KR102447478B1 - Electrolytic copper plating additive for embedded trace substrate process and manufacturing thereof - Google Patents

Abstract

The present invention relates to an electrolytic copper plating additive for an embedded trace substrate method, which can minimize a surface defect by preventing growth of a crystal grain in an electrolytic copper plating process during a manufacturing process of an embedded trace substrate, and a manufacturing method thereof. In order to solve an above problem, the present invention provides the electrolytic copper plating additive for the embedded trace substrate method, comprising a compound having a structure of formula 1 as a smoothing agent.

Description

Electrolytic copper plating additive for embedded trace substrate process and manufacturing thereof

The present invention relates to an electrolytic copper plating additive for an embedded trace substrate method and a manufacturing method thereof, and more particularly, to an embedded trace substrate capable of minimizing surface defects by preventing the growth of crystal grains in the electrolytic copper plating process during the manufacturing process of the embedded trace substrate. It relates to an electrolytic copper plating additive for a manufacturing method and a method for manufacturing the same.

In recent years, the development of semiconductor substrates with a fine line width that enables input/output signals of high integration is actively being made, and these fine line width substrates are relatively expensive to implement. is being developed

In particular, in computers, laptops, and mobile phones, the chip capacity is increasing, such as large-capacity random access memory (RAM) and flash memory, as the storage capacity increases, but the package tends to be miniaturized. to be.

As a technique for achieving such miniaturization, the case of applying a substrate (eg, an embedded trace substrate) having a structure in which circuit patterns are embedded (embedded) is increasing significantly.

As a representative example, a coreless PCB may be exemplified. A coreless PCB is a PCB that has removed a core from the existing standard core PCB, and has the advantage of reducing the thickness while having similar electrical performance compared to the core PCB. In addition, it is relatively easy to implement a fine circuit due to the nature of the coreless method.

As another example, consider an active element or a passive element embedded PCB, and it can be seen that not only the role of the electrical connection of the PCB but also the role of a power supply, a capacitor, an inductor, etc. are required at the same time.

Recently, coreless PCB and electronic device embedded PCB method are simultaneously applied, which is a structure that utilizes the advantages of both methods at the same time. The structure is in the spotlight.

The double embedded trace board can have the advantage of reducing the size of the board including the circuit pattern as shown above, but after the heat treatment process of the bottom surface of the circuit pattern, the circuit pattern is coarsened and surface defects often occur. Therefore, it is necessary to develop a new technology to improve it.

(0001) Republic of Korea Patent No. 10-1585554 (0002) Republic of Korea Patent Registration No. 10-2333084

In order to solve the above problem, the present invention is to provide an electrolytic copper plating additive for an embedded trace substrate method and a method for manufacturing the same, which can minimize surface defects by preventing the growth of crystal grains in the electrolytic copper plating process during the manufacturing process of the embedded trace substrate. do.

In order to solve the above problems, the present invention provides an electrolytic plating additive for an embedded trace substrate method comprising a compound having a structure of the following Chemical Formula 1 as a smoothing agent.

[Formula 1]

(in Formula 1 above

A is C1~ C30 substituted or unsubstituted linear aliphatic hydrocarbon group, C1~ C30 substituted or unsubstituted branched aliphatic hydrocarbon group, C6~ C40 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted already It is selected from a dazole group, a substituted or unsubstituted biimidazole group, a substituted or unsubstituted benzimidazole group, and a substituted or unsubstituted bibenzimidazole group,

X1, X2, X3 and X4 are each independently a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl group, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group It is selected from a ken group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkene group, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, and a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyyl group,

n is an integer from 1 to 20)

In one embodiment, A may be a substituted or unsubstituted biimidazole group or a substituted or unsubstituted bibenzimidazole group.

In one embodiment, the X1, X2, X3 and X4 are each independently a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyl group, and a substituted or unsubstituted It may be selected from an ether group of C1 to C10.

In an embodiment, the plating additive may further include a compound having a structure of Chemical Formula 2 below.

[Formula 2]

(In Formula 2,

M is 1~ C30 substituted or unsubstituted linear aliphatic hydrocarbon group, C1~ C30 substituted or unsubstituted branched aliphatic hydrocarbon group, C6~ C40 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted already A dazole group, a substituted or unsubstituted biimidazole group, a substituted or unsubstituted benzimidazole group, a substituted or unsubstituted bibenzimidazole group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted urea group, and It is selected from a substituted or unsubstituted alanine group,

R is a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl group, a substituted or unsubstituted C ₁ to C ₁₀ alkene group, a substituted or unsubstituted C ₁ To C ₁₀ Heteroalkene group, substituted or unsubstituted C ₁ ~ C ₁₀ Selected from alkyl group and substituted or unsubstituted C ₁ ~ C ₁₀ Heteroalkyyl group,

z is an integer from 1 to 10)

In one embodiment, M may be selected from a substituted or unsubstituted imidazole group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted urea group, and a substituted or unsubstituted alanine group.

In one embodiment, R is selected from a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyl group, and a substituted or unsubstituted C 1 ~ C 10 ether group it could be

In an embodiment, the electrolytic copper plating additive may inhibit the growth of copper grains during electrolytic copper plating.

In one embodiment, the copper crystal grains may have an average particle diameter of 1 ~ 6㎛.

The present invention also provides a metal ion source; the electrolytic plating additive; inhibitors; And it provides an electroplating composition comprising a brightener.

In one embodiment, the inhibitor may be an alkoxylate alcohol-based polymer.

In one embodiment, the brightener has a disulfide bond and may be a compound including one or more mercapto functional groups.

The electrolytic copper plating additive for the embedded trace substrate method according to the present invention can prevent the crystal grains from coarsening by interfering with the growth of the crystal grains of the electroplating machine, and accordingly, large crystal grains are exposed on the surface, resulting in reduced surface roughness. can prevent

In addition, in the past, low current plating was performed to prevent crystal grain growth. However, when the electrolytic copper plating additive for the embedded trace substrate method of the present invention is used, high current plating can be performed, thereby enabling more efficient electrolytic copper plating.

1 schematically shows an embedded trace substrate method according to an embodiment of the present invention.
2 is a diagram illustrating an electroplating process and a defective portion appearing in the embedded trace substrate method according to an embodiment of the present invention.
Figure 3 shows the coarsening of grains according to the heat treatment according to an embodiment of the present invention.
4 shows an outline of grain coarsening by heat treatment and an actual cross section thereof according to an embodiment of the present invention.
5 is a photograph showing crystal grains in a cross-section of plating according to an embodiment of the present invention.
6 is a photograph showing a plating cross-section (a-c) having coarsened crystal grains and a plating cross-section (d-f) in which coarsening is prevented due to the addition of an additive, respectively, according to an embodiment of the present invention.
7 is a photograph showing the results before and after heat treatment according to an embodiment of the present invention.
8 is a photograph of a grain size measured before and after heat treatment according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. Throughout the specification, the singular expression is to be understood as including the plural expression unless the context clearly dictates otherwise, and terms such as “comprises” or “have” refer to the described feature, number, step, operation, or element. , parts or combinations thereof are intended to designate the existence of one or more other features or numbers, steps, operations, components, parts, or combinations thereof, it is to be understood that it does not preclude the possibility of addition or existence in advance. . In addition, in performing the method or the manufacturing method, each process constituting the method may occur differently from the specified order unless a specific order is clearly described in context. That is, each process may occur in the same order as specified, may be performed substantially simultaneously, or may be performed in the reverse order.

The technology disclosed herein is not limited to the implementations described herein and may be embodied in other forms. However, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the technical spirit of the present technology may be sufficiently conveyed to those skilled in the art. In the drawings, in order to clearly express the components of each device, the sizes of the components such as width and thickness are somewhat enlarged. In the description of the drawings as a whole, it has been described from an observer's point of view, and when an element is referred to as being positioned on another element, this means that the element may be positioned directly on the other element or an additional element may be interposed between the elements. include In addition, those of ordinary skill in the art will be able to implement the spirit of the present invention in various other forms without departing from the technical spirit of the present invention. And the same reference numerals in the plurality of drawings refer to elements that are substantially the same as each other.

In this specification, the term 'and/or' includes a combination of a plurality of listed items or any of a plurality of listed items. In this specification, 'A or B' may include 'A', 'B', or 'both A and B'.

The present invention relates to an electrolytic copper plating additive for an embedded trace substrate method comprising a compound having a structure of the following Chemical Formula 1 as a smoothing agent.

[Formula 1]

(in Formula 1 above

A is C1~ C30 substituted or unsubstituted linear aliphatic hydrocarbon group, C1~ C30 substituted or unsubstituted branched aliphatic hydrocarbon group, C6~ C40 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted already It is selected from a dazole group, a substituted or unsubstituted biimidazole group, a substituted or unsubstituted benzimidazole group, and a substituted or unsubstituted bibenzimidazole group,

X1, X2, X3 and X4 are each independently a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl group, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group It is selected from a ken group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkene group, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, and a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyyl group,

n is an integer from 1 to 20)

In the present invention, the term “linear aliphatic hydrocarbon group” refers to a hydrocarbon group formed by linear bonding of carbons. In general, it may be formed only by a single bond, but one or more carbons may have a double bond and may be connected. That is, in the case of the linear aliphatic hydrocarbon, it may be composed of an alkyl group having a linearity, or an alkene group having one or more double bonds.

In the present invention, the term “branched aliphatic hydrocarbon group” means that one or more hydrogens are substituted with a linear aliphatic hydrocarbon group in the linear aliphatic hydrocarbon group. Through this, the branched hydrocarbon group may have a kind of branched shape. In addition, it may be divided into a main chain hydrocarbon serving as a basic skeleton and a branched chain hydrocarbon in which hydrogen is substituted.

In the present invention, the term “aromatic hydrocarbon group” refers to a hydrocarbon containing a benzene ring, and one or more hydrogens may be substituted with another alkyl group, an alkene group or an alkyl group based on the benzene ring. In addition, in the case of the aromatic hydrocarbon, one or more units based on the benzene ring as described above may be combined (eg, bibenzene). In addition, other types of cyclic compounds may be bonded to the benzene ring (eg, benzimidazole).

In the present invention, the term imidazole group refers to a compound having the structure of Formula 3 below.

[Formula 3]

In this case, the imidazole may be used as the imidazole itself, but one or more hydrogens may be substituted with an alkyl group, an alkene group, an alkyl group, or a cyclic hydrocarbon.

In the present invention, the term biimidazole group means that the two imidazole groups are linked.

In the present invention, the term benzimidazole group refers to a compound having the structure of Formula 4 below.

[Formula 4]

In this case, in the case of the benzimidazole, the benzimidazole itself may be used, but one or more hydrogens may be substituted with an alkyl group, an alkene group, an alkyl group, or a cyclic hydrocarbon.

In the present invention, the term bibenzimidazole group means that the two benzimidazole groups are linked.

As used herein, the term "alkyl" or "alkyl group" by itself or as part of another substituent means a straight or branched chain, or cyclic hydrocarbon radical, or a combination thereof, unless otherwise specified, which is fully saturated or It may be partially or fully unsaturated, and may include divalent and polyvalent radicals having the specified number of carbon atoms (eg C 1 -C 10 means 1 to 10 carbons). Examples of saturated hydrocarbon radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, cyclohexyl, (cyclohexyl)methyl, cyclopropylmethyl, for example n -pentyl, n-hexyl, n-heptyl, n-octyl and the like homologues and isomers, and the like. An unsaturated alkyl group is one having one or more double or triple bonds. Examples of unsaturated alkyl groups include vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), in thynyl, 1- and 3-propynyl, 3-butynyl, and higher homologs and isomers.

In the present invention, the term “heteroalkyl” or “heteroalkyl group” by itself or in combination with another term means at least one selected from the group consisting of the stated number of carbon atoms and O, N, Si and S, unless otherwise specified. means a stable straight or branched chain, or cyclic hydrocarbon radical consisting of heteroatoms, or combinations thereof, wherein the nitrogen and sulfur atoms may optionally be oxidized and the nitrogen heteroatom may optionally be quaternized. The heteroatom(s) O, N and S and Si may be placed at any internal position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule. Examples are -CH2-CH2-O-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S=CH2-CH3, -CH2-CH2-S(O )-CH3, -CH2-CH2-S(O)2-CH3, -CH=CH-O-CH3, -Si(CH3)3, -CH2-CH=N-OCH3, and -CH=CH-N( CH3)-CH3. Up to two heteroatoms may be contiguous, for example -CH2-NH-OCH3 and -CH2-OSi(CH3)3.

In the present invention, the term “alkene” or “alkene group” refers to an unsaturated alkyl group having a double bond, and one or more of the carbon-carbon bonds of the alkyl group means having a double bond. The term "heteroalkene" also denotes an alkene group containing 1 to 4 heteroatoms selected from the group consisting of N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom(s) are optionally 4 is accelerated

As used herein, the term “alkyyl” or “alkyyl group” refers to an unsaturated alkyl group having a triple bond, and one or more of the carbon-carbon bonds of the alkyl group means having a triple bond. The term "heteroalkyyl" also refers to an alkyyl group containing 1 to 4 heteroatoms selected from the group consisting of N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom(s) are arbitrarily 4th grade.

In the present invention, the term ether refers to a compound in which the alkyl group, alkene group, or alkyl group is bonded to both sides around an oxygen atom.

In the present invention, the term pyridine group refers to a compound in which the carbon of the benzene ring is substituted with nitrogen. In the present invention, the pyridine group may be one in which one or more hydrogens are substituted with the alkyl group, alkene group, alkyl group, or aromatic hydrocarbon group.

In the present invention, the term urea group refers to a compound in which oxygen and NH2 are bonded to each other around carbon. In general, one or more of NH2 may be substituted with an alkyl group, an alkene group, an alkyl group, or an aromatic hydrocarbon group.

In the present invention, the term alanine group refers to a compound having the structure of the following Chemical Formula 5.

[Formula 5]

In this case, one or more hydrogens in the alanine group may be substituted with an alkyl group, an alkene group, an alkyl group, or a cyclic hydrocarbon.

In the case of A, as shown above, a C1-C30 substituted or unsubstituted linear aliphatic hydrocarbon group, a C1-C30 substituted or unsubstituted branched aliphatic hydrocarbon group, a C6-C40 substituted or unsubstituted aromatic hydrocarbon group, It may be selected from a substituted or unsubstituted imidazole group, a substituted or unsubstituted biimidazole group, a substituted or unsubstituted benzimidazole group and a substituted or unsubstituted bibenzimidazole group, but preferably A may be a substituted or unsubstituted biimidazole group or a substituted or unsubstituted bibenzimidazole group.

Wherein X1, X2, X3 and X4 are each independently a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ Can be selected from an alkene group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkene group, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, and a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyyl group However, it may be preferably selected from a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyl group, and a substituted or unsubstituted C 1 ~ C 10 ether group.

Here, the functional group bonded to both ends of the compound represented by the structural unit represented by Formula 1 (a monomer having n=1) or a compound in which a plurality of structural units are bonded (a polymer having n=2 to 20) is not specifically defined. It may be one hydrogen (H).

Specifically, when the electrolytic copper plating additive for the embedded trace substrate method according to the present invention has the structure of Chemical Formula 1, a structural unit selected from the group consisting of structural units represented by Chemical Formulas 6 to 10 (n=an integer of 1 to 20) It may be embodied as a compound comprising, but is not limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In addition, the electrolytic copper plating additive for the embedded trace substrate method of the present invention may further include a compound having the structure of the following Chemical Formula 2 to improve performance.

[Formula 2]

(In Formula 2,

M is 1~ C30 substituted or unsubstituted linear aliphatic hydrocarbon group, C1~ C30 substituted or unsubstituted branched aliphatic hydrocarbon group, C6~ C40 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted already A dazole group, a substituted or unsubstituted biimidazole group, a substituted or unsubstituted benzimidazole group, a substituted or unsubstituted bibenzimidazole group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted urea group, and It is selected from a substituted or unsubstituted alanine group,

R is a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl group, a substituted or unsubstituted C ₁ to C ₁₀ alkene group, a substituted or unsubstituted C ₁ To C ₁₀ Heteroalkene group, substituted or unsubstituted C ₁ ~ C ₁₀ Selected from alkyl group and substituted or unsubstituted C ₁ ~ C ₁₀ Heteroalkyyl group,

z is an integer from 1 to 10)

Specifically, M may be selected from a substituted or unsubstituted imidazole group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted urea group, and a substituted or unsubstituted alanine group. In addition, R may be selected from a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyl group, and a substituted or unsubstituted C 1 ~ C 10 ether group.

Here, the functional group bonded to both ends of the compound represented by the structural unit represented by Formula 2 (a monomer having z=1) or a compound in which a plurality of structural units are bonded (a polymer having z=2 to 10) is not specifically defined. It may be one hydrogen (H).

Specifically, when the electrolytic copper plating additive for an embedded trace substrate method according to the present invention has the structure of Chemical Formula 2, a structural unit selected from the group consisting of structural units represented by Chemical Formulas 11 to 15 below (n=an integer of 1 to 10) It may be embodied as a compound comprising, but is not limited thereto.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

On the other hand, the method of synthesizing the compound of Formula 1 among the electrolytic copper plating additives for the embedded trace substrate method according to the present invention is not particularly limited, but an alkylation agent compound and an amine compound are reacted in the presence of a solvent to increase the synthesis efficiency. method can be applied. Specifically, an electrolytic copper plating additive for an embedded trace substrate method according to the present invention can be synthesized through a process of adding and reacting an amine compound after dissolving an alkylating agent compound in a solvent. Here, the alkylating agent compound may be defined as a compound that imparts an alkyl group or an alkylene group in a molecule while performing a substitution reaction with the amine-based compound.

The alkylating agent compound is not particularly limited, but 1,2-Bis(2-chloroethoxy)ethane, 1,3-dichloro-2-propanol (1,3- Dichloro-2-propanol), 1,6-dichlorohexane (1,6-Dichlorohexane), 1,8-dichlorooctane (1,8-Dichlorooctane), bis (2-bromoethyl) ether (Bis (2-bromoethyl) ) ether) and a first alkylating agent selected from the group of bis (2-chloroethyl) ether (Bis (2-Chloromoethyl) ether) and 2- [2- (2-chloroethoxy) ethoxy] ethanol (2- [ 2- (2-Chloroethoxy) ethoxy] ethanol), 2- (2-chloroethoxy) ethanol (2- (2-Chloroethoxy) ethanol), 1- (2-chloroethoxy) -2- (2-methoxy A mixture of second alkylating agents selected from the group of 1-(2-chloroethoxy)-2-(2-methoxyethoxy)ethane may be used.

The amine-based compound is not particularly limited, but 1,1′-dipropyl-1H,1′H-2,2′-biimidazole (1,1′-Dipropyl-1H,1′H-2,2) '-biimidazole), 2,2'-biimidazole (2,2'-Biimidazole), 2,2'-bis (4,5-dimethylimidazole) (2,2'-Bis (4,5- dimethylimidazole)), 1-ethyl-1H-benzimidazole (1-Ethyl-1H-benzimidazole), 1H,1`H-2,2`-bibenzimidazole (1H,1'H-2,2'- Bibenzimidazole), it may be at least one selected from the group of benzimidazole (Benzimidazole).

The temperature for dissolving the alkylating agent compound in the solvent is not particularly limited, but may be 50 to 180 °C. In addition, the reaction ratio (a:b) of the alkylating agent compound (a) and the amine compound (b) is not particularly limited, but may be a weight ratio of 1:2 to 6:1. In addition, when two or more kinds of the alkylating agent (a, a') are added, the reaction ratio (a:b) is 1:1 to 6:1 by weight, and the reaction ratio of a':b is 1:1 to 6:1 may be a weight ratio of

The alkylating agent compound may be added to form X1, X2, X3, and X4, and in this case, the alkylating agent for forming X1, X2, X3 and X4 may be added simultaneously or sequentially. In the present invention, since X1 and X2 are derived from the same alkyl group, and X3 and X4 are also derived from the same alkyl group, an alkylating agent for forming X1 and X2 is added, and then a predetermined time (about 2 to 5 hours) is It is preferable to add an alkylating agent to form X3 and X4 after elapsed time. In this case, the weight ratio of the amine-based compound and the alkylating agent for forming X1 and X2 may be 2:1 to 1:3, which is the same as the weight ratio of X3 and X4.

The solvent used for dissolving the alkylating agent compound is not particularly limited as long as it is a commonly known solvent, but in consideration of solubility and synthesis efficiency, an aqueous solvent (water, purified water, deionized water, etc.), an alcoholic solvent (ethanol, methanol, At least one selected from the group consisting of ethylene glycol, etc.) and organic solvents (acetonitrile, dimethylformamide, dimethylacetamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide, etc.) may be used.

The compound of Formula 2 may also be prepared in a manner similar to the compound of Formula 1 above. That is, in the case of the compound of Formula 2, it may be prepared through a reaction between an alkylating agent (third alkylating agent) and an amine-based compound (second amine-based compound).

The alkylating agent is not particularly limited, but 1,2-bis (2-chloroethoxy) ethane (1,2-Bis (2-chloroethoxy) ethane), 1,3-dichloro-2-propanol (1,3- Dichloro-2-propanol), from the group of 1,6-hexanediol diglycidyl ether (1,6-Hexanediol Diglycidyl Ether) and 1,4-butanediol diglycidyl ether (1,4-Butanediol Diglycidyl Ether) One or more selected may be used.

The amine-based compound is not particularly limited. Benzimidazole, Amino Pyridine, 2,6-diaminopyridine, Urea, Thiourea, Alanine and 1,2- It may include at least one selected from diphenyl urea (1,3-Diphenyl urea).

The temperature for dissolving the third alkylating agent compound in the solvent is not particularly limited, but may be 50 to 180°C. In addition, the reaction ratio (M:R) of the third alkylating agent compound (M) and the amine compound (R) is not particularly limited, but may be a weight ratio of 4:1 to 3:2.

The solvent used for dissolving the third alkylating agent compound is not particularly limited as long as it is a commonly known solvent, but in consideration of solubility and synthesis efficiency, an aqueous solvent (water, purified water, deionized water, etc.), an alcoholic solvent (ethanol, At least one selected from the group consisting of methanol, ethylene glycol, etc.) and organic solvents (acetonitrile, dimethylformamide, dimethylacetamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide, etc.) may be used.

The present invention provides an electroplating composition comprising the electroplating additive. Specifically, the electroplating composition according to the present invention comprises an ion source; the electrolytic plating additive; inhibitors; and brighteners.

The description of the electroplating additive included in the electroplating composition according to the present invention is the same as described above, and thus will be omitted. The concentration (content) of the electrolytic plating additive is not particularly limited, but may be 3 to 50 ml/L, specifically, 7.5 to 20 ml/L, in consideration of the uniformity of the circuit pattern and plating efficiency, etc. .

The metal ion source included in the electroplating composition according to the present invention supplies metal ions in the composition, and a commonly known material may be used. Specifically, the metal ion source may be a copper ion source. The concentration (content) of the metal ion source is not particularly limited, but in consideration of the uniformity and density of the circuit pattern, it may be 100 to 300 g/L, and specifically 100 to 250 g/L.

The brightener included in the electroplating composition according to the present invention promotes plating by increasing the reduction rate of metal ions, and a commonly known material may be used. Specifically, the brightener has a disulfide bond, and it is preferable to use one containing at least one mercapto functional group, and more specifically, bis-(3-sulfopropyl) disulfide (sodium salt) (bis -(3-sulfopropyl)disulfide, sodium salt), 3-mercapto-1-propanesulfonic acid (sodium salt) (3-mercapto-1-propanesulfonic acid, sodium salt), 3-amino-1-propanesulfonic acid ( 3-Amino-1-propanesulfonic acid), O-ethyl-S-(3-sulfopropyl)dithiocarbonate (sodium salt) (O-Ethyl-S-(3-sulphopropyl) dithiocarbonate, sodium salt), 3-( 2-Benzthiazolyl-1-thio)-1-propanesulfonic acid (sodium salt) (3-(2-Benzthiazoly-1-thio)-1-propanesulfonic acid, sodium salt) and N,N-dimethyldithiocarb It may be at least one selected from the group consisting of bamic acid-(3-sulfopropyl)ester (sodium salt) (N,N-Dimethyldithiocarbamic acid-(3-sulfopropyl)ester, sodium salt). The concentration (content) of such a brightener is not particularly limited, but may be 0.5 to 5 ml/L, specifically, 1 to 2.0 ml/L, in consideration of the plating speed and the like. When the brightener is contained below the above range, it is difficult to expect the effect of the brightener, and when the above range is exceeded, plating growth is excessively promoted and voids may occur inside the via hole.

The inhibitor included in the electroplating composition according to the present invention is to increase the surface flatness of the circuit pattern, and a commonly known material may be used. Specifically, the inhibitor may be an alkoxylate alcohol-based polymer, and a polymer in which propylene oxide and ethylene oxide are mixed in a weight ratio of 0.4:5 to 5:0.4 may be used. In addition, when the polymer is used, the molecular weight of the polymer may be 3,000 to 10,000 g/mol, preferably 2000 to 5000 g/mol. Within the molecular weight, normal plating and via hole filling performance may be exhibited, but if the molecular weight is out of the above range, the smoothness of the surface may be lowered, resulting in staining or a deeper dimple. The concentration (content) of the inhibitor is not particularly limited, but considering the uniformity of the circuit pattern and plating efficiency, it may be 5 to 30 ml/L, and specifically, 7.5 to 20 ml/L. When the inhibitor is included below the above range, it is difficult to expect the effect of the inhibitor, and when it exceeds the above range, stains may occur on the surface.

The present invention provides an embedded trace substrate (ETS) method using the electroplating composition. Embedded trace substrate method used in the present invention The same method as the existing method can be used (refer to FIG. 1), however, when copper plating, coarsening of copper crystals is reduced by using the electrolytic copper plating additive for the embedded trace substrate method. can be prevented

As used herein, the term "coarse" means that copper crystals are grown or coalesced during copper plating to form large copper crystals.

In general, in the case of a copper crystal, it is known that the less the interface occurs, the lower the resistance thereof. However, in the case of the copper crystal of the present invention, when a large crystal is formed as described above, the size of the crystal exposed to the surface increases, so that brilliance can be observed (see FIG. 2 ). In the present invention, since adhesion is formed by increasing surface roughness by exposing a large amount of copper crystals to the surface, the growth of copper crystals as described above corresponds to a defect that causes a decrease in adhesion. However, when the additive of the present invention is used, it is possible to prevent the grains from coarsening by preventing the growth of copper crystals as described above.

In addition, the coarsening may occur due to coalescence between grains during heat treatment as well as during the growth process of grains as described above. Coalesce of such grains is a spontaneous reaction that occurs due to a decrease in internal energy according to the supply of external thermal energy, so it is important to control this to prevent the growth of grains when heat treatment is performed (see FIGS. 3 and 4) . In the case of the conventional method, this was achieved by controlling the heat treatment temperature, time, and pressure, but in the present invention, coalescence of crystal grains can be minimized due to the addition of the additive, so that surface defects can be minimized.

In addition, due to the effect of these additives, in the case of the present invention, it is possible to perform plating with a higher current than conventional copper plating. In the case of the existing ETS method, low current plating was performed to prevent coarsening of copper crystals as described above, but in the case of such low current plating, a lot of plating time is required, which has a problem in economic feasibility. However, in the case of the present invention, coarsening of grains can be prevented even when high current plating is performed due to the effect of the additive.

In addition, in order to further reduce such coarsening, the current density applied during electroplating with the electroplating composition may be applied in a specific waveform. That is, referring to FIG. 4 , a current density of a stepped pulse (+ current applied)-reverse (-current applied) waveform having a cycle of 't1+t2+t3+t4+t5+t6' may be applied. Specifically, the positive current I1 is maintained for time t1, then the positive current I2 is maintained for the time t2, then the negative current I3 is held for the time t3, then the negative current I4 is held for the time t4, and then the negative current I3 is Electroplating is performed by periodically applying a waveform that is maintained for a time t5 and then a positive current I2 is maintained for a time t6 for a predetermined time.

Here, in order to prevent grain coarsening, I1 may be 2 to 5 ASD, I2 may be 1 to 2 ASD, I3 may be -1 to -2 ASD, and I4 may be -3 to -10 ASD. Also, t1, t2, and t6 may each be 10 to 80 ms (specifically, 30 to 50 ms), and t3, t4, and t5 may each be 1 to 5 ms (specifically, 2 to 4 ms).

As described above, during electroplating, it is a stepped pulse-reverse waveform representing a cycle of 't1+t2+t3+t4+t5+t6'. 20 to 40 minutes).

Hereinafter, preferred embodiments of the present invention will be described so that those of ordinary skill in the art can easily implement them with reference to the accompanying drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known function or a known configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, certain features presented in the drawings are enlarged, reduced, or simplified for ease of description, and the drawings and their components are not necessarily drawn to scale. However, those skilled in the art will readily appreciate these details.

Preparation Example 1

1,1'-Dipropyl-1H,1'H-2,2'-biimidazole as an amine compound was put in ethylene glycol and completely dissolved at a temperature of 140 °C.

Thereafter, 1,2-Bis(2-chloroethoxy)ethane (X1, X2 groups) is added as a first alkylating agent and reacted. At this time, the amine-based compound and the first alkylating agent were added in a weight ratio of 1:1. After the first alkylating agent was added, the reaction was carried out for 3 hours, and then 2-[2-(2-Chloroethoxy)ethoxy]ethanol (X3, X4 groups) as the second alkylating agent was added in a weight ratio of 1:1 with the amine compound. to obtain an electrolytic plating additive (Formula 6).

Preparation 2

2,2'-Biimidazole as an amine compound was put in ethylene glycol and completely dissolved at a temperature of 140 °C.

Thereafter, 1,2-Bis(2-chloroethoxy)ethane (X1, X2 groups) is added as a first alkylating agent and reacted. At this time, the amine-based compound and the first alkylating agent were added in a weight ratio of 1:1. After the first alkylating agent was added, the reaction was carried out for 3 hours, and then 2-[2-(2-Chloroethoxy)ethoxy]ethanol (X3, X4 groups) as the second alkylating agent was added in a weight ratio of 1:1 with the amine compound. Thus, an electrolytic copper plating additive was obtained.

Preparation 2

2,2'-Biimidazole as an amine compound was put in ethylene glycol and completely dissolved at a temperature of 140 °C.

Thereafter, 1,2-Bis(2-chloroethoxy)ethane (X1, X2 groups) is added as a first alkylating agent and reacted. At this time, the amine-based compound and the first alkylating agent were added in a weight ratio of 1:1. After the first alkylating agent was added, the reaction was carried out for 3 hours, and then 2-[2-(2-Chloroethoxy)ethoxy]ethanol (X3, X4 groups) as the second alkylating agent was added in a weight ratio of 1:1 with the amine compound. Thus, an electrolytic plating additive (Formula 7) was obtained.

Preparation 3

2,2'-Bis(4,5-dimethylimidazole) as an amine compound was put in ethylene glycol and completely dissolved at a temperature of 140 °C.

After that, 1,3-Dichloro-2-propanol (X1, X2 groups) is added as a first alkylating agent and reacted. At this time, the amine-based compound and the first alkylating agent were added in a weight ratio of 1:1. After the first alkylating agent was added, the reaction was carried out for 3 hours, and then, as the second alkylating agent, 2-(2-chloroethoxy)ethanol (X3, X4 groups) was added with the amine compound in a weight ratio of 1:1 to add an electrolytic plating additive ( Formula 8) was obtained.

Preparation 4

1H,1'H-2,2'-Bibenzimidazole as an amine compound was put into water and completely dissolved in reflux at a temperature of 120 °C.

After that, 1,6-Dichlorohexane (X1, X2 groups) is added as a first alkylating agent and reacted. At this time, the amine-based compound and the first alkylating agent were added in a weight ratio of 1:1. After the first alkylating agent was added, the reaction was carried out for 3 hours, and then 1-(2-chloroethoxy)-2-(2-methoxyethoxy)ethane (X3, X4 groups) as the second alkylating agent was mixed with the amine compound in a 1:1 ratio. By weight ratio, an electrolytic copper plating additive (Formula 9) was obtained.

Preparation 5

2,2'-Bis(4,5-dimethylimidazole) as an amine compound was added to ethanol and completely dissolved at a temperature of 60 °C.

Thereafter, Bis(2-Chloromoethyl) ether (X1, X2 groups) as a first alkylating agent is added and reacted. At this time, the amine-based compound and the first alkylating agent were added in a weight ratio of 1:1. After the first alkylating agent was added, the reaction was carried out for 3 hours, and then 1-(2-chloroethoxy)-2-(2-methoxyethoxy)ethane (X3, X4 groups) as the second alkylating agent was mixed with the amine compound in a 1:1 ratio. By weight ratio, an electrolytic copper plating additive (Formula 10) was obtained.

Preparation 6

Benzimidazole (M) was added to a round-bottom reaction flask at room temperature, and then 30 ml of ethylene glycol was added. An oil bath was used to completely dissolve the compound at a temperature of 140°C. Then, 1,2-Bis(2-chloroethoxy)ethane (R) used for synthesis was added and reacted. The weight ratio of M and R is 2:1. After adding the R compound, the reaction was terminated after 10 hours to synthesize a compound of Formula 11.

Preparation 7

Amino Pyridine (M) was added to a round-bottom reaction flask at room temperature, and then 30 ml of ethylene glycol was added. An oil bath was used to completely dissolve the compound at a temperature of 140°C. Then, 1,2-Bis(2-chloroethoxy)ethane (R) used for synthesis was added and reacted. The weight ratio of M and R is 2:1. After adding the R compound, the reaction was terminated after 10 hours to synthesize a compound of Formula 12.

Preparation 8

Amino Pyridine (M) was added to a round-bottom reaction flask at room temperature, and then 30 ml of ethylene glycol was added. An oil bath was used to completely dissolve the compound at a temperature of 140°C. Then, 1,3-Dichloro-2-propanol (R) used for synthesis was added and reacted. The weight ratio of M and R is 2:1. After adding the R compound, the reaction was terminated after 10 hours to synthesize a compound of Formula 13.

Preparation 9

Urea (M) was placed in a round-bottom reaction flask at room temperature, and then 40 ml of purified water was added. Reflux was performed at a temperature of 100° C. using an oil bath to completely dissolve the compound. Then, 1,6-Hexanediol Diglycidyl Ether (R) used for synthesis was added and reacted. The weight ratio of M and R is 2:1. After adding the R compound, the reaction was terminated after 10 hours to synthesize a compound of Formula 14.

Preparation 10

1,3-Diphenyl urea (M) was placed in a round-bottom reaction flask at room temperature, and then 30 ml of ethanol was added. An oil bath was used to completely dissolve the compound at a temperature of 700°C. Then, 1,6-Hexanediol Diglycidyl Ether (R) used for synthesis was added and reacted. The weight ratio of M and R is 2:1. After adding the R compound, the reaction was terminated after 7 hours to synthesize a compound of Formula 15.

Examples 1-10

The compound (additive 1) prepared in Preparation Examples 1-5 and the compound (additive 2) prepared in Preparation Examples 6-10 were combined as shown in Table 1 below to prepare an additive for plating. In addition, as a comparative example, an additive for plating (JGB-Janus Green B, Sigma Aldrich) used in the past was used. At this time, the ratio of each additive was used by mixing the same amount (1:1) as a weight ratio.

Additive 1 Additive 2 conventional additives Example 1 Preparation Example 1 Preparation 6 - Example 2 Preparation Example 1 Preparation 7 - Example 3 Preparation Example 1 Preparation 8 - Example 4 Preparation 2 - Example 5 Preparation 2 Preparation 6 - Example 6 Preparation 3 Preparation 6 - Example 7 Preparation 4 Preparation 9 - Example 8 Preparation 5 Preparation 10 - Example 9 Preparation Example 1 - JGB Comparative Example 1 Preparation Example 1 - - Comparative Example 2 - Preparation 6 - Comparative Example 3 - - JGB

Experimental Example 1

Copper sulfate pentahydrate 200 g/L, sulfuric acid 100 g/L, hydrochloric acid 50 mg/L, bis-(sodium sulfopropyl)-disulfide) 1.3 ml/L, carrier 10 ml/L , an electroplating composition containing 10 ml/L of additive (Example 1) was prepared.

Via holes having diameters of 120 and 140 μm and depth of 100 μm were formed by laser processing on an epoxy resin substrate having a thickness of 200 μm. Next, an epoxy resin substrate having via holes was put into an electroless plating solution containing copper sulfate, EDTA, formalin, caustic soda and an additive for surface stabilization, and electroless plating was performed at 65° C. to form a copper seed layer. Then, electroplating was performed with the electroplating composition including the additive (Example 1) to fill the via hole. When plating with the electroplating composition, plating conditions were set as follows.

- Electroplating composition temperature: 21 to 24 ℃

- Stirring: 0.5 to 1.5 LPM/con.

- Electrode: Insoluble electrode

- Current density: 3ASD

At this time, in order to check the effect of filling according to time, the via holes were filled with different plating times. In addition, it was confirmed that plating was normally completed in less than 70 minutes. In particular, when plating was carried out with a plating time of 70 minutes, 18 μm was plated, when it was 60 minutes, it was 15 μm, and when it was 50 minutes, it was 13 μm. appeared to be controllable.

Experimental Example 2

Copper sulfate pentahydrate 200 g/L, sulfuric acid 100 g/L, hydrochloric acid 50 mg/L, bis-(sodium sulfopropyl)-disulfide) 1.3 ml/L, carrier 10 ml/L , An electroplating composition containing 10 ml/l of the additive of Example 1 and Comparative Example 2 was prepared.

A via hole having a diameter of 90 μm and a depth of 100 μm was formed by laser processing on an epoxy resin substrate having a thickness of 200 μm. Next, an epoxy resin substrate having via holes was put into an electroless plating solution containing copper sulfate, EDTA, formalin, caustic soda and an additive for surface stabilization, and electroless plating was performed at 65° C. to form a copper seed layer. Then, electroplating was performed with the electroplating composition including each of the additives prepared in Example 1 and Comparative Example 2 to fill the via hole. When plating with the electroplating composition, plating conditions were set as follows.

- Electroplating composition temperature: 21 to 24 ℃

- Stirring: 0.5 to 1.5 LPM/con.

- Electrode: Insoluble electrode

- Current density: Step-step pulse-repulse waveform under the conditions of Table 2 below

current density Authorization time Frequency
(Hz) average current duty cycle I _for
(ASD) I _rev
(ASD) T _for
(sec) T _rev
(sec) T _off
(sec) I _for,AVG
(ASD) I _{rev, AVG}
(ASD) 3.6 12 0.04 0.004 0.002 22 3.27 2.09 0.91

After the plating was completed, the cross section of the substrate was checked with an optical microscope, and when the additive of Example 1 of the present invention was used and a stepped pulse-reverse waveform was used, high-speed plating was possible, and coarsening of the crystal grains was also minimized, In the case of the comparative example, coarsening of the crystal grains appeared, and defects (shining) were observed on the surface.

Experimental Example 3

In order to check the conditions for applying the current density during plating with the electroplating additive of Example 1, the plating was performed by adjusting as shown in Table 3 below. After the plating was completed, it was evaluated whether coarsening of the crystal grains was formed on the cross section of the substrate, and the results are shown in Table 4 below. In this case, a direct current (DC) waveform was applied as a comparison condition, not a stepped pulse-reverse waveform. In addition, coarsening of the grains was evaluated as coarsening when the average grain diameter of the grains exceeded 3 μm.

division current density Authorization time Frequency
(Hz) average current duty cycle I _for
(ASD) I _rev
(ASD) T _for
(sec) T _rev
(sec) T _off
(sec) I _for,AVG
(ASD) I _{rev, AVG}
(ASD) Condition 1 3.6 12 0.04 0.004 0.002 22 3.27 2.09 0.91 condition 2 3 6 0.04 0.002 0.002 23 2.86 2.45 0.95 condition 3 3.6 8 0.04 0.004 0.002 22 3.27 2.43 0.91 condition 4 3 5 0.04 0.002 0.002 23 2.86 2.50 0.95 Comparison condition 1 1.2 0 0 0 - One 1.20 0.00 - Comparison condition 2 2.4 0 0 0 - One 2.40 0.00 - Comparison condition 3 3.6 0 0 0 - One 3.60 0.00 -

division Plating time (min) Maximum grain size (㎛) Condition 1 61 1.3 condition 2 62 1.4 condition 3 62 2.1 condition 4 61 1.5 Comparison condition 1 69 2.8 Comparison condition 2 70 2.6 Comparison condition 3 69 2.9

Referring to Tables 3 and 4, it was confirmed that the plating time can be shortened when the electroplating additive according to the present invention is used, and coarsening of the crystal grains can also be minimized. However, it was confirmed that the plating time increased when the DC waveform was applied, and the size of the grains was also increased, although not to the level of coarsening.

Experimental Example 4

Experiments were carried out in the same manner as in Experimental Example 1 using Examples 1 to 10 and Comparative Examples 1 to 2, respectively. After the plating was completed, the cross-section of the substrate was observed to confirm whether the grains were coarsened.

division Plating time (min) Maximum grain size (㎛) Example 1 68 2.5 Example 2 62 2.1 Example 3 63 1.9 Example 4 62 2.0 Example 5 67 2.8 Example 6 64 2.6 Example 7 62 2.4 Example 8 64 2.1 Example 9 63 2.0 Comparative Example 1 82 6.3 Comparative Example 2 74 6.8 Comparative Example 3 81 5.9

As shown in Table 5, in the case of the example of the present invention, the plating time was measured to be less than 70 minutes, and the grain size was also measured to be less than 3 μm. However, in the case of Examples 1 and 5 in which only additive 1 was used alone, it was confirmed that the plating time and the grain size of the crystal grains slightly increased. It was confirmed to be effective. In addition, it was confirmed that when only additive 2 was used alone (Comparative Example 1), the effect hardly appeared.

In addition, the cross section was directly observed to confirm the effect of these additives. As shown in FIG. 5 , in Comparative Example 2 using the conventional additive, it was confirmed that the size of the crystal grains increased, and in the case of Example 1 of the present invention, it was confirmed that crystal grains having a small size were formed. In addition, in the case of Example 2 in which the two additives were mixed, the size of the crystal grains was further reduced. In addition, in the case of Examples 1 and 2 of the present invention, it was confirmed that the crystal growth direction was randomly generated, and the growth of crystal grains may be reduced due to this random crystal growth direction, and as a result, coarsening of the crystal grains was suppressed. was able to confirm that

In addition, as shown in a, b, and c of FIG. 6 , when the grains are coarsened, the size of the crystals exposed to the surface increases and sparkle may occur, but when the additive used in the embodiment of the present invention is used In (d, e, f of FIG. 6), the size of the crystal grains may be reduced, so that the size of the crystals exposed to the surface may be reduced. This means that the roughness of the surface is increased, and also means that adhesion to the surface can be increased.

Experimental Example 5

After plating using the additives of Example 1 and Comparative Example 3, heat treatment was performed, and the grain size change of the crystal structure was confirmed. Experiments were conducted in the same manner as in Experimental Example 1 using the additives of Example 1 and Comparative Example 3, and after the experiment was completed, heat treatment was performed while pressing at a pressure of 35 kg/cm 2 at 230° C. for 1 hour to compress the substrate. carried out. After the heat treatment was completed, the cross-section of the substrate was observed to confirm whether the grains were coarsened.

Maximum grain size (㎛) Example 1 3.7 Comparative Example 3 10.7

In the case of Comparative Example 3 using the existing additives, it was found that the grains coalesce after heat treatment and coarsening becomes more severe. was able to confirm that

7 (a) shows a cross section of Example 2 before heat treatment, and FIG. 7 (b) shows a cross section after heat treatment. In addition, (c) of FIG. 7 shows a cross section of Comparative Example 2 before heat treatment, and (d) of FIG. 7 shows a cross section after heat treatment. 7, when the additive of the present invention is used, it is possible to form a sizing size at the level of that using the conventional additive even after heat treatment, and when the conventional additive is used, coarsening of the grains is observed after heat treatment could check

This can also be confirmed through the grain size mapping shown in FIG. 8 . In the case of the example of the present invention, it can have a grain size of 3.67 μm even after heat treatment, but in the case of the comparative example, it has a size of 5.88 μm.

Claims (11)

An electrolytic copper plating additive for an embedded trace substrate method comprising a compound having the structure of the following Chemical Formula 1 as a smoothing agent.
[Formula 1]

(in Formula 1 above
A is C1~ C30 substituted or unsubstituted linear aliphatic hydrocarbon group, C1~ C30 substituted or unsubstituted branched aliphatic hydrocarbon group, C6~ C40 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted already It is selected from a dazole group, a substituted or unsubstituted biimidazole group, a substituted or unsubstituted benzimidazole group, and a substituted or unsubstituted bibenzimidazole group,
X1, X2, X3 and X4 are each independently a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl group, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group It is selected from a ken group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkene group, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, and a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyyl group,
n is an integer from 1 to 20)
According to claim 1,
wherein A is a substituted or unsubstituted biimidazole group or a substituted or unsubstituted bibenzimidazole group. An electrolytic copper plating additive for an embedded trace substrate method.
According to claim 1,
Wherein X1, X2, X3 and X4 are each independently a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyl group, and a substituted or unsubstituted C 1 ~ C 10 ether group An electrolytic copper plating additive for a trace substrate method that is selected from.
According to claim 1,
The plating additive is an electrolytic copper plating additive for an embedded trace substrate method further comprising a compound having a structure of the following formula (2).
[Formula 2]

(In Formula 2,
M is 1~ C30 substituted or unsubstituted linear aliphatic hydrocarbon group, C1~ C30 substituted or unsubstituted branched aliphatic hydrocarbon group, C6~ C40 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted already A dazole group, a substituted or unsubstituted biimidazole group, a substituted or unsubstituted benzimidazole group, a substituted or unsubstituted bibenzimidazole group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted urea group, and It is selected from a substituted or unsubstituted alanine group,
R is a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl group, a substituted or unsubstituted C ₁ to C ₁₀ alkene group, a substituted or unsubstituted C ₁ To C ₁₀ is selected from a heteroalkene group, a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, and a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyyl group,
z is an integer from 1 to 10)
5. The method of claim 4,
Wherein M is selected from a substituted or unsubstituted imidazole group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted urea group, and a substituted or unsubstituted alanine group.
5. The method of claim 4,
Wherein R is selected from a substituted or unsubstituted C ₁ ~ C ₁₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₁₀ heteroalkyl group, and a substituted or unsubstituted C 1 ~ C 10 ether group for the trace substrate method Electrocopper Plating Additives.
According to claim 1,
The electrolytic copper plating additive is an electrolytic copper plating additive for a trace substrate method that interferes with the growth of copper grains during electrolytic copper plating.
8. The method of claim 7,
The copper crystal grains are an electrolytic copper plating additive for a trace substrate method having an average particle diameter of 1 to 6㎛.
a source of metal ions;
The electrolytic plating additive of any one of claims 1 to 8;
inhibitors; and
varnish;
An electroplating composition comprising a.
10. The method of claim 9,
The inhibitor is an alkoxylate alcohol-based polymer electroplating composition.
10. The method of claim 9,
The brightener has a disulfide bond, the electroplating composition is a compound comprising at least one mercapto (Mercapto) functional group.

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