TW201934811A - High flatness copper electroplating method and copper electroplating product having immersion in the pretreatment solution performed prior to electroplating so as to enable adsorption of the first leveling agent to obtain the high flatness copper film coating - Google Patents

Abstract

The present invention provides a high flatness copper electroplating method and a copper electroplating product. The copper electroplating method includes: a pretreatment step for immersing a substrate in a pretreatment solution containing a first leveling agent but no copper precursor; an immersing step for immersing the pretreated substrate in a plating solution including the first leveling agent, the second leveling agent, an inhibitor, an accelerator and a copper precursor; and an electrodepositing step for applying current to the substrate immersed in the plating solution to electrodeposit the copper film. According to an embodiment of the present invention, when copper electroplating is performed, immersion in the pretreatment solution is performed prior to electroplating so as to enable adsorption of the first leveling agent to obtain the high flatness copper film coating.

Description

High flatness copper electroplating method and copper electroplating product

The present invention relates to a copper plating method and a copper electroplating product, and more specifically, to a high flatness copper plating method and a copper electroplating product.

Electroplating is a method of depositing a metal or a metal oxide using electrons supplied from the outside. Like a common electrochemical system, a plating system includes an electrode, an electrolyte, and a power source for supplying electrons. To perform copper electroplating, a patterned substrate is used as a cathode, and phosphorus-containing copper or an insoluble material is used as an anode. The electrolyte basically contains copper ions. To reduce the resistance of the electrolyte itself, it contains sulfuric acid, and to improve the adsorption of copper ions and additives, it contains chloride ions.

In recent years, in order to improve the performance of semiconductor wafers and save manufacturing costs, the demand for developing products using a panel level package (PLP) process has increased. Technical requirements have also increased.

[Prior Art Document] [Patent Document] Patent Document 1: Korean Granted Patent No. 10-1705734.

[Problems to be Solved by the Invention]

The technical problem to be solved by the present invention is to provide a high flatness copper plating method and a copper electroplated product.

The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and those with ordinary knowledge in the technical field to which this case belongs can clearly understand other technical problems not mentioned by the following description.

[Means to solve the problem]

In order to achieve the technical problem, an embodiment of the present invention provides a high-flatness copper electroplating method.

The copper electroplating method may include a pretreatment step of immersing the substrate in a pretreatment solution, the pretreatment solution contains a first leveling agent but does not contain a copper precursor; the immersion step, after the pretreatment, The substrate is immersed in a plating solution, the plating solution includes the first leveling agent, the second leveling agent, an inhibitor, an accelerator, and a copper precursor; and an electrodeposition step, wherein the substrate is immersed in the plating solution. A current is applied to the liquid substrate to deposit a copper film.

In this case, the substrate has a wiring pitch of 20 μm or less.

At this time, it is characterized in that, in the pretreatment step, the first leveling agent is added to the pretreatment solution at a concentration of 100 mg / l to 5000 mg / l.

At this time, it is characterized in that the first leveling agent is used for manufacturing the protruding copper film.

At this time, it is characterized in that the second leveling agent is used for manufacturing the recessed copper film.

At this time, it is characterized in that, in the step of immersing the substrate after the pretreatment in the plating solution, the first leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. .

At this time, it is characterized in that in the step of immersing the substrate after the pretreatment in the plating solution, the second leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. .

At this time, the inhibitor includes polyoxyalkylene glycol, carboxymethyl cellulose, N-nonylphenol polyethylene glycol ether, octanediol diethylene glycol ether, oleic acid polyethylene glycol ester, Polyethylene glycol, polyethylene glycol dimethyl ether, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol, polypropylene glycol, polyvinyl alcohol, stearyl alcohol polyethylene glycol ether, stearin Acid polyethylene glycol ester, 3-methyl-1-butyn-3-ol, 3-methyl-penten-3-ol, L-ethynylcyclohexanol, phenylpropynol, 3-phenyl 1-butyn-3-ol, propargyl alcohol, methylbutanol-ethylene oxide, 2-methyl-4-chloro-3-butyn-2-ol, dimethylhexanediol, Methylhexylene glycol-ethylene oxide, dimethyl octanediol, phenylbutynol or 1,4-butanediol diglycidyl ether.

At this time, the accelerator contains (O- (dithiocarbonate) -S- (3-sulfopropyl) -ester, 3-[(amino-iminomethyl) -thiol] -1- Propanesulfonic acid, 3- (benzothiazole-2-mercapto) -propylsulfonic acid, bis- (sulfopropyl) -sodium disulfide, N, N-dimethyldithiocarbamoylpropanesulfonic acid , 3,3-thiobis (1-propanesulfonic acid), 2-hydroxy-3- [tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, sodium 2,3-dimercaptopropanepropanesulfonic acid , 3-mercapto-1-propanesulfonic acid, N, N-bis (4-sulfobutyl) -3,5-dimethylaniline, 2-mercapto-5-benzimidazole sulfonate, 5,5 ' -Dithiobis (2-nitrobenzoic acid), DL-cysteine, 4-mercapto-benzenesulfonic acid or 5-mercapto-1H-tetrazole-1-methanesulfonic acid.

At this time, the accelerator and the inhibitor each independently have a molecular weight in a range of 100 g / mol to 100,000 g / mol.

At this time, it is characterized in that the accelerator and the inhibitor are independently added to the plating solution at a concentration ranging from 0.1 mg / l to 1,000 mg / l.

At this time, it is characterized in that in the step of electrodepositing the copper film, a current is applied in a current density range of 1 ASD to 15 ASD (Ampere per square Decimeter).

In order to achieve the technical problem, an embodiment of the present invention provides a copper electroplated product, which is characterized in that the copper electroplated product is manufactured by the copper electroplating method.

[Inventive effect]

According to an embodiment of the present invention, a substrate is immersed in a pre-treatment solution containing a first leveling agent but not containing a copper precursor, and the first leveling agent is adsorbed on the substrate, so that a high-flatness copper plating film can be formed. .

It should be understood that the effects of the present invention are not limited to the effects described, but include all the effects that can be deduced from the detailed description of the present invention or the constitution of the present invention described in the scope of the patent application.

Hereinafter, the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different ways, so it is not limited to the embodiments described here. In addition, in order to clearly explain the present invention, parts irrelevant to the description are omitted, and similar elements are marked with similar elements throughout the specification.

Throughout the description, when a part is "connected (connected, contacted, or combined)" with another part, this includes not only the case of "directly connected" but also the case of "indirect connection" with other components in between. In addition, when a certain part “includes” a certain component, unless there is a particularly contradictory record, it means that another component can also be included, that is, it does not exclude having another component.

The terms used in the present specification are used to describe specific embodiments, and do not limit the present invention. Regarding the expression of the singular, unless the context clearly indicates different meanings, it includes the expression of the plural. It should be understood that terms such as "including" or "having" in this specification are used to specify the existence of features, digits, steps, actions, components, accessories or combinations thereof described in the specification, rather than excluding one or more of them in advance. Presence or other possibility of other features or digits, steps, actions, components, parts or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

An embodiment of the present invention describes a high-flatness copper plating method.

FIG. 1 is a flowchart showing a copper plating method according to an embodiment of the present invention.

Referring to FIG. 1, the copper electroplating method may include a pre-processing step S100, in which a substrate is immersed in a pre-processing solution, the pre-processing solution contains a first leveling agent but does not contain a copper precursor; the dipping step S200 Immersing the substrate after the pretreatment in a plating solution, the plating solution including the first leveling agent, the second leveling agent, an inhibitor, an accelerator, and a copper precursor; and an electrodeposition step S300, A current is applied to a substrate immersed in the plating solution to deposit a copper film by electric current.

At this time, the substrate is characterized in that the substrate has a wiring pitch of 20 μm or less in order to realize high performance of mobile semiconductor wafers and save manufacturing costs.

At this time, in the pre-processing step S100, the first leveling agent functions to activate the interface and guide the plating solution to penetrate into the wiring, and uniformly supplies the electrolyte in the plating solution to the surface of the substrate, thereby enabling Get high flatness effect.

At this time, in the pre-processing step S100, by immersing the substrate in a pre-treatment solution containing a first leveling agent but not containing a copper precursor, the first leveling agent is adsorbed on the substrate, thereby Able to form high flatness copper plating film.

At this time, it is characterized in that, in the pre-processing step S100, the first leveling agent is added to the pre-processing solution at a concentration of 100 mg / l to 5000 mg / l.

At this time, when the concentration of the first leveling agent is less than 100 mg / l, the first leveling agent cannot sufficiently penetrate into the wiring, so it cannot be expected that the first leveling agent will affect the plating result.

At this time, when the concentration of the first leveling agent exceeds 5000 mg / l, the first leveling agent is adsorbed excessively, which may cause uneven coating.

At this time, it is characterized in that, in step S200 of immersing the substrate after the pretreatment in the plating solution, the first leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. in.

At this time, it is characterized in that the first leveling agent is used for manufacturing the protruding copper film.

At this time, in the copper electroplating process of forming a copper film on the substrate, the first leveling agent is adsorbed on a portion where a high current density plating film is formed to suppress reduction of copper ions, thereby improving the uniformity and flatness of the copper plating film. As a result, the uniformity and flatness of the pattern can be improved after plating.

At this time, it is characterized in that in step S200 of immersing the substrate after the pretreatment in the plating solution, the second leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. in.

At this time, it is characterized in that the second leveling agent is used for manufacturing the recessed copper film.

At this time, in the copper electroplating process of forming a copper film on the substrate, the second leveling agent is adsorbed on a portion where a high current density plating film is formed to suppress reduction of copper ions, thereby improving the uniformity and flatness of the copper plating film As a result, the uniformity and flatness of the pattern can be improved after plating.

For example, the first leveling agent may have a structure of the following Chemical Formula 1.

[Chemical Formula 1]

At this time, as a saturated heterocyclic compound containing one or two atoms of nitrogen, oxygen, sulfur, and phosphorus, R ₁ may include aziridine, ethylene oxide, episulfide, and diaziridine. , Oxaziridine, dioxirane, azetidine, oxetane, cyclopropane sulfide, diazetidine, dioxetane, dithiatidine Alkane, pyrrolidine, thiacyclopentane, phosphatidamine, imidazolidine, pyrazolidine, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiopentane, pyridine , Ethylene oxide, thiocyclohexane, phosphinocyclohexane, verazine, morpholine, thiomorpholine, dioxane, dithiane, azacycloheptane, oxepane, sulfur Heterane heptane, homopyrazine, azaoctane, oxane, thiaoctane, azetane, oxonane or thianonane.

At this time, it is characterized in that the R ₂ and the R ₃ are each a linear alkyl group having 1 to 10 carbon atoms containing hydrogen and ether functional groups, or a branched type having 5 to 20 carbon atoms including ether functional groups, respectively. alkyl.

At this time, it is characterized in that the m is an integer of 300 to 4500.

At this time, the X may include chlorine (Cl), bromine (Br), iodine (I), nitrate (NO ₃ ), sulfate (SO ₄ ), carbonate (CO ₃ ), or hydroxyl (OH).

For example, the second leveling agent may have a structure of the following Chemical Formula 2.

Chemical formula 2

At this time, it is characterized in that R ₄ is a linear alkyl group containing 1 to 10 carbon atoms containing hydrogen and ether functional groups, or a branched alkyl group containing 5 to 20 carbon atoms containing ether functional groups.

In this case, it is characterized in that R ₅ contains an aromatic hydrocarbon.

At this time, R ₆ is a hydrogen-containing linear alkyl group having 1 to 5 carbon atoms, or a nitrogen-containing functional group having 1 to 2 carbon atoms such as nitrile, imine, urea, isocyanate, ammonium, amine, or Hydrazine.

At this time, it is characterized in that R ₇ is a linear alkyl group containing 1 to 10 carbon atoms containing hydrogen and ether functional groups, or a branched alkyl group containing 5 to 20 carbon atoms containing ether functional groups.

At this time, it is characterized in that the n is an integer of 50 to 300.

At this time, the inhibitor may include polyoxyalkylene glycol, carboxymethyl cellulose, N-nonylphenol polyethylene glycol ether, octanediol diethylene glycol ether, and oleic acid polyethylene glycol ester. , Polyethylene glycol, polyethylene glycol dimethyl ether, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol, polypropylene glycol, polyvinyl alcohol, stearyl alcohol polyethylene glycol ether, hard Polyethylene glycol fatty acid, 3-methyl-1-butyn-3-ol, 3-methyl-penten-3-ol, L-ethynylcyclohexanol, phenylpropynol, 3-benzene Methyl-1-butyn-3-ol, propargyl alcohol, methylbutanol-ethylene oxide, 2-methyl-4-chloro-3-butyn-2-ol, dimethylhexanediol, Dimethyl hexanediol-ethylene oxide, dimethyl octanediol, phenylbutynol or 1,4-butanediol diglycidyl ether.

At this time, the inhibitor is characterized in that the reduction of copper is suppressed in the copper plating process, and the wettability of the plating solution is improved, so that a copper film is easily formed on a substrate having a pattern.

At this time, the accelerator may include (O- (dithioethyl carbonate) -S- (3-sulfopropyl) -ester, 3-[(amino-iminomethyl) -thiol] -1 -Propanesulfonic acid, 3- (benzothiazole-2-mercapto) -propylsulfonic acid, bis- (sulfopropyl) -sodium disulfide, N, N-dimethyldithiocarbamoylpropanesulfonic acid Acid, 3,3-thiobis (1-propanesulfonic acid), 2-hydroxy-3- [tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, 2,3-dimercaptopropanepropanesulfonic acid Sodium, 3-mercapto-1-propanesulfonic acid, N, N-bis (4-sulfobutyl) -3,5-dimethylaniline, 2-mercapto-5-benzimidazole sulfonate, 5,5 '-Dithiobis (2-nitrobenzoic acid), DL-cysteine, 4-mercapto-benzenesulfonic acid or 5-mercapto-1H-tetrazole-1-methanesulfonic acid.

At this time, it is characterized in that the accelerator is a substance that reduces the overvoltage of the plating solution to generate high-density nuclei during the copper plating process, accelerates the copper reduction reaction speed, and promotes the generation and growth of nuclei.

At this time, in the plating solution of step S200 in which the substrate after the pretreatment is immersed in the plating solution, the inhibitor and the accelerator each have a molecular weight in a range of 100 g / mol to 100,000 g / mol, It may be added at a concentration ranging from 0.1 mg to 1000 mg per liter of the plating solution.

At this time, it is characterized in that, in step S300 of electrodepositing the copper film, a current is applied in a current density range of 1 ASD to 15 ASD (Ampere per square Decimeter, Ampere per square decimeter).

[Example]

Copper plating is performed according to an embodiment of the present invention.

First, prepare a substrate.

Next, the prepared substrate is immersed in a pretreatment solution.

Next, the substrate immersed in the pretreatment solution is immersed in a copper plating solution to perform electroplating.

According to one embodiment, the copper plating is performed by multi-stage current application from the first stage to the fourth stage, and the current is applied in a current density range of 1 ASD to 15 ASD.

According to the above embodiment, a polyethylene oxide derivative containing an aromatic hydrocarbon is added as an inhibitor to the copper plating solution, and an organic compound containing a mercapto group is added as an accelerator.

According to one embodiment, in the copper plating solution, as a saturated heterocyclic compound containing nitrogen, R _{1 of the} first leveler is one of pyrrolidine, pyrazolidine, oxazolidine, and thiazolidine. R ₂ and R _{3 of the} first leveling agent contain hydrogen alone. The m of the first leveling agent is an integer of 500 to 1000, and X of the first leveling agent is one of halogen elements.

According to one embodiment, R ₄ and R ₆ of the second leveler in the copper plating solution contain hydrogen alone. R ₅ of the second leveler is one of phenyl or benzyl. R ₇ contains an amino group containing one nitrogen. The n of the leveling agent is an integer of 80 to 180.

An optical microscope and a laser scanning confocal microscope were used to analyze the plated product manufactured in the first embodiment.

FIG. 2 is a diagram observed with an optical microscope after copper plating according to an embodiment of the present invention.

FIG. 3 is a three-dimensional scanning image measured by a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.

FIG. 4 is a profile result measured using a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.

Referring to FIG. 2 to FIG. 4, according to an embodiment of the present invention, when the substrate is immersed in the pretreatment solution and then electroplated, the unevenness of the thickness in the wiring is measured to be 2.5%.

Comparative example

For comparison with an embodiment of the present invention, plating is performed directly without being immersed in a pre-treatment solution containing a first leveling agent.

First, prepare a substrate.

Next, the pickled substrate is immersed in a copper plating solution to perform electroplating.

According to the embodiment, the copper plating is performed by multi-stage current application from the first stage to the fourth stage, and the current is applied in a current density range of 1 ASD to 15 ASD.

According to the above embodiment, a polyethylene oxide derivative containing an aromatic hydrocarbon is added as an inhibitor to the copper plating solution, and an organic compound containing a mercapto group is added as an accelerator.

According to one embodiment, in the copper plating solution, as a saturated heterocyclic compound containing nitrogen, R _{1 of the} first leveler is one of pyrrolidine, pyrazolidine, oxazolidine, and thiazolidine. R ₂ and R _{3 of the} first leveling agent contain hydrogen alone. The m of the first leveling agent is an integer of 500 to 1000, and X of the first leveling agent is one of halogen elements.

According to one embodiment, R ₄ and R ₆ of the second leveler in the copper plating solution contain hydrogen alone. R ₅ of the second leveler is one of phenyl or benzyl. R ₇ contains an amino group containing one nitrogen. The n of the leveling agent is an integer of 80 to 180.

In the same manner as in the above-mentioned Example, a plated product prepared as a comparative example was analyzed using an optical microscope and a laser scanning confocal microscope.

FIG. 5 is a diagram observed with an optical microscope after copper plating according to a comparative example of the present invention.

FIG. 6 is a three-dimensional scanning view of a comparative example of the present invention, which was measured using a laser scanning confocal microscope after copper plating.

FIG. 7 is a profile result measured using a laser scanning confocal microscope after copper plating according to a comparative example of the present invention.

Referring to FIGS. 5 to 7, when the plating was performed directly without being immersed in the pretreatment solution, the unevenness of the thickness in the wiring was measured to be 14.1%.

It was confirmed that the unevenness of the thickness in the wiring during the experiment according to an example of the present invention was 2.5%, which was an 11.6% improvement over the experimental result of the comparative example, which was 14.1%.

This is because the first leveling agent was adsorbed in advance by the immersion of the pretreatment solution before plating. In the case of performing the pretreatment according to an embodiment of the present invention, since the first leveling agent has been adsorbed on the substrate before electroplating, it plays a role of activating the interface and guiding the plating solution to penetrate into the wiring. The electrolytic solution in the plating solution is uniformly supplied to the surface of the substrate, and a high flatness effect can be produced.

It can be seen that if a copper plating film is formed according to an embodiment of the present invention, a copper plating film with high flatness can be obtained.

The copper electroplated product is described, characterized in that the copper electroplated product is made according to the copper electroplating method according to an embodiment of the present invention.

At this time, the copper electroplated product is characterized in that the substrate is immersed in a pretreatment solution before electroplating.

For example, the copper plating product may include a circuit substrate having a copper wiring or a semiconductor having a copper wiring.

In the copper electroplated product according to an embodiment of the present invention, the first leveling agent is adsorbed in advance because the copper electroplated product is immersed in the pre-treatment solution before electroplating, so that a plated product having a high flatness copper plating film can be obtained.

As described above, the description of the present invention is for illustration, and a person having ordinary knowledge in the technical field to which this case pertains can easily change to other specific methods without comprehending the technical idea or necessary technical features of the present invention. Therefore, it should be understood that the various embodiments described above are exemplified in all aspects and are not limited. For example, the technical features described in a single type may be implemented in a decentralized manner, and the technical features described in a decentralized manner may also be implemented in a combined manner.

The scope of the present invention is indicated by the scope of patent application to be described later, and it should be construed that all changes or modifications derived from the meaning, scope and equivalent concept of the scope of patent application are included in the scope of the invention.

S100 ~ S300‧‧‧step

FIG. 1 is a flowchart showing a copper plating method according to an embodiment of the present invention.

FIG. 2 is a diagram observed with an optical microscope after copper plating according to an embodiment of the present invention.

FIG. 3 is a three-dimensional scanning image measured by a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.

FIG. 4 is a profile result measured using a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.

FIG. 5 is a diagram observed with an optical microscope after copper plating in a comparative example of the present invention.

FIG. 6 is a three-dimensional scanning diagram measured by a laser scanning confocal microscope after copper plating of a comparative example of the present invention.

FIG. 7 is a profile result measured using a laser scanning confocal microscope after copper plating in a comparative example of the present invention.

Claims (13)

A copper electroplating method includes the following steps: a pre-processing step, immersing a substrate in a pre-processing solution, the pre-processing solution containing a first leveling agent but no copper precursor; The substrate is immersed in a plating solution, and the plating solution includes the first leveling agent, the second leveling agent, an inhibitor, an accelerator, and a copper precursor; A current is applied to deposit a copper film. The copper plating method according to claim 1, wherein the substrate has a wiring pitch of 20 μm or less. The copper electroplating method according to claim 1, wherein in the pretreatment step, the first leveling agent is added to the pretreatment solution at a concentration of 100 mg / l to 5000 mg / l. The copper electroplating method according to claim 1, wherein the first leveling agent is used for manufacturing the copper film that is convex. The copper electroplating method according to claim 1, wherein the second leveling agent is used for manufacturing the copper film having depressions. The copper electroplating method according to claim 1, wherein in the step of immersing the substrate after the pretreatment in the plating solution, the first leveling agent is at a concentration of 0.1 mg / l to 1000 mg / l Add in the plating solution. The copper plating method according to claim 1, wherein in the step of immersing the substrate after the pretreatment in the plating solution, the second leveling agent is at a concentration of 0.1 mg / l to 1000 mg / l Add in the plating solution. The copper plating method according to claim 1, wherein the inhibitor comprises polyoxyalkylene glycol, carboxymethyl cellulose, N-nonylphenol polyethylene glycol ether, and octanediol diethylene glycol Ether, polyethylene glycol oleate, polyethylene glycol, polyethylene glycol dimethyl ether, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol, polypropylene glycol, polyvinyl alcohol, hard Fatty alcohol polyethylene glycol ether, stearic acid polyethylene glycol ester, 3-methyl-1-butyn-3-ol, 3-methyl-penten-3-ol, L-ethynylcyclohexanol , Phenylpropynol, 3-phenyl-1-butyn-3-ol, propargyl alcohol, methylbutanol-ethylene oxide, 2-methyl-4-chloro-3-butyne-2- Alcohols, dimethylhexanediol, dimethylhexanediol-ethylene oxide, dimethyloctanediol, phenylbutynol or 1,4-butanediol diglycidyl ether. The copper plating method according to claim 1, wherein the accelerator comprises (O- (dithioethyl carbonate) -S- (3-sulfopropyl) -ester, 3-[(amino-imino (Methyl) -thiol] -1-propanesulfonic acid, 3- (benzothiazole-2-mercapto) -propylsulfonic acid, bis- (sulfopropyl) -sodium disulfide, N, N-dimethyl Dithiocarbamoylpropanesulfonic acid, 3,3-thiobis (1-propanesulfonic acid), 2-hydroxy-3- [tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, 2 Sodium 3-dimercaptopropanepropanesulfonate, 3-mercapto-1-propanesulfonic acid, N, N-bis (4-sulfobutyl) -3,5-dimethylaniline, 2-mercapto-5-benzene Sodium benzimidazole sulfonate, 5,5'-dithiobis (2-nitrobenzoic acid), DL-cysteine, 4-mercapto-benzenesulfonic acid or 5-mercapto-1H-tetrazole-1- Methanesulfonic acid. The copper plating method according to claim 1, wherein the accelerator and the inhibitor each independently have a molecular weight in a range of 100 g / mol to 100,000 g / mol. The copper plating method according to claim 1, wherein the accelerator and the inhibitor are each independently added to the plating solution at a concentration ranging from 0.1 mg / l to 1,000 mg / l. The copper electroplating method according to claim 1, wherein in the step of electrodepositing the copper film, a current is applied in a current density range of 1 ASD to 15 ASD. A copper electroplated product manufactured by the copper electroplating method according to claim 1.