WO2017052002A1

WO2017052002A1 - Organic additive for electrolytic copper plating comprising two types of levelers, and electrolytic copper plating solution containing same

Info

Publication number: WO2017052002A1
Application number: PCT/KR2016/000990
Authority: WO
Inventors: 이민형; 이운영
Original assignee: 한국생산기술연구원
Priority date: 2015-09-25
Filing date: 2016-01-29
Publication date: 2017-03-30
Also published as: CN108026656B; JP2018530675A; JP6554608B2; KR101657675B1; CN108026656A

Abstract

An organic additive for electrolytic copper plating, according to one aspect of the present invention, is added to a copper plating solution for forming a copper film on a substrate having a pattern formed thereon by an electrolytic plating method, and comprises at least two types of levelers in order to increase the uniformity and flatness of the copper film formed on the pattern.

Description

Organic additives for electrolytic copper plating comprising two planarizers and electrolytic copper plating solutions containing the same

The present invention relates to a plating composition, and more particularly, to an electrolytic copper plating composition capable of improving the flatness of a copper plating film on a substrate.

Electrolytic plating is a method of electrodepositing a metal or metal oxide using electrons supplied from the outside. The electroplating system is composed of an electrode, an electrolyte, and a power supply for electrons in the same way as a general electrochemical system. For copper electroplating, a substrate on which a pattern is formed is used as a cathode, and copper or an insoluble material containing phosphorus is used as an anode. The electrolyte basically contains copper ions, sulfuric acid to lower the resistance of the electrolyte itself, and chlorine ions to improve the adsorption of copper ions and additives.

Recently, as bonding technology using an electrolytic plating process is applied due to development of a flip chip packaging process, a demand for high flattening of a plating film on a pattern is increasing.

An object of the present invention is to provide an organic additive for electrolytic copper plating and an electrolytic copper plating solution to increase planarization of a pattern after plating when electrolytic copper plating on a substrate on which a pattern is formed. However, these problems are exemplary, and the scope of the present invention is not limited thereby.

An organic additive for electrolytic copper plating according to one aspect of the present invention. It is added to a copper plating solution for forming a copper film on the substrate on which the pattern is formed by electroplating, and includes at least two planarizers to increase the uniformity and flatness of the copper film formed on the pattern.

In the organic additive for electrolytic copper plating, the flattening agent may include a first flattening agent which makes the surface of the copper film convex, and a second flattening agent which makes the surface of the copper film concave.

In the organic additive for electrolytic copper plating, the first flattening agent may include a compound having a structure represented by the following Chemical Formula 1.

(Formula 1)

(A comprises at least one of ether functionality, ester functionality and carbonyl functionality,

T ₁ and T ₂ alone are hydrogen, or are linear alkyl having from 1 to 10 carbons containing ether functional groups, or from 5 to 20 carbons containing ether functional groups Branched alkyl,

T ₃ and T ₄ alone are hydrogen, linear alkyl having from 1 to 10 carbons, or branched alkyl having from 5 to 20 carbons,

The sum of m and n is an integer from 1 to 50,

o is an integer from 1 to 100,

X is one or more selected from the group of ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO ₃ ), sulfate (SO ₄ ), carbonate (CO ₃ ) and hydroxyl group (OH) Included)

In the organic additive for electrolytic copper plating, the second flattening agent may include a compound having a structure represented by the following Chemical Formula 2.

(Formula 2)

(R ₁ is alone hydrogen or linear alkyl having from 1 to 10 carbons, or branched alkyl having from 5 to 20 carbons,

R ₂ is a substance consisting of glycidoxypropyltrimethoxysilane, butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl ester, glycidyl amine, glycidol Containing at least one of the counties.

R ₃ and R ₄ are unsaturated heterocyclic compounds containing one or two hetero atoms which are azirin, oxyline, thyrine, diazirine, azet, oxet, thiet, dioct, dietiate, pyrrole, Furan, thiophene, phosphol, imidazole, pyrazole, oxosol, isoxazole, thiazole, isothiazole, pyridine, pyran, thiopyran, phosphinine, diazine, oxazine, thiazine, dioxin, One or more selected from the group consisting of dityine, azepine, oxepin, thiedepine, diazepine, tiazine, and azocin,

The sum of q and r is an integer from 1 to 50,

The organic additive for electrolytic copper plating may further include an inhibitor and an accelerator.

In the organic additive for electrolytic copper plating, the inhibitor is Polyoxyalkylene glycol, Carboxymethylcellulose, N-nonylphenolpoly glycol ether, Octandiobis glycol ether, Oleic acid polyglycol ester, Polyethylene glycol, Polyethylene glycol dimethyl ether, Poly (ethylene glycol) -block- poly (propylene glycol) -block-poly (ethylene glycol), Polypropylene glycol, Poly vinyl alcohol, Stearyl alcoholpolyglycol ether, Stearic acidpolyglycol ester, 3-Methyl-l-butyne-3-ol, 3-Methyl-pentene-3-ol , L-ethynylcyclohexanol, phenyl-propynol, 3-Phenyl-l-butyne-3-ol, Propargyl alcohol, Methyl butynol-ethylene oxide, 2-Methyl-4-chloro-3-butyne-2-ol, Dimethyl hexynediol, Dimethylhexynediol It may include one or more selected from the group consisting of -ethylene oxide, Dimethyloctynediol, Phenylbutynol, and 1,4-Butandiol Diglycidyl Ether.

In the organic additive for electrolytic copper plating, the accelerator is (O-Ethyldithiocarbonato) -S- (3-sulfopropyl) -ester, 3-[(Amino-iminomethyl) -thiol] -1-propanesulfonic acid, 3- (Benzothiazolyl-2-mercapto) -propyl-sulfonic acid, sodium bis- (sulfopropyl) -disulfide, N, N-Dimethyl-dithiocarbamyl propyl sulfonic acid, 3,3-Thiobis (1-propanesulfonic acid), 2-Hydroxy-3 -[tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, sodium 2,3-dimercaptopropanesulfonate, 3-Mercapto-1-propanesulfonic acid, N, N-Bis (4-sulfobutyl) -3,5-dimethylaniline, sodium 2- Mercapto-5-benzimidazolesulfonic acid, 5,5′-Dithiobis (2-nitrobenzoic acid), DL-Cysteine, 4-Mercapto-Benzenesulfonic acid, and 5-Mercapto-1H-tetrazole-1-methanesulfonic acid It may include one or more.

An electrolytic copper plating solution according to another aspect of the present invention is an electrolytic copper plating solution containing copper ions and an organic additive, wherein the organic additive is an accelerator, to increase the uniformity and flatness of the copper film formed on the substrate on which the pattern is formed. Inhibitors and at least two planarizers.

In the electrolytic copper plating solution, the planarizing agent may include a first planarizing agent which makes the surface of the copper film convex, and a second planarizing agent which makes the surface of the copper film concave.

In the electrolytic copper plating solution, the molecular weight range of the first flattening agent is 100 g / mol to 500,000 g / mol, and may be added at a concentration of 0.1 mg to 1000 mg per liter of the electrolytic copper plating solution.

In the electrolytic copper plating solution, the second flattening agent may have a molecular weight ranging from 100 g / mol to 500,000 g / mol and may be added at a concentration ranging from 0.1 mg to 1000 mg per liter of the plating solution.

In the electrolytic copper plating solution, the inhibitor and the accelerator may have a molecular weight in the range of 100 g / mol to 100,000 g / mol, respectively, and may be added at a concentration in the range of 0.1 mg to 1000 mg per liter of the plating solution.

According to the organic additive and the electrolytic copper plating solution for electrolytic copper plating according to an embodiment of the present invention made as described above, it is possible to deposit a uniform and flat copper plated film inside the pattern on the substrate electrical properties of the device manufactured using the same This can be excellent and reliable. Of course, the scope of the present invention is not limited by these effects.

1A is a scanning electron microscope (SEM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Experimental Example 1 according to the present invention.

FIG. 1B is a profile of a copper plated film scanned using a surface profiler for the resultant of FIG. 1A.

Figure 2a is a scanning electron microscope (SEM) photograph showing the result of the electrolytic copper plating on the substrate under the conditions of Experimental Example 2 according to the present invention.

FIG. 2B is a profile of a copper plated film scanned using a surface profiler for the resultant of FIG. 2A.

Figure 3a is a scanning electron microscope (SEM) photograph showing the result of the electrolytic copper plating on the substrate under the conditions of Experimental Example 3 according to the present invention.

FIG. 3B is a profile of a copper plated film scanned using a surface profiler for the resultant of FIG. 3A.

Hereinafter, an experimental example of the present invention with reference to the accompanying drawings in detail as follows. However, the present invention is not limited to the experimental examples disclosed below, but may be embodied in various different forms. The following experimental examples make the disclosure of the present invention complete and the scope of the invention to those skilled in the art. It is provided to inform you completely. In addition, the components may be exaggerated or reduced in size in the drawings for convenience of description.

In the figures, for example, variations in the shape shown may be expected, depending on manufacturing techniques and / or tolerances. Therefore, the experimental example of the inventive concept should not be construed as limited to the specific shape of the region shown in the present specification, but should include, for example, a change in shape caused by manufacturing.

In embodiments of the present invention, the electrolytic plating method may be distinguished from the electroless plating method in that electricity is applied. In addition, in embodiments of the present invention, electrolytic copper plating may refer to plating copper by an electrolytic plating method.

An organic additive for electrolytic copper plating according to embodiments of the present invention may be added to a copper plating solution for forming a copper film by an electrolytic plating method. For example, the copper plating liquid basically includes an electrolyte containing copper ions, and may additionally include an additive added thereto. For example, the copper plating solution may include sulfuric acid for lowering the resistance to the electrolyte, chlorine ions for improving the adsorption of copper ions and additives.

The organic additive for electrolytic copper plating according to an embodiment of the present invention is added to a copper plating solution for forming a copper film by an electroplating method on a substrate on which a pattern is formed, and the uniformity and flatness of the copper film formed on the pattern At least two planarizers may be included to increase. In this manner, when the uniformity and flatness of the copper film are increased, the uniformity and flatness of the pattern after the copper film is formed are also increased.

For example, such a planarizer may include a first planarizer that makes the surface of the copper film convex, and a second planarizer that makes the surface of the copper film concave.

The first flattening agent may include a compound having a structure represented by Formula 1 below.

(Formula 1)

The sum of m and n is an integer from 1 to 50,

o is an integer from 1 to 100,

X is one or more selected from the group of ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO ₃ ), sulfate (SO ₄ ), carbonate (CO ₃ ) and hydroxyl group (OH) It may include.

The molecular weight range of the first planarizer is 100 g / mol to 500,000 g / mol, and may be added at a concentration of 0.1 mg to 1000 mg per liter of the electrolytic copper plating solution.

Such a first flattening agent is adsorbed to a plating film portion having a high current density in an electrolytic copper plating process for forming a copper film on a substrate having a pattern, thereby suppressing the reduction of copper ions, thereby providing uniformity and flatness of the copper plating film. As a result, the uniformity and flatness of the pattern after plating can be improved.

The second planarizer may include a compound having a structure represented by Formula 2 below.

(Formula 2)

R ₂ is a substance consisting of glycidoxypropyltrimethoxysilane, butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl ester, glycidyl amine, glycidol One or more selected from the group.

R ₃ and R ₄ are unsaturated heterocyclic compounds containing one or two heteroatoms (nitrogen, oxygen, sulfur, phosphorus, etc.), which are azirin, oxyline, thyrine, diazirin, azet, oxet, thiet , Dioct, dietite, pyrrole, furan, thiophene, phosphol, imidazole, pyrazole, oxosol, isoxazole, thiazole, isothiazole, pyridine, pyran, thiopyran, phosphinine, diazine At least one selected from the group consisting of oxazine, thiazine, dioxin, dityine, azepine, oxepin, tidepine, diazepine, thiazepine and azocin,

The sum of q and r is an integer from 1 to 50,

Such a second flattener has a molecular weight ranging from 100 g / mol to 500,000 g / mol and may be added at a concentration ranging from 0.1 mg to 1000 mg per liter of the plating liquid.

Such a second flattening agent is adsorbed to a plating film portion having a high current density in an electrolytic copper plating process for forming a copper film on a substrate having a pattern, thereby suppressing reduction of copper ions, thereby making uniformity and flatness of the copper plating film. As a result, the uniformity and flatness of the pattern after plating can be improved.

The organic additive for electrolytic copper plating according to some embodiments of the present invention may further include a suppressor and / or an accelerator.

For example, the inhibitor may help to easily form a copper film on a substrate having a pattern by improving the wettability of the plating liquid while suppressing copper reduction in the electrolytic copper plating process. For example, the inhibitor may be polyoxyalkylene glycol, Carboxymethylcellulose, N-nonylphenolpoly glycol ether, Octandiobis glycol ether, Oleic acid polyglycol ester, Polyethylene glycol, Polyethylene glycol dimethyl ether, Poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), Polypropylene glycol, Poly vinyl alcohol, Stearyl alcohol polyglycol ether, Stearic acid polyglycol ester, 3-Methyl-l-butyne-3-ol, 3-Methyl-pentene-3-ol, L-ethynylcyclohexanol, phenyl-propynol, 3-Phenyl-l-butyne-3-ol, Propargyl alcohol, Methyl butynol-ethylene oxide, 2-Methyl-4-chloro-3-butyne-2-ol, Dimethyl hexynediol, Dimethylhexynediol-ethylene oxide, Dimethyloctynediol, Phenylbutynol, and It may include one or more selected from the group consisting of 1,4-Butandiol Diglycidyl Ether.

Such inhibitors have a molecular weight ranging from 100 g / mol to 100,000 g / mol and can be added at concentrations ranging from 0.1 mg to 1000 mg per liter of plating solution.

The accelerator may reduce the overvoltage of the plating solution in the electrolytic copper plating process to generate a high density of nuclei, and may accelerate the copper reduction reaction rate to increase nucleation and growth. For example, the accelerator is (O-Ethyldithiocarbonato) -S- (3-sulfopropyl) -ester, 3-[(Amino-iminomethyl) -thiol] -1-propanesulfonic acid, 3- (Benzothiazolyl-2-mercapto) -propyl -sulfonic acid, sodium bis- (sulfopropyl) -disulfide, N, N-Dimethyl-dithiocarbamyl propyl sulfonic acid, 3,3-Thiobis (1-propanesulfonic acid), 2-Hydroxy-3- [tris (hydroxymethyl) methylamino]- 1-propanesulfonic acid, Sodium 2,3-dimercaptopropanesulfonate, 3-Mercapto-1-propanesulfonic acid, N, N-Bis (4-sulfobutyl) -3,5- -dimethylaniline, Sodium 2-Mercapto-5-benzimidazolesulfonic acid, 5, 5′-Dithiobis (2-nitrobenzoic acid), DL-Cysteine, 4-Mercapto-Benzenesulfonic acid, and 5-Mercapto-1H-tetrazole-1-methanesulfonic acid. .

Such accelerators have a molecular weight ranging from 100 g / mol to 100,000 g / mol and may be added at concentrations ranging from 0.1 mg to 1000 mg per liter of plating liquid.

The electrolytic copper plating solution according to some embodiments of the present invention may include the aforementioned organic additive in an electrolyte containing copper ions. In addition, the electrolytic copper plating solution may further include sulfuric acid for lowering the resistance of the electrolyte, chlorine ions for improving the adsorption property of the copper ions and the additive.

Such an electrolytic copper plating solution may be useful when a pattern is formed on a substrate, such as a semiconductor wafer, and selectively copper plating in such a pattern. Furthermore, such an electrolytic copper plating solution may be used in the formation of a passive device such as an inductor requiring a thick film copper plating, a power device, etc., as the plating speed is high and thick film plating is possible.

The electrolytic copper plating method according to some embodiments of the present invention may include forming a copper film by an electrolytic plating method using the electrolytic copper plating solution containing the aforementioned electrolytic copper plating organic additive. Such an electrolytic copper plating method may be performed through a multi-step direct current application or pulse current application.

For example, the substrate may use a structure in which a photoresist pattern is formed on a silicon wafer, and a copper film may be formed on the substrate by an electrolytic copper plating method. For example, such a copper film may be thick film copper formed thickly on the pattern with a thickness of 10 μm or more, and in this case, may be used as a wiring of a passive device such as an inductor or a power device. Further, the thick film copper film may have a thickness of 10 μm to 50 μm for the inductor or the wiring. However, the thickness of the copper film formed using the electrolytic copper plating additive or the electrolytic copper plating solution according to the present invention is not limited to this thickness.

Hereinafter, experimental examples of concretely implementing the technical idea of the present invention are provided. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

Experimental Example

In this Experimental Example, copper plating was performed on a wafer having a pattern with a thickness of 10 μm or more. In addition, copper electroplating was performed through the multi-step current application of 1 to 4 steps, and current was applied in the current density range of 1 ASD to 15 ASD (Ampere per Square Deci-metre).

In Experimental Examples 1 to 3, a polyethylene oxide derivative containing an aromatic hydrocarbon as an inhibitor and 100 g of copper ions, 150 g of sulfate ions, 50 mg of chlorine ions and an inhibitor in common, and an accelerator, An organic compound containing a mercapto group was added. In addition, Experimental Example 1 further added a first leveling agent as an organic additive, Experimental Example 2 further added a second leveling agent as an organic additive, and Experimental Example 3 added the first leveling agent and the second leveling agent as an organic additive. More was added. In Experimental Examples 1 to 3, the first leveling agent and the second leveling agent were variously tested, and the following shows the conditions of the exemplary experimental example.

For example, in Experimental Examples 1 and 3, A of the first flattener is one of N-nitrosommethanamine, N'-hydroxyimidoformamide, diazenylmethanol, 3-diaziridinol.

T ₁ of the first leveling agent alone contains hydrogen, and T ₂ of the first leveling agent is branched alkyl having 6 carbons containing an ether functional group.

The sum of m and n of a 1st planarizer is an integer of 5-10, and o of a 1st planarizer is an integer of 2-30.

X of the first planarizing agent is one of halogen ions.

R ₁ of the second leveling agent is linear alkyl having three carbons, and R ₂ of the second leveling agent is one of butyl methacrylate, ethyl methacrylate, or glycidyl methacrylate.

R ₃ and R ₄ of the second leveling agent are unsaturated heterocyclic compounds, which are one of azirin, pyrrole, pyrazole, imidazole or thiazine.

The sum of q and r of the second leveling agent is an integer from 3 to 20, and X of the second leveling agent is one of halogen ions.

FIG. 1A is a scanning electron microscope (SEM) photograph showing a result of electrolytic copper plating performed on a substrate under the conditions of Experimental Example 1 according to the present invention. FIG. 1B is a surface profiler of the resultant of FIG. 1A. It is the profile of the copper plating film scanned using.

As shown in FIGS. 1A and 1B, in the case of the plating film according to Experimental Example 1, the copper plating film was formed in a convex shape at the center of the upper part of the pattern, and the thickness difference of the copper plating film on the upper part of the pattern was about 5.3 μm.

FIG. 2A is a scanning electron microscope (SEM) photograph showing a result of electrolytic copper plating performed on a substrate under the conditions of Experimental Example 2 according to the present invention. FIG. 2B is a surface profiler of the resultant of FIG. 2A. It is the profile of the copper plating film scanned using.

As shown in FIGS. 2A and 2B, in the case of the plating film according to Experimental Example 2, the copper plating film was formed in a concave shape at the center of the upper part of the pattern, and the difference in thickness of the copper plating film from the highest point to the lowest point of the upper part of the pattern was about 6.3 μm. appear.

3A is a scanning electron microscope (SEM) photograph showing a result of electrolytic copper plating on a substrate under the conditions of Experimental Example 3 according to the present invention, and FIG. 3B is a surface profiler of the resultant of FIG. 3A. It is the profile of the copper plating film scanned using.

As shown in FIGS. 3A and 3B, in the case of the plating film according to Experimental Example 3, the copper plating film was formed in a substantially flat shape in the center of the upper part of the pattern, and the difference in thickness of the lowest copper plating film at the highest point of the upper part of the pattern was about 1.7 μm. Appeared.

Experimental Example 3 can be seen that the flatness of the pattern surface is improved compared to Experimental Example 1 and Experimental Example 2.

Thus, from the above experimental examples, the first flattening agent can make the surface of the copper film convex, and the second flattening agent can make the surface of the copper film concave. It turns out that the uniformity and flatness of a copper plating film can be improved by mixing.

Although the present invention has been described with reference to the experimental examples shown in the drawings, this is merely exemplary, and those skilled in the art will understand that various modifications and equivalent other experimental examples are possible therefrom. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims

It is added to the copper plating liquid for forming a copper film by the electroplating method on the board | substrate with which the pattern was formed,

An organic additive for electrolytic copper plating comprising at least two planarizing agents for increasing the uniformity and flatness of the copper film formed on the pattern.
The method of claim 1,

The flattening agent

A first planarizing agent that makes the surface of the copper film convex; And

An organic additive for electrolytic copper plating, comprising a second flattening agent that concave the surface of the copper film.
The method of claim 2,

Wherein the first flat agent comprises a compound having a structure represented by the formula (1), an organic additive for electrolytic copper plating.

(Formula 1)

(A comprises at least one of ether functionality, ester functionality and carbonyl functionality,

T 1 and T 2 alone are hydrogen, or are linear alkyl having from 1 to 10 carbons containing ether functional groups, or from 5 to 20 carbons containing ether functional groups Branched alkyl,

T 3 and T 4 alone are hydrogen, linear alkyl having from 1 to 10 carbons, or branched alkyl having from 5 to 20 carbons,

The sum of m and n is an integer from 1 to 50,

o is an integer from 1 to 100,

X is one or more selected from the group of ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO 3 ), sulfate (SO 4 ), carbonate (CO 3 ) and hydroxyl group (OH) Included)
The method of claim 2,

Wherein the first flattening agent has a molecular weight in the range of 100 g / mol to 500,000 g / mol.
The method of claim 2,

Wherein the second flat agent comprises a compound having a structure represented by the following formula (2), an organic additive for electrolytic copper plating.

(Formula 2)

(R 1 is alone hydrogen or linear alkyl having from 1 to 10 carbons, or branched alkyl having from 5 to 20 carbons,

R 2 is a material consisting of glycidoxypropyltrimethoxysilane methoxy silane, butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl ester, glycidyl amine, glycidol One or more selected from the group,

R 3 and R 4 are unsaturated heterocyclic compounds containing one or two hetero atoms which are azirin, oxyline, thyrine, diazirine, azet, oxet, thiet, dioct, dietiate, pyrrole, Furan, thiophene, phosphol, imidazole, pyrazole, oxosol, isoxazole, thiazole, isothiazole, pyridine, pyran, thiopyran, phosphinine, diazine, oxazine, thiazine, dioxin, One or more selected from the group consisting of dityine, azepine, oxepin, thiedepine, diazepine, tiazine, and azocin,

The sum of q and r is an integer from 1 to 50,

X is one or more selected from the group of ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO 3 ), sulfate (SO 4 ), carbonate (CO 3 ) and hydroxyl group (OH) Included)
The method of claim 2,

Wherein the second flattening agent has a molecular weight in the range of 100 g / mol to 500,000 g / mol.
The method according to any one of claims 1 to 6,

An organic additive for electrolytic copper plating, further comprising an inhibitor and an accelerator.
The method of claim 7, wherein

The inhibitor,

Polyoxyalkylene glycol, Carboxymethylcellulose, N-nonylphenolpoly glycol ether, Octandiobis glycol ether, Oleic acid polyglycol ester, Polyethylene glycol, Polyethylene glycol dimethyl ether, Poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), Polypropylene glycol, Poly vinyl alcohol, Stearyl alcohol polyglycol ether, Stearic acid polyglycol ester, 3-Methyl-l-butyne-3-ol, 3-Methyl-pentene-3-ol, L-ethynylcyclohexanol, phenyl-propynol, 3-Phenyl-l -butyne-3-ol, Propargyl alcohol, Methyl butynol-ethylene oxide, 2-Methyl-4-chloro-3-butyne-2-ol, Dimethyl hexynediol, Dimethylhexynediol-ethylene oxide, Dimethyloctynediol, Phenylbutynol, and 1,4-Butandiol An electrolytic copper plating organic additive comprising one or more selected from the group of materials consisting of Diglycidyl Ether.
The method of claim 7, wherein

The accelerator,

(O-Ethyldithiocarbonato) -S- (3-sulfopropyl) -ester, 3-[(Amino-iminomethyl) -thiol] -1-propanesulfonic acid, 3- (Benzothiazolyl-2-mercapto) -propyl-sulfonic acid, sodium bis -(sulfopropyl) -disulfide, N, N-Dimethyl-dithiocarbamyl propyl sulfonic acid, 3,3-Thiobis (1-propanesulfonic acid), 2-Hydroxy-3- [tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, sodium 2,3-dimercaptopropanesulfonate, 3-Mercapto-1-propanesulfonic acid, N, N-Bis (4-sulfobutyl) -3,5-dimethylaniline, sodium 2-Mercapto-5-benzimidazolesulfonic acid, 5,5′-Dithiobis (2 nitrobenzoic acid), DL-Cysteine, 4-Mercapto-Benzenesulfonic acid, and 5-Mercapto-1H-tetrazole-1-methanesulfonic acid, comprising one or more selected from the group of organic additives for electrolytic copper plating.
The method of claim 7, wherein

Wherein said accelerator and said inhibitor each have a molecular weight ranging from 100 g / mol to 100,000 g / mol.
Electrolytes containing copper ions; And

It includes an organic additive added to the electrolyte,

The organic additive comprises an accelerator, an inhibitor, and at least two planarizing agents to increase the uniformity and flatness of the copper film formed on the patterned substrate.
The method of claim 11,

The flattener,

A first planarizing agent that makes the surface of the copper film convex; And

An electrolytic copper plating solution, comprising a second planarizing agent to concave the surface of the copper film.
The method of claim 12,

The first flat agent comprises an electrolytic copper plating solution containing a compound having a structure represented by the following formula (1).

(Formula 1)

(A comprises at least one of ether functionality, ester functionality and carbonyl functionality,

T 1 and T 2 alone are hydrogen, or are linear alkyl having from 1 to 10 carbons containing ether functional groups, or from 5 to 20 carbons containing ether functional groups Branched alkyl,

T 3 and T 4 alone are hydrogen, linear alkyl having from 1 to 10 carbons, or branched alkyl having from 5 to 20 carbons,

The sum of m and n is an integer from 1 to 50,

o is an integer from 1 to 100,

X is one or more selected from the group of ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO 3 ), sulfate (SO 4 ), carbonate (CO 3 ) and hydroxyl group (OH) Included)
The method of claim 11,

The first planarizing agent has a molecular weight range of 100 g / mol to 500,000 g / mol and is added at a concentration of 0.1 mg to 1000 mg per liter of the electrolytic copper plating solution.
The method of claim 12,

The second flat agent comprises an electrolytic copper plating solution containing a compound having a structure represented by the following formula (2).

(Formula 2)

(R 1 is alone hydrogen or linear alkyl having from 1 to 10 carbons, or branched alkyl having from 5 to 20 carbons,

R 2 consists of glycidoxypropyltrimethoxysilane, butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl ester, glycidyl amine, and glycidol One or more selected from the group of substances.

R 3 and R 4 are unsaturated heterocyclic compounds containing one or two heteroatoms (nitrogen, oxygen, sulfur, phosphorus, etc.), which are azirin, oxyline, thyrine, diazirin, azet, oxet, thiet , Dioct, dietite, pyrrole, furan, thiophene, phosphol, imidazole, pyrazole, oxosol, isoxazole, thiazole, isothiazole, pyridine, pyran, thiopyran, phosphinine, diazine At least one selected from the group consisting of oxazine, thiazine, dioxin, dityine, azepine, oxepin, tidepine, diazepine, thiazepine and azocin,

The sum of q and r is an integer from 1 to 50,

X is one or more selected from the group of ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO 3 ), sulfate (SO 4 ), carbonate (CO 3 ) and hydroxyl group (OH) Included)
The method of claim 11,

Wherein said second planarizer has a molecular weight ranging from 100 g / mol to 500,000 g / mol and is added at a concentration ranging from 0.1 mg to 1000 mg per liter of plating solution.
The method of claim 11,

The inhibitor,

Polyoxyalkylene glycol, Carboxymethylcellulose, N-nonylphenolpoly glycol ether, Octandiobis glycol ether, Oleic acid polyglycol ester, Polyethylene glycol, Polyethylene glycol dimethyl ether, Poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), Polypropylene glycol, Poly vinyl alcohol, Stearyl alcohol polyglycol ether, Stearic acid polyglycol ester, 3-Methyl-l-butyne-3-ol, 3-Methyl-pentene-3-ol, L-ethynylcyclohexanol, phenyl-propynol, 3-Phenyl-l -butyne-3-ol, Propargyl alcohol, Methyl butynol-ethylene oxide, 2-Methyl-4-chloro-3-butyne-2-ol, Dimethyl hexynediol, Dimethylhexynediol-ethylene oxide, Dimethyloctynediol, Phenylbutynol, 1,4-Butandiol Diglycidyl An electrolytic copper plating organic additive comprising one or more selected from the group of materials consisting of Ether.
The method of claim 11,

The accelerator,

(O-Ethyldithiocarbonato) -S- (3-sulfopropyl) -ester, 3-[(Amino-iminomethyl) -thiol] -1-propanesulfonic acid, 3- (Benzothiazolyl-2-mercapto) -propyl-sulfonic acid, sodium bis -(sulfopropyl) -disulfide, N, N-Dimethyl-dithiocarbamyl propyl sulfonic acid, 3,3-Thiobis (1-propanesulfonic acid), 2-Hydroxy-3- [tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, sodium 2,3-dimercaptopropanesulfonate, 3-Mercapto-1-propanesulfonic acid, N, N-Bis (4-sulfobutyl) -3,5-dimethylaniline, sodium 2-Mercapto-5-benzimidazolesulfonic acid, 5,5′-Dithiobis (2 -nitrobenzoic acid), DL-Cysteine, 4-Mercapto-Benzenesulfonic acid, and 5-Mercapto-1H-tetrazole-1-methanesulfonic acid.
The method of claim 11,

The inhibitor and the accelerator each have a molecular weight ranging from 100 g / mol to 100,000 g / mol, and are added at concentrations ranging from 0.1 mg to 1000 mg per liter of plating solution, respectively.