Organic additive for electrolytic copper plating comprising two types of levelers and electrolytic copper plating solution comprising same

Abstract

An embodiment of the present invention provides an organic additive for electrolytic copper plating and an electrolytic copper plating solution comprising same. The electrolytic copper plating solution according to an embodiment of the present invention comprises at least two types of levelers to form a flat and uniform copper film on a substrate, on which a pattern is formed, by an electrolytic plating method.

Description

Organic additive for electrolytic copper plating containing two types of leveling agents and electrolytic copper plating solution containing the same

[0001] The present invention relates to a copper plating solution, and more particularly, to an electrolytic copper plating solution capable of improving the flatness and uniformity of a copper plating film on a substrate.

[0002] Electroplating is a method of depositing metals or metal oxides using externally supplied electrons. Electroplating systems, like typical electrochemical systems, consist of electrodes, an electrolyte, and a power source for supplying electrons. For copper electroplating, a patterned substrate serves as the cathode, and copper or an insoluble material containing phosphorus serves as the anode. The electrolyte typically contains copper ions, sulfuric acid to lower its resistance, and chloride ions to improve the adsorption of copper ions and additives.

[0003] Recently, with the development of flip chip packaging processes and the application of bonding technology using electroplating processes, the demand for high smoothness of plating films on patterns is increasing.

[0004] Accordingly, leveling agents are added to increase surface smoothness. Previously, polyglycine, polyacrylamide, polyaminoamide, and polyalkanolamine have been disclosed as leveling agents. Furthermore, polyvinylpyridine, polyvinylpyrrolidone, and copolymers of vinylimidazole and vinylpyrrolidone have also been disclosed as leveling agents.

[0005] Additionally, electrolytic copper plating may typically include the following individual steps:

[0006] 1) A plating solution is formed by including an electrolyte solution, an accelerator, an inhibitor, and a leveling agent.

[0007] 2) Place the above plating target in the plating tank.

[0008] 3) Supply the plating solution to the plating tank until the above plating target is sufficiently submerged.

[0009] 4) Power is supplied to the above plating tank to form a copper film on the metal base film of the plating target.

[0010] 5) Remove the plated object from the plating bath after plating is completed.

[0011] Currently, various plating solutions are being used to improve the flatness of the plated surface of the plating target. However, while various copper plating solutions are known, no solution is known that can ensure a satisfactory plating speed without compromising the surface flatness of the plating target. Therefore, there is a need for a new copper plating solution that exhibits superior plating efficiency and provides superior surface uniformity and flatness, and a copper plating method utilizing the solution.

[0012] (Patent Document 1) Republic of Korea Patent Publication No. 10-1738701

[0013] (Patent Document 2) Republic of Korea Patent Publication No. 10-2445636

[0014] (Patent Document 3) Republic of Korea Patent Publication No. 10-2446480

[0015] The present invention is a method for solving the problems of the above-described prior art, and is intended to provide an electrolytic copper plating solution having excellent surface flatness and uniformity of the plating surface when electrolytic copper is plated on a substrate having a pattern formed thereon.

[0016] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0017] In order to achieve the above technical task, one embodiment of the present invention provides an organic additive for electrolytic copper plating.

[0018] An organic additive for electrolytic copper plating according to one embodiment of the present invention is an organic additive added to a copper plating solution for forming a copper film by electrolytic plating on a substrate having a pattern formed thereon, and comprises at least two kinds of planarizing agents to increase the uniformity and flatness of the copper film formed on the pattern, wherein the two kinds of planarizing agents include a convex planarizing agent that makes the surface of the copper film convex; and a concave planarizing agent having a structure of the following <Chemical Formula 1> that makes the surface of the copper film concave.

[0019] <Chemical Formula 1>

[0020]

[0021] In the above chemical formula 1,

[0022] A is a non-metallic element with an electronegativity of 2.0 or higher,

[0023] R1' and R1'' are each independently,

[0024] (1) a monomer or polymer comprising at least one alkylene oxide or ester functional group containing oxygen; or

[0025] (2) a linear or branched alkyl having 1 to 20 carbon atoms and containing 1 to 5 amine groups; or

[0026] (3) A linear or branched alkyl having 1 to 20 carbon atoms, comprising a monomer or polymer comprising 1 to 5 amine groups and at least one alkylene oxide or ester functional group containing oxygen at the chain terminal;

[0027] R2' and R2'' are each independently a chain-like alkyl group having 1 to 10 carbon atoms; a hydroxyl group; or an amine group;

[0028] R3 is a chain-like alkyl group having 1 to 10 carbon atoms; or an alkylene oxide;

[0029] The sum of m and n is from 1 to 1000, and m and n are integers greater than or equal to 0.

[0030] In an embodiment of the present invention, A in the above <chemical formula 1> may be an organic additive for electrolytic copper plating, characterized in that it is CH or N.

[0031] In an embodiment of the present invention, the convex flattener may be an organic additive for electrolytic copper plating characterized by being expressed by the following <Chemical Formula 2> or <Chemical Formula 3>.

[0032] <Chemical Formula 2>

[0033]

[0034] In the above chemical formula 2,

[0035] A' contains at least one of an ether functional group, an ester functional group, and a carbonyl functional group,

[0036] T1 and T2 are alkyl having a linear structure containing hydrogen alone or having 1 to 10 carbon atoms containing an ether functional group, or alkyl having a branched structure containing 5 to 20 carbon atoms containing an ether functional group,

[0037] T3 and T4 are either a linear alkyl group containing hydrogen alone or having between 1 and 10 carbon atoms, or a branched alkyl group containing between 5 and 20 carbon atoms,

[0038] The sum of m and n is an integer from 1 to 50,

[0039] o is an integer from 1 to 100,

[0040] X contains one or more ions selected from the group consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO3), sulfate (SO4), carbonate (CO3), and hydroxyl (OH),

[0041] <Chemical Formula 3>

[0042]

[0043] In the above chemical formula 3,

[0044] R4 is a saturated heterocyclic compound comprising at least one member selected from the group consisting of aziridine, oxirane, thiirane, diaziridine, oxaziridine, dioxirane, azetidine, oxetane, thietane, diazetidine, dioxetane, dithietane, pyrrolidine, thiolane, phosphorane, imidazolidine, pyrazolidine, oxazolidine, isooxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiolane, piperidine, oxane, thiane, phosphinane, piperazine, morpholine, thiomorpholine, dioxane, dithiane, azepane, oxepane, thiepane, homopyrerazine, azocane, oxocane, thiocane, azonane, oxonane, thionane,

[0045] R5 and R6 are each independently a single hydrogen, a linear alkyl having 1 to 10 carbon atoms and containing an ether functional group, or a branched alkyl having 5 to 20 carbon atoms and containing an ether functional group,

[0046] p is an integer between 300 and 4500,

[0047] X contains one or more of the ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO3), sulfate (SO4), carbonate (CO3), and hydroxyl (OH).

[0048] In an embodiment of the present invention, the concave flattener may be an organic additive for electrolytic copper plating characterized in that it has a concentration of 0.1 mg / L to 1000 mg / L in the organic additive for copper plating.

[0049] In an embodiment of the present invention, the concave flattener expressed by the above <chemical formula 1> may be an organic additive for electrolytic copper plating characterized by having a molecular weight in the range of 150 g / mol to 280,000 g / mol.

[0050] In an embodiment of the present invention, the convex flattener expressed by the above <chemical formula 2> may be an organic additive for electrolytic copper plating characterized by having a molecular weight in the range of 100 g / mol to 500,000 g / mol.

[0051] In an embodiment of the present invention, the convex flattening agent expressed by the above <chemical formula 2> may be an organic additive for electrolytic copper plating characterized in that the concentration is 0.1 mg to 1000 mg per 1 L of electrolytic copper plating solution.

[0052] In an embodiment of the present invention, the convex flattener represented by the above <chemical formula 3> may be an organic additive for electrolytic copper plating characterized by having a molecular weight in the range of 50,000 g / mol to 700,000 g / mol.

[0053] In an embodiment of the present invention, the convex flattening agent expressed by the above <chemical formula 3> may be an organic additive for electrolytic copper plating characterized in that the concentration is 0.1 mg to 1000 mg per 1 L of electrolytic copper plating solution.

[0054] In an embodiment of the present invention, it may be an organic additive for electrolytic copper plating characterized by further including an inhibitor and an accelerator.

[0055] In an embodiment of the present invention, 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-ethylene oxide, It may be an organic additive for electrolytic copper plating, characterized in that it includes one or more selected from the group of substances consisting of dimethyloctynediol, phenylbutynol, and 1,4-butandiol diglycidyl ether.

[0056] In an embodiment of the present invention, 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,NDimethyl-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, It may be an organic additive for electrolytic copper plating, characterized in that it includes one or more selected from the group of substances consisting of 5,5′-Dithiobis(2-nitrobenzoic acid), DL-Cysteine, 4-Mercapto-Benzenesulfonic acid, and 5-Mercapto-1H-tetrazole-1-methanesulfonic acid.

[0057] In an embodiment of the present invention, the accelerator and the inhibitor may be organic additives for electrolytic copper plating, each characterized by having a molecular weight in the range of 100 g / mol to 100,000 g / mol.

[0058] In order to achieve the above technical task, another embodiment of the present invention provides an electrolytic copper plating solution.

[0059] An electrolytic copper plating solution according to one embodiment of the present invention comprises: an electrolyte containing copper ions; and an organic additive added to the electrolyte, wherein the organic additive comprises an accelerator, an inhibitor, and at least two kinds of leveling agents to increase the uniformity and flatness of a copper film formed on a substrate having a pattern formed thereon, and the leveling agents include a concave leveling agent having a structure expressed by the following <Chemical Formula 1> that makes the surface of the copper film concave; and a convex leveling agent that makes the surface of the copper film convex.

[0060] <Chemical Formula 1>

[0061]

[0062] In the above chemical formula 1,

[0063] A is a non-metallic element with an electronegativity of 2.0 or higher,

[0064] R1' and R1'' are each independently,

[0065] (1) a monomer or polymer comprising at least one alkylene oxide or ester functional group containing oxygen; or

[0066] (2) a linear or branched alkyl having 1 to 20 carbon atoms and containing 1 to 5 amine groups; or

[0067] (3) A linear or branched alkyl having 1 to 20 carbon atoms, comprising a monomer or polymer comprising 1 to 5 amine groups and at least one alkylene oxide or ester functional group containing oxygen at the chain terminal;

[0068] R2' and R2'' are each independently a chain-like alkyl group having 1 to 10 carbon atoms; a hydroxyl group; or an amine group;

[0069] R3 is a chain-like alkyl group having 1 to 10 carbon atoms; or an alkylene oxide;

[0070] The sum of m and n is from 1 to 1000, and m and n are integers greater than or equal to 0.

[0071] In an embodiment of the present invention, A in the above <chemical formula 1> may be an organic additive for electrolytic copper plating, characterized in that it is CH or N.

[0072] In an embodiment of the present invention, the convex flattener may be an organic additive for electrolytic copper plating characterized by being expressed by the following <Chemical Formula 2> or <Chemical Formula 3>.

[0073] According to an embodiment of the present invention, a copper plating film having a uniform and excellent flatness can be deposited within a pattern on a substrate, thereby providing an effect of improving the electrical characteristics and reliability of a device manufactured using the same.

[0074] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

[0075] Figure 1a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 1 according to the present invention.

[0076] Figure 1b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 1 according to the present invention.

[0077] Figure 2a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 2 according to the present invention.

[0078] Figure 2b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 2 according to the present invention.

[0079] FIG. 3a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 3 according to the present invention.

[0080] Figure 3b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 3 according to the present invention.

[0081] FIG. 4a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 4 according to the present invention.

[0082] Figure 4b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 4 according to the present invention.

[0083] FIG. 5a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 5 according to the present invention.

[0084] Figure 5b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 5 according to the present invention.

[0085] FIG. 6a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 6 according to the present invention.

[0086] Figure 6b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 6 according to the present invention.

[0087] Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention can be implemented in various different forms and is therefore not limited to the embodiments described herein. In the drawings, irrelevant parts have been omitted for clarity of description, and similar parts have been designated with similar reference numerals throughout the specification.

[0088] Throughout the specification, when a part is said to be "connected (connected, contacted, or coupled)" to another part, this includes not only cases where it is "directly connected," but also cases where it is "indirectly connected" with another part in between. Furthermore, when a part is said to "include" a component, this does not exclude other components, but rather implies that it may include other components, unless otherwise specifically stated.

[0089] The terminology used herein is merely used to describe specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprises" or "has" indicate the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0090] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

[0091]

[0092] An organic additive for electrolytic copper plating according to one embodiment of the present invention is described.

[0093] First, in the embodiments of the present invention, the electrolytic plating method can be distinguished from the electroless plating method in that electricity is applied, and in the embodiments of the present invention, electrolytic copper plating can refer to plating copper by the electrolytic plating method.

[0094] The organic additive for electrolytic copper plating according to embodiments of the present invention is added to a copper plating solution for forming a copper film by the above-described electrolytic plating method. For example, the copper plating solution basically includes an electrolyte containing copper ions, and may additionally include additional additives added thereto. Specifically, the copper plating solution may include sulfuric acid to lower the resistance of the electrolyte, and chlorine ions to improve the adsorption properties of the copper ions and the additives.

[0095] In addition, 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 plating film by electrolytic plating on a substrate having a pattern formed thereon, and may include at least two types of planarizing agents to increase the uniformity and flatness of the copper film formed on the pattern. As the uniformity and flatness of the copper film increase in this way, the uniformity and flatness of the pattern after the copper film is formed also increase, and it becomes possible to manufacture a semiconductor having excellent performance including the same.

[0096] At this time, the present invention includes at least two types of planarizers, a convex planarizer that makes the surface of the copper film convex and a concave planarizer that makes the surface of the copper film concave. By adding an organic additive having the convex planarizer and the concave planarizer, the uniformity and flatness of the copper film can be improved.

[0097]

[0098] An organic additive for electrolytic copper plating according to one embodiment of the present invention is an organic additive added to a copper plating solution for forming a copper film by electrolytic plating on a substrate having a pattern formed thereon, and comprises at least two kinds of planarizing agents to increase the uniformity and flatness of the copper film formed on the pattern, wherein the two kinds of planarizing agents include a convex planarizing agent that makes the surface of the copper film convex; and a concave planarizing agent having a structure of the following <Chemical Formula 1> that makes the surface of the copper film concave.

[0099] At this time, in the concave flat plate having the structure of the above <chemical formula 1>, <chemical formula 1> is as follows.

[0100] <Chemical Formula 1>

[0101]

[0102] In the above chemical formula 1,

[0103] A is a non-metallic element with an electronegativity of 2.0 or higher,

[0104] R1' and R1'' are each independently,

[0105] (1) a monomer or polymer comprising at least one alkylene oxide or ester functional group containing oxygen; or

[0106] (2) a linear or branched alkyl having 1 to 20 carbon atoms and containing 1 to 5 amine groups; or

[0107] (3) A linear or branched alkyl having 1 to 20 carbon atoms, comprising a monomer or polymer comprising 1 to 5 amine groups and at least one alkylene oxide or ester functional group containing oxygen at the chain terminal;

[0108] R2' and R2'' are each independently a chain-like alkyl group having 1 to 10 carbon atoms; a hydroxyl group; or an amine group;

[0109] R3 is a chain-like alkyl group having 1 to 10 carbon atoms; or an alkylene oxide;

[0110] The sum of m and n is from 1 to 1000, and m and n are integers greater than or equal to 0.

[0111] At this time, in the above <Chemical Formula 1>, A is a non-metallic element and may further include an appropriate hydrogen group. For example, A may be CH or N.

[0112] At this time, the concave flattener having the structure of the above <Chemical Formula 1> may have a molecular weight ranging from 150 g / mol to 280,000 g / mol, and may be included in the entire electrolytic copper plating solution at a concentration of 0.1 mg to 1000 mg per 1 L.

[0113]

[0114] Meanwhile, in the embodiment of the present invention, the convex flattener serves to make the surface of the copper film convex, and may be, for example, a material expressed by <Chemical Formula 2> or <Chemical Formula 3> below, but is not limited thereto.

[0115]

[0116] <Chemical Formula 2>

[0117]

[0118] In the above chemical formula 2,

[0119] A' contains at least one of an ether functional group, an ester functional group, and a carbonyl functional group,

[0120] T1 and T2 are alkyl having a linear structure containing hydrogen alone or having 1 to 10 carbon atoms containing an ether functional group, or alkyl having a branched structure containing 5 to 20 carbon atoms containing an ether functional group,

[0121] T3 and T4 are either a linear alkyl group containing hydrogen alone or having between 1 and 10 carbon atoms, or a branched alkyl group containing between 5 and 20 carbon atoms,

[0122] The sum of m and n is an integer from 1 to 50,

[0123] o is an integer from 1 to 100,

[0124] X comprises one or more ions selected from the group consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO3), sulfate (SO4), carbonate (CO3), and hydroxyl (OH).

[0125] At this time, the convex flattener expressed by the above <Chemical Formula 2> may preferably have a molecular weight range of 100 g / mol to 500,000 g / mol, and may be added at a concentration of 0.1 mg to 1,000 mg per liter of the electrolytic copper plating solution.

[0126]

[0127] <Chemical Formula 3>

[0128]

[0129] In the above chemical formula 3,

[0130] R4 is a saturated heterocyclic compound comprising at least one member selected from the group consisting of aziridine, oxirane, thiirane, diaziridine, oxaziridine, dioxirane, azetidine, oxetane, thietane, diazetidine, dioxetane, dithietane, pyrrolidine, thiolane, phosphorane, imidazolidine, pyrazolidine, oxazolidine, isooxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiolane, piperidine, oxane, thiane, phosphinane, piperazine, morpholine, thiomorpholine, dioxane, dithiane, azepane, oxepane, thiepane, homopyrerazine, azocane, oxocane, thiocane, azonane, oxonane, thionane,

[0131] R5 and R6 are each independently a single hydrogen, a linear alkyl having 1 to 10 carbon atoms and containing an ether functional group, or a branched alkyl having 5 to 20 carbon atoms and containing an ether functional group,

[0132] p is an integer between 300 and 4500,

[0133] X contains one or more of the ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO3), sulfate (SO4), carbonate (CO3), and hydroxyl (OH).

[0134] At this time, the molecular weight range of the convex flattener expressed by the above <Chemical Formula 3> may preferably be 50,000 g / mol to 700,000 g / mol, and may be added at a concentration of 0.1 mg to 1,000 mg per liter of the electrolytic copper plating solution.

[0135]

[0136] A convex flattener such as the above <Chemical Formula 2> or <Chemical Formula 3> is adsorbed to a portion of a plating film where a high current density is formed in an electrolytic copper plating process for forming a copper film on a substrate having a pattern, thereby inhibiting the reduction of copper ions and improving the uniformity and flatness of the copper plating film, thereby improving the uniformity and flatness of the pattern after plating.

[0137] Additionally, the organic additive for electrolytic copper plating according to some embodiments of the present invention may further include a suppressor and / or an accelerator.

[0138] The above inhibitor can help to easily form a copper film on a patterned substrate by improving the wettability of the plating solution while suppressing copper reduction in an electrolytic copper plating process.

[0139] For example, inhibitors include 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-Methylpentene-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, It may include one or more selected from the group of substances consisting of Dimethyloctynediol, Phenylbutynol, and 1,4-Butandiol Diglycidyl Ether.

[0140] These inhibitors have molecular weights ranging from 100 g / mol to 100,000 g / mol and can be added in concentrations ranging from 0.1 mg to 1000 mg per liter of the plating solution.

[0141] The above accelerator is a substance that lowers the overvoltage of the plating solution in the electrolytic copper plating process to generate high-density nuclei, and can play a role in accelerating the copper reduction reaction rate to increase the generation and growth of nuclei.

[0142] For example, the accelerator is (OEthyldithiocarbonato)-S-(3-sulfopropyl)-ester, 3-[(Amino-iminomethyl)-thiol]-1-propanesulfonic acid, 3-(Benzothiazolyl-2-mercapto)-propyl-sulfonic acid, sodium bis-(sulfopropyl)-disulfide, N,N-Dimethyldithiocarbamyl 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, It may include one or more selected from the group consisting of 5,5′-Dithiobis(2-nitrobenzoic acid), DL-Cysteine, 4-Mercapto-Benzenesulfonic acid, and 5-Mercapto-1H-tetrazole-1-methanesulfonic acid.

[0143] These accelerators have molecular weights ranging from 100 g / mol to 100,000 g / mol and can be added in concentrations ranging from 0.1 mg to 1000 mg per liter of the plating solution.

[0144]

[0145] An electrolytic copper plating solution according to some embodiments of the present invention may include an electrolyte containing copper ions and the aforementioned organic additive. Additionally, the electrolytic copper plating solution may further include sulfuric acid to lower the resistance of the electrolyte and chloride ions to improve the adsorption properties of the copper ions and additives.

[0146] This electrolytic copper plating solution can be useful when forming a pattern on a substrate, such as a semiconductor wafer, and selectively plating copper within this pattern. Furthermore, this electrolytic copper plating solution has a high plating speed, enabling thick film plating, and thus can be used in the formation of passive components such as inductors and power components that require thick film copper plating.

[0147] An electrolytic copper plating method according to some embodiments of the present invention may include a step of forming a copper film by electrolytic plating using an electrolytic copper plating solution containing the aforementioned electrolytic copper plating organic additive. This electrolytic copper plating method may be performed by applying a direct current or pulse current in multiple stages.

[0148] For example, the substrate may utilize a structure in which a photoresist pattern is formed on a silicon wafer, and a copper film may be formed on this substrate using an electrolytic copper plating method. For example, this copper film may be a thick copper film formed to a thickness of 10 μm or more on the pattern, and in this case, it may be used for a passive element such as an inductor or a wiring of a power element. Furthermore, the thick copper film may have a thickness of 10 μm to 50 μm for use in an inductor or 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.

[0149] The present invention will be described in more detail below through experimental examples. However, the present invention is not limited to the following experimental examples.

[0150]

[0151] Manufacturing Example 1: Concave flattener <Chemical Formula 1A>

[0152] In Manufacturing Example 1, a concave flattener represented by the following chemical formula 1A was used.

[0153] Specifically, a plating solution was prepared by adding 60 g of copper ions, 150 g of sulfuric acid ions, 50 mg of chloride ions, a polyethylene oxide derivative containing an aromatic hydrocarbon, an organic compound containing a mercapto group as an accelerator, and a concave-flattening agent of the following <Chemical Formula 1A> to 1 liter of the plating solution.

[0154] Formula 1A: 2-{2-[2-(5-Dodecanyloxy)ethoxy]ethoxy}ethanol

[0155]

[0156] Manufacturing Example 2: Concave flattener <Chemical Formula 1B>

[0157] In Manufacturing Example 2, a concave flattener represented by the following chemical formula 1B was used.

[0158] Specifically, a plating solution was prepared by adding 60 g of copper ions, 150 g of sulfuric acid ions, 50 mg of chloride ions, a polyethylene oxide derivative containing an aromatic hydrocarbon, an organic compound containing a mercapto group as an accelerator, and a concave-flattening agent of the following <Chemical Formula 1B> per liter of the plating solution.

[0159] Formula 1B: Poly(aminoethyl-dimethylethane-diamine)

[0160]

[0161] Manufacturing Example 3: Concave flattener <Chemical Formula 1C>

[0162] In Manufacturing Example 3, a concave flattener represented by the following chemical formula 1C was used.

[0163] Specifically, a plating solution was prepared by adding 60 g of copper ions, 150 g of sulfuric acid ions, 50 mg of chloride ions, a polyethylene oxide derivative containing an aromatic hydrocarbon, an organic compound containing a mercapto group as an accelerator, and a concave-flattening agent of the following <Chemical Formula 1C> to 1 liter of the plating solution.

[0164] Chemical Formula 1C: 2-Hydroxydecanoic acid

[0165]

[0166] Manufacturing Example 4: Concave flattener of <Chemical Formula 1A> + convex flattener of <Chemical Formula 2A>

[0167] In Manufacturing Example 4, the same <Chemical Formula 1A> as Manufacturing Example 1 and the convex flattener represented by the following Chemical Formula 2A were used.

[0168] Specifically, a plating solution was prepared by adding 60 g of copper ions, 150 g of sulfuric acid ions, 50 mg of chloride ions, a polyethylene oxide derivative containing an aromatic hydrocarbon, an organic compound containing a mercapto group as an accelerator, and two leveling agents of the above <Chemical Formula 1A> and the following <Chemical Formula 2A> per liter of the plating solution.

[0169] Chemical Formula 2A: Quaternized Poly[dimethylaminopropyl)carbamide], X is chlorine

[0170]

[0171] Manufacturing Example 5: Concave flattener of <Chemical Formula 1B> + convex flattener of <Chemical Formula 3A>

[0172] In Manufacturing Example 4, the same <Chemical Formula 1B> as Manufacturing Example 2 and the convex flattener represented by the following Chemical Formula 3A were used.

[0173] Specifically, a plating solution was prepared by adding 60 g of copper ions, 150 g of sulfuric acid ions, 50 mg of chloride ions, a polyethylene oxide derivative containing an aromatic hydrocarbon, an organic compound containing a mercapto group as an accelerator, and two leveling agents of the above <Chemical Formula 1B> and the following <Chemical Formula 3A> per liter of the plating solution.

[0174] Chemical Formula 3A: Quaternized Poly(diethyl dimethylpyrazolidine), X is chlorine

[0175]

[0176] Manufacturing Example 6: Concave flattener of <Compound 1C> + convex flattener of <Chemical Formula 3A>

[0177] In Manufacturing Example 6, <Chemical Formula 1C>, the same as Manufacturing Example 3, and <Chemical Formula 3A> used in Manufacturing Example 5 were used.

[0178] A plating solution was prepared by adding 60 g of copper ions, 150 g of sulfuric acid ions, 50 mg of chloride ions, a polyethylene oxide derivative containing an aromatic hydrocarbon, an organic compound containing a mercapto group as an accelerator, and two leveling agents, <Compound 1A> and <Compound 3B>, to 1 liter of the plating solution.

[0179]

[0180] The above manufacturing examples 1 to 6 commonly contain 60 g of copper ions, 150 g of sulfuric acid ions, 50 mg of chloride ions, a polyethylene oxide derivative containing an aromatic hydrocarbon as an inhibitor, and an organic compound containing a mercapto group as an accelerator per liter of the plating solution.

[0181] In Manufacturing Examples 1 to 3, only different concave levelers having the structure of <Chemical Formula 1> were added, in Manufacturing Example 4, a concave leveler having the structure of <Chemical Formula 1A> and a convex leveler having <Chemical Formula 2A> were further added, in Manufacturing Example 5, a concave leveler having the structure of <Chemical Formula 1B> and a convex leveler having <Chemical Formula 3A> were further added, and in Experimental Example 6, a concave leveler having the structure of <Chemical Formula 1C> and a convex leveler having <Chemical Formula 3A> were further added.

[0182]

[0183] Experimental Example 1: Electroplating experiment of Manufacturing Example 1

[0184] Figure 1a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 1 according to the present invention.

[0185] Figure 1b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 1 according to the present invention.

[0186] After preparing a plating solution containing only 90 mg / l of <Chemical Formula 1A> in the above Manufacturing Example 1, plating was performed at a current density of 10ASD, and as a result, a concave copper plating film was formed as shown in FIGS. 1a and 1b.

[0187]

[0188] Experimental Example 2: Electroplating Experiment of Manufacturing Example 2

[0189] Figure 2a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 2 according to the present invention.

[0190] Figure 2b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 2 according to the present invention.

[0191] In the above Manufacturing Example 2, after preparing a plating solution containing only 70 mg / l of <Chemical Formula 1B>, plating was performed at a current density of 10ASD, and as a result, a concave copper plating film was formed as shown in FIGS. 2a and 2b.

[0192]

[0193] Experimental Example 3: Electroplating Experiment of Manufacturing Example 3

[0194] Figure 3a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 3 according to the present invention.

[0195] Figure 3b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 3 according to the present invention.

[0196] In the above Manufacturing Example 3, after preparing a plating solution containing only 15 mg / l of <Chemical Formula 1C>, plating was performed at a current density of 10ASD, and as a result, a concave copper plating film was formed as shown in FIGS. 3a and 3b.

[0197]

[0198] Experimental Example 4: Electroplating Experiment of Manufacturing Example 4

[0199] Figure 4a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 4 according to the present invention.

[0200] Figure 4b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 4 according to the present invention.

[0201] In the above manufacturing example 4, after preparing a plating solution containing 90 mg / l of <Chemical Formula 1A> and 100 mg / l of <Chemical Formula 2A>, plating was performed at a current density of 10ASD, and as a result, a copper plating film having a flat shape was formed as shown in FIGS. 4a and 4b.

[0202]

[0203] Experimental Example 5: Electroplating Experiment of Manufacturing Example 5

[0204] Figure 5a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 5 according to the present invention.

[0205] Figure 5b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 5 according to the present invention.

[0206] In the above manufacturing example 5, after preparing a plating solution containing 100 mg / l of <Chemical Formula 1B> and 180 mg / l of <Chemical Formula 3A>, plating was performed at a current density of 10ASD, and as a result, a copper plating film having a flat shape was formed as shown in FIGS. 5a and 5b.

[0207]

[0208] Experimental Example 6: Electroplating Experiment of Manufacturing Example 6

[0209] Figure 6a is an optical microscope (OM) photograph showing the result of electrolytic copper plating performed on a substrate under the conditions of Manufacturing Example 6 according to the present invention.

[0210] Figure 6b is a profile of a copper plating film analyzed using a confocal laser microscope for the copper plating result obtained by using the copper plating solution of Manufacturing Example 6 according to the present invention.

[0211] In the above manufacturing example 6, after preparing a plating solution containing 20 mg / l of <Chemical Formula 1C> and 180 mg / l of <Chemical Formula 3A>, plating was performed at a current density of 10ASD, and as a result, a copper plating film having a flat shape was formed as shown in FIGS. 6a and 6b.

[0212]

[0213] Therefore, from the experimental examples described above, it can be seen that the concave leveling agent having the structure of chemical formula 1 can make the surface of the copper film concave, and that the uniformity and flatness of the copper plating film can be increased by mixing the concave leveling agent and a convex leveling agent compound that can make the surface of the copper film convex.

[0214] In conclusion, according to an embodiment of the present invention, a copper plating film can be deposited uniformly and with excellent flatness within a pattern on a substrate, thereby providing an effect of improving the electrical characteristics and reliability of a device manufactured using the same.

[0215] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0216] The scope of the present invention is indicated by the claims described below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. An organic additive added to a copper plating solution for forming a copper film by electroplating on a substrate on which a pattern has been formed. In order to increase the uniformity and flatness of the copper film formed on the pattern, at least two types of flattening agents are included. The above two types of flatteners are convex flatteners that make the surface of the copper film convex; and An organic additive for electrolytic copper plating, characterized in that it includes a concave flattening agent having a structure of the following <chemical formula 1> that makes the surface of the copper film concave: <Chemical Formula 1> In the above chemical formula 1, A is a non-metallic element with an electronegativity of 2.0 or higher, R1' and R1'' are each independently, (1) a monomer or polymer comprising at least one alkylene oxide or ester functional group containing oxygen; or (2) a linear or branched alkyl having 1 to 20 carbon atoms and containing 1 to 5 amine groups; or (3) A linear or branched alkyl having 1 to 20 carbon atoms, comprising a monomer or polymer comprising 1 to 5 amine groups and at least one alkylene oxide or ester functional group containing oxygen at the chain terminal; R2' and R2'' are each independently a chain-like alkyl group having 1 to 10 carbon atoms; a hydroxyl group; or an amine group; R3 is a chain-like alkyl group having 1 to 10 carbon atoms; or an alkylene oxide; The sum of m and n is from 1 to 1000, and m and n are integers greater than or equal to 0.

2. In paragraph 1, An organic additive for electrolytic copper plating, characterized in that in the above <chemical formula 1>, A is CH or N.

3. In paragraph 1, The above convex flattener is an organic additive for electrolytic copper plating characterized by being expressed by the following <chemical formula 2> or the following <chemical formula 3>: <Chemical Formula 2> In the above chemical formula 2, A' contains at least one of an ether functional group, an ester functional group, and a carbonyl functional group, T1 and T2 are alkyl having a linear structure containing hydrogen alone or having 1 to 10 carbon atoms containing an ether functional group, or alkyl having a branched structure containing 5 to 20 carbon atoms containing an ether functional group, T3 and T4 are either a linear alkyl group containing hydrogen alone or having between 1 and 10 carbon atoms, or a branched alkyl group containing between 5 and 20 carbon atoms, The sum of m and n is an integer from 1 to 50, o is an integer from 1 to 100, X contains one or more ions selected from the group consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO3), sulfate (SO4), carbonate (CO3), and hydroxyl (OH), <Chemical Formula 3> In the above chemical formula 3, R4 is a saturated heterocyclic compound comprising at least one member selected from the group consisting of aziridine, oxirane, thiirane, diaziridine, oxaziridine, dioxirane, azetidine, oxetane, thietane, diazetidine, dioxetane, dithietane, pyrrolidine, thiolane, phosphorane, imidazolidine, pyrazolidine, oxazolidine, isooxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiolane, piperidine, oxane, thiane, phosphinane, piperazine, morpholine, thiomorpholine, dioxane, dithiane, azepane, oxepane, thiepane, homopyrerazine, azocane, oxocane, thiocane, azonane, oxonane, thionane, R5 and R6 are each independently a single hydrogen, a linear alkyl having 1 to 10 carbon atoms and containing an ether functional group, or a branched alkyl having 5 to 20 carbon atoms and containing an ether functional group, p is an integer between 300 and 4500, X contains one or more of the ions consisting of chlorine (Cl), bromine (Br), iodine (I), nitrate (NO3), sulfate (SO4), carbonate (CO3), and hydroxyl (OH).

4. In paragraph 1, An organic additive for electrolytic copper plating, characterized in that the above concave flattening agent has a concentration of 0.1 mg / L to 1000 mg / L in the organic additive for copper plating.

5. In paragraph 1, An organic additive for electrolytic copper plating, characterized in that the above concave flattening agent has a molecular weight in the range of 150 g / mol to 280,000 g / mol.

6. In paragraph 3, An organic additive for electrolytic copper plating, characterized in that the convex flattening agent expressed by the above <chemical formula 2> has a molecular weight in the range of 100 g / mol to 500,000 g / mol.

7. In paragraph 3, An organic additive for electrolytic copper plating, characterized in that the convex flattening agent expressed by the above <chemical formula 2> has a concentration of 0.1 mg / L to 1000 mg / L.

8. In paragraph 3, An organic additive for electrolytic copper plating, characterized in that the convex flattening agent expressed by the above <chemical formula 3> has a molecular weight in the range of 50,000 g / mol to 700,000 g / mol.

9. In paragraph 3, An organic additive for electrolytic copper plating, characterized in that the convex flattening agent expressed by the above <chemical formula 3> has a concentration of 0.1 mg / L to 1000 mg / L.

10. In paragraph 1, An organic additive for electrolytic copper plating, characterized in that it further comprises an inhibitor and an accelerator.

11. In paragraph 10, The above inhibitors are, 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-ethylene oxide, Dimethyloctynediol, An organic additive for electrolytic copper plating, characterized in that it comprises one or more substances selected from the group consisting of phenylbutynol, and 1,4-butandiol diglycidyl ether.

12. In paragraph 10, The above 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,NDimethyl-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, An organic additive for electrolytic copper plating, characterized in that it comprises one or more selected from the group of substances consisting of 5,5′-Dithiobis(2-nitrobenzoic acid), DL-Cysteine, 4-Mercapto-Benzenesulfonic acid, and 5-Mercapto-1H-tetrazole-1-methanesulfonic acid.

13. In paragraph 10, An organic additive for electrolytic copper plating, characterized in that the accelerator and the inhibitor each have a molecular weight in the range of 100 g / mol to 100,000 g / mol.

14. An electrolyte containing copper ions; and Contains an organic additive added to the above electrolyte, The organic additive includes an accelerator, an inhibitor, and at least two kinds of leveling agents to increase the uniformity and flatness of a copper film formed on a patterned substrate. The above flattener is, A concave flattener having a structure expressed by the following <Chemical Formula 1> that makes the surface of the copper film concave; and An electrolytic copper plating solution characterized by including a convex flattening agent that makes the surface of the copper film convex: <Chemical Formula 1> In the above chemical formula 1, A is a non-metallic element with an electronegativity of 2.0 or higher, R1' and R1'' are each independently, (1) a monomer or polymer comprising at least one alkylene oxide or ester functional group containing oxygen; or (2) a linear or branched alkyl having 1 to 20 carbon atoms and containing 1 to 5 amine groups; or (3) A linear or branched alkyl having 1 to 20 carbon atoms, comprising a monomer or polymer comprising 1 to 5 amine groups and at least one alkylene oxide or ester functional group containing oxygen at the chain terminal; R2' and R2'' are each independently a chain-like alkyl group having 1 to 10 carbon atoms; a hydroxyl group; or an amine group; R3 is a chain-like alkyl group having 1 to 10 carbon atoms; or an alkylene oxide; The sum of m and n is from 1 to 1000, and m and n are integers greater than or equal to 0.

Images