
1 Non-occurrence (plating is well performed in stages from a base surface)
Condition 2 Non-occurrence (plating is well performed in stages from a base surface)
Condition 3 Occurrence in the central portion
Referring to Table 4, it was confirmed that when a via hole was plated with an electroplating composition according to the present invention, the plating of the via hole was well performed without occurrence of voids by sequentially applying a stepwise pulse-reverse waveform and a DC waveform.

Claims (8)

  1. A leveling agent for an electroplating composition, wherein the leveling agent is selected from the group consisting of compounds represented by Formulae 1 to 3 below:
    [Formula 1]
    Figure PCTKR2022011179-appb-img-000021
    [Formula 2]
    Figure PCTKR2022011179-appb-img-000022
    [Formula 3]
    Figure PCTKR2022011179-appb-img-000023
    wherein, in Formulae 1 to 3,
    R1 and R6 are each independently selected from the group consisting of a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a C1-C10 alkyl group, a C6-C20 aryl group, and a C2-C20 heteroaryl group,
    R2 to R5 are each independently selected from the group consisting of a hydroxyl group (-OH), a C2-C20 heteroaryl group, -NR7R8, and -NR9-L3-R10,
    L1 and L2 are each independently selected from the group consisting of oxygen (O) and a C2-C20 heteroarylene group,
    a and b are each independently an integer from 1 to 5, and n is an integer from 1 to 10,
    R7 to R10 are each independently selected from the group consisting of hydrogen (H), a hydroxyl group (-OH), a C6-C20 aryl group, and a C2-C20 heteroaryl group,
    L3 is a C1-C5 alkylene group, and
    an alkyl group, an aryl group, and a heteroaryl group of each of R1 and R6 and a heteroarylene group of each of L1 and L2 are each independently unsubstituted or substituted with at least one substituent selected from the group consisting of a hydroxyl group (-OH), an amino group (-NH2), a halogen group, and a C1-C10 alkyl group.
  2. The leveling agent of claim 1, wherein R1 and R6 are each independently selected from the group consisting of a sulfonic acid group (-SO3H), a hydroxyl group (-OH),
    Figure PCTKR2022011179-appb-img-000024
    ,
    Figure PCTKR2022011179-appb-img-000025
    ,
    Figure PCTKR2022011179-appb-img-000026
    , and
    Figure PCTKR2022011179-appb-img-000027
    .
  3. The leveling agent of claim 1, wherein R2 to R5 are each independently selected from the group consisting of a hydroxyl group (-OH),
    Figure PCTKR2022011179-appb-img-000028
    ,　
    Figure PCTKR2022011179-appb-img-000029
    ,　
    Figure PCTKR2022011179-appb-img-000030
    ,　
    Figure PCTKR2022011179-appb-img-000031
    , and　
    Figure PCTKR2022011179-appb-img-000032
    .
  4. The leveling agent of claim 1, wherein L1 and L2 are each independently selected from the group consisting of oxygen (O) and
    Figure PCTKR2022011179-appb-img-000033
    .
  5. The leveling agent of claim 1, wherein a and b are each independently an integer from 1 to 3, and n is an integer of 1.
  6. An electroplating composition comprising:
    a metal ion source; and
    the leveling agent according to any one of claims 1 to 5.
  7. A method of plating a via hole of a glass via hole substrate, the method comprising:
    forming a via hole in a glass substrate;
    forming an electroless plating layer by performing electroless plating on the glass substrate in which the via hole is formed; and
    forming an electrolytic plating layer by performing electrolytic plating on the glass substrate on which the electroless plating layer is formed, wherein the electrolytic plating is performed by using the electroplating composition according to claim 6.
  8. The method of claim 7, wherein a current density in a stepwise pulse-reverse waveform and a current density in a direct current waveform are sequentially applied in the electrolytic plating.
PCT/KR2022/011179 2021-08-04 2022-07-29 A leveling agent and an electroplating composition including the same WO2023013987A1 (en)

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KR20180051865A (en) * 2016-11-09 2018-05-17 솔브레인 주식회사 Leveling agent and electroplating composition comprising the same
KR102339866B1 (en) * 2021-08-04 2021-12-16 와이엠티 주식회사 Leveler and electroplating compositior plating through glass via substrate

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KR102339866B1 (en) * 2021-08-04 2021-12-16 와이엠티 주식회사 Leveler and electroplating compositior plating through glass via substrate

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