Leveler and electroplating composition for filling via hole

Abstract

The present invention relates to a leveler capable of efficiently filling the inside of via holes formed during the manufacturing process of a printed circuit board, and an electroplating composition comprising the same. When via holes on a substrate are filled with the electroplating composition according to the present invention, the via holes can be filled in a relatively short time while minimizing the formation of dimples or voids.

Claims

1. A leveler represented by a compound, wherein the compound is Chemical Formula 8, ##STR00005## wherein x is an integer, and y is an integer.

2. An electroplating composition comprising a metal ion source; the leveler according to claim 1; an inhibitor; and a brightener.

3. The electroplating composition according to claim 2, wherein the inhibitor is an alkoxylate alcohol-based polymer.

4. The electroplating composition according to claim 3, wherein the inhibitor is a polymer in which propylene oxide and ethylene oxide are mixed in a weight ratio of 0.4:5 to 5:0.4.

5. The electroplating composition according to claim 2, wherein the brightener is a compound having a disulfide bond and containing at least one mercapto functional group.

Description

BEST MODE

(1) 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 related known technologies may obscure the gist of the present invention, the detailed description thereof will be omitted. Throughout the specification, it is to be understood that the singular forms a, an, and the comprise plural referents unless the context clearly dictates otherwise, and it is to be understood that the terms such as comprise or have as used in the present specification, are intended to designate the presence of stated features, numbers, steps, operations, components, parts or combinations thereof, but not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof. In addition, in performing the method or preparation method, each process constituting the method may occur in a different order 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.

(2) The technology disclosed in this specification is not limited to the embodiments described herein and may be embodied in other forms. However, the embodiments introduced herein are provided so that the content disclosed herein may be thorough and complete, and the technical spirit of the present technology may be sufficiently understood by those skilled in the art. In the drawings, in order to clearly express the components of each device, the size of the components, such as width or thickness, is shown somewhat enlarged. Overall, when describing the drawings, it was described from the observer's point of view, and when one element is referred to as being located on another element, this comprises all meanings that one element may be located directly on another element or additional elements may be interposed between them. In addition, those skilled in the art will be able to implement the spirit of the present invention in various other forms within the scope that does not depart from the technical spirit of the present invention. In addition, the same reference numerals on a plurality of drawings refer to elements that are substantially the same as each other.

(3) In this specification, the term and/or comprises a combination of a plurality of recited items or any one of a plurality of recited items. In this specification, A or B may comprise A, B, or both A and B.

(4) The present invention relates to a leveler comprising a structural unit represented by Formula 1 or Formula 2 below.

(5) ##STR00002## (wherein, R.sub.1, R.sub.2, R.sub.3, and RA are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted C.sub.1 to C.sub.10 alkyl group, a substituted or unsubstituted C.sub.1 to C.sub.10 heteroalkyl group, a substituted or unsubstituted C.sub.6 to C.sub.20 aryl group, a substituted or unsubstituted C.sub.2 to C.sub.20 heteroaryl group, a substituted or unsubstituted C.sub.6 to C.sub.20 arylene group and a substituted or unsubstituted C.sub.6 to C.sub.20 heteroarylene group, A.sub.1 and A.sub.2 are each independently selected from the group consisting of a substituted or unsubstituted C.sub.1 to C.sub.10 alkyl group, a substituted or unsubstituted C.sub.1 to C.sub.10 heteroalkyl group, a substituted or unsubstituted C.sub.1 to C.sub.10 alkene group, a substituted or unsubstituted C.sub.1 to C.sub.10 heteroalkene group, a substituted or unsubstituted C.sub.1 to C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.1 to C.sub.10 heteroalkynyl group, a substituted or unsubstituted C.sub.6 to C.sub.20 arylene group, a substituted or unsubstituted C.sub.6 to C.sub.20 heteroarylene group, a substituted or unsubstituted C.sub.3 to C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.1 to C.sub.20 heterocycloalkyl group and a substituted or unsubstituted imidazole group, and n is an integer from 1 to 10).

(6) As used herein, the term alkyl or alkyl group, by itself or as part of another substituent, means a straight-chain or branched-chain, or cyclic hydrocarbon radical, or a combination thereof, unless otherwise specified, and it may be fully saturated, partially or fully unsaturated, and may contain divalent and polyvalent radicals having a specified number of carbon atoms (e.g., C1 to C10 means 1 to 10 carbons). Examples of saturated hydrocarbon radicals comprise, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, cyclohexyl, (cyclohexyl)methyl, cyclopropylmethyl, for example, homologues and isomers of n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. The unsaturated alkyl group has one or more double bonds or triple bonds. Examples of the unsaturated alkyl group include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and higher homologs and isomers.

(7) As used herein, the term heteroalkyl or heteroalkyl group, by itself or in combination with another term, refers to a stable straight or branched chain, or cyclic hydrocarbon radical, or combinations thereof consisting of the stated number of carbon atoms and one or more heteroatoms selected from the group consisting of O, N, Si and S, unless otherwise stated, wherein the nitrogen and sulfur atoms may optionally be oxidized, and nitrogen heteroatoms may optionally be quaternized. The heteroatom(s), i.e., O, N and S and Si, can be placed at any internal position of the heteroalkyl group or at the position where the alkyl group is attached to the rest of the molecule. Examples thereof comprise, but are not limited to, CH2-CH2-OCH3, CH2-CH2-NHCH3, CH2-CH2-N(CH3)-CH3, CH2SCH2-CH3, CH2-CH2-S(O)CH3, CH2-CH2-S(O)2-CH3, CHCHOCH3, Si(CH3)3, CH2-CHNOCH3, and CHCHN(CH3)-CH3. For example, up to two heteroatoms may be consecutive, as in CH2-NHOCH3 and CH2-OSi(CH3)3.

(8) As used herein, the term aryl or aryl group refers to a polyunsaturated aromatic substituent which may be a single ring or multiple rings (preferably 1 to 3 rings) fused or covalently linked together, unless otherwise stated. In addition, the term heteroaryl refers to an aryl group (or ring) 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) is optionally quaternized. The heteroaryl group can be attached to the rest of the molecule through a heteroatom. Non-limiting examples of the aryl and heteroaryl groups comprise, but are not limited to, phenyl, benzyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3-quinolyl and 6-quinolyl. Substituents for each of the aforementioned aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below.

(9) As used herein, the term arylene refers to a polyunsaturated aromatic substituent which may be a single ring or multiple rings (preferably 1 to 3 rings) fused or covalently linked together. In the case of aryl, it is generally formed by removing one hydrogen atom from an aromatic hydrocarbon, the site of the removed hydrogen atom acts as a bonding site, but in the case of arylene, it means a compound in which two hydrogen atoms are removed and two bonding sites exist. Also, the term heteroarylene represents an arylene group (or ring) 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) is optionally quaternized. The heteroarylene group can be attached to the rest of the molecule through a heteroatom.

(10) As used herein, the term alkene or alkene group refers to an unsaturated alkyl group having a double bond, wherein one or more of the carbon-carbon bonds of the alkyl group have a double bond. Also, the term heteroalkene refers to 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) is optionally quaternized.

(11) As used herein, the term alkynyl or alkynyl group refers to an unsaturated alkyl group having a triple bond, wherein one or more of the carbon-carbon bonds of the alkyl group have a triple bond. Also, the term heteroalkynyl refers to an alkynyl 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) is optionally quaternized.

(12) As used herein, the term cycloalkyl or cycloalkyl group refers to a cyclic compound formed by three or more carbons, which does not have a benzene structure, unlike the aryl or arylene. Also, the term heterocycloalkyl refers to a cycloalkyl group (or ring) 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) is optionally quaternized. The heterocycloalkyl group can be attached to the rest of the molecule through a heteroatom.

(13) As used herein, the term imidazole refers to a compound having a pentagonal ring structure composed of 3 carbon atoms and 2 nitrogen atoms, and may have the same structure as imidazole, which is generally manufactured and sold.

(14) Specifically, when considering the interaction between the leveler and additives added to the electroplating composition (e.g., brightener, carrier, accelerator, etc.), R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may be each independently selected from the group consisting of hydrogen, a C.sub.1 to C.sub.10 alkyl group, a C.sub.1 to C.sub.10 heteroalkyl group and a C.sub.6 to C.sub.20 arylene group.

(15) In addition, A.sub.1 and A.sub.2 may be each independently selected from the group consisting of a substituted or unsubstituted C.sub.1 to C.sub.10 heteroalkyl group, a substituted or unsubstituted C.sub.6 to C.sub.20 heteroarylene group, a substituted or unsubstituted C.sub.1 to C.sub.20 heterocycloalkyl group and a substituted or unsubstituted imidazole group.

(16) Here, the functional groups bonded to both ends of the compounds (monomers with n=1) represented by the structural units represented by Formula 1 and Formula 2 or the compounds (polymers with n=2 to 10) formed by combining a plurality of the structural units may be hydrogen (H) unless otherwise specified.

(17) Specifically, when the leveler according to the present invention has the structure of Formula 1, it may be embodied as a compound containing a structural unit selected from the group consisting of structural units represented by Formulas 3 to 7 below (n=an integer of 1 to 10), but is not limited thereto.

(18) ##STR00003##

(19) In addition, when the leveler of the present invention has the structure of Formula 2, it may be embodied as a compound containing a structural unit selected from the group consisting of structural units represented by Formulas 8 to 12 below (n=an integer of 1 to 10), but is not limited thereto.

(20) ##STR00004##

(21) Meanwhile, the method for synthesizing the leveler according to the present invention is not particularly limited, but a method of reacting an alkylation agent compound with an amine-based compound in the presence of a solvent in order to increase synthesis efficiency may be applied. Specifically, the leveler according to the present invention can be synthesized by dissolving an alkylation agent compound in a solvent and then adding and reacting an amine-based compound. Here, the alkylation 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.

(22) The alkylation agent compound is not particularly limited, but may be at least one selected from the group consisting of 1,4-dibromo benzene, 1-chloropropane, benzyl chloride, 1,6-dichlorohexane, 1,2-bis(2-chloroethoxy) ethane, dichloro-p-xylene and dichloro-m-xylene.

(23) The amine-based compound is not particularly limited, but may be at least one selected from the group consisting of 1,2-bis(2-aminoethoxy) ethane, imidazole, pyrazine, piperazine, 4-chloro pyridine, 3-chloro pyridine, pyridazine, pyrimidine, 2-amino imidazole, 2,4-bipyridyl, 2,4-bipyridyl, 4,4-bipyridyl and benzimidazole.

(24) The temperature for dissolving the alkylation 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 alkylation agent compound (a) and the amine-based compound (b) is not particularly limited, but may be a weight ratio of 1:2 to 6:1. In addition, when two or more alkylation agents (a, a) are added, the reaction ratio (a:b) may be a weight ratio of 1:1 to 6:1, and the reaction ratio of a:b may be a weight ratio of 1:1 to 6:1.

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

(26) The present invention provides an electroplating composition comprising the leveler. Specifically, the electroplating composition according to the present invention includes a metal ion source; the above-described leveler; an inhibitor; and a brightener.

(27) The description of the leveler 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 this leveler is not particularly limited, but when considering the uniformity of the circuit pattern and plating efficiency, it may be 3 to 50 ppm, and specifically 7.5 to 20 ppm.

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

(29) The brightener included in the electroplating composition according to the present invention is to promote plating by increasing the reduction rate of metal ions, and may be a commonly known material. Specifically, it is preferable that the brightener has a disulfide bond and contains one or more mercapto functional groups, and more specifically, it may be at least one selected from the group consisting of bis-(3-sulfopropyl) disulfide (sodium salt), 3-mercapto-1-propanesulfonic acid (sodium salt), 3-amino-1-propanesulfonic acid, O-ethyl-S-(3-sulphopropyl) dithiocarbonate (sodium salt), 3-(2-benzthiazoly-1-thio)-1-propanesulfonic acid (sodium salt) and N, N-dimethyldithiocarbamic acid-(3-sulfopropyl) ester (sodium salt). The concentration (content) of the brightener is not particularly limited, but considering the plating rate and the like, it may be 0.001 to 1 ml/L, and specifically may be 0.001 to 0.1 ml/L. If the brightener is less than the above range, it is difficult to expect the effect of the brightener. If the brightener exceeds the above range, plating growth is excessively promoted, and voids may occur inside the via hole.

(30) The inhibitor comprised in the electroplating composition according to the present invention is to increase the surface flatness of the circuit pattern, and commonly known materials may be used. Specifically, an alkoxylate alcohol-based polymer may be used as this inhibitor, 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 using the polymer, the molecular weight of the polymer may be 3,000 to 10,000 g/mol, preferably 2000 to 5000 g/mol. Within the above 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 reduced, resulting in staining, which may deepen the depth of the dimple. The concentration (content) of the inhibitor is not particularly limited, but when considering the uniformity and plating efficiency of the circuit pattern, it may be 0.1 to 10 ml/L, and specifically 0.2 to 1.0 ml/L. If the inhibitor is included below the above range, it is difficult to expect the effect of the inhibitor. If the inhibitor is included in excess of the above range, staining may occur on the surface.

(31) The present invention provides a method of filling via holes in a substrate with the electroplating composition. Specifically, the method of filling via holes in the substrate according to the present invention comprises the steps of forming a via hole in the substrate; forming an electroless plating layer by performing electroless plating on the substrate on which the via hole is formed; and filling the via hole by performing electrolytic plating on the substrate on which the electroless plating layer is formed, which will be described in detail with reference to FIG. 1 as follows.

(32) First, a via hole H is formed in the substrate 201. The substrate 201 may be a substrate 201 made of a conventionally known insulating resin. The via hole H may be formed by laser processing or CNC processing. Here, the via hole H may be formed in the form of a groove that does not penetrate the substrate 201 or a hole that penetrates the substrate 201. In addition, in the case of the via hole, it may be manufactured in a form penetrating only one substrate, or each via hole may be vertically and continuously stacked (stacked via), and it may be manufactured in a form penetrating two or more substrate layers (skip via) (see FIGS. 1 and 2A-2C).

(33) Next, the electroless plating is performed on the substrate 201, on which the via hole H is formed, to form an electroless plating layer 202 on the inside of the via hole H and the surface of the substrate 201. As a plating solution composition for performing the electroless plating, a commonly known composition may be used. As an example, a plating solution composition comprising copper ions, a copper ion complexing agent, a copper ion reducing agent, a pH adjusting agent and an additive may be used. In addition, the conditions of the electroless plating are not particularly limited, but may be made at a rate of 10 m/hr in a temperature range of 20 to 60 C. and pH 11 to 14.

(34) Then, electrolytic plating is performed on the substrate 201, on which the electroless plating layer 202 is formed, to fill the via hole H. That is, the electrolytic plating layer 203 is formed. As the plating solution composition for performing the electrolytic plating, the electroplating composition described above may be used.

(35) Here, the current density applied during electrolytic plating with the electroplating composition may be applied as a specific waveform. That is, referring to FIG. 4, a current density of a step-wise pulse (+ current applied)-reverse ( current applied) waveform having a cycle of t.sub.1+t.sub.2+t.sub.3+t.sub.4+t.sub.5+t.sub.6 may be applied. Specifically, a waveform maintaining the positive current I.sub.1 for a time t.sub.1, then the positive current I.sub.2 for a time t.sub.2, then the negative current I.sub.3 for a time t.sub.3, then the negative current I.sub.4 for a time t.sub.4, then the negative current I.sub.3 for a time t.sub.5, and then the positive current I.sub.2 for a period for a time t.sub.6 is periodically applied for a predetermined period of time to perform the electrolytic plating.

(36) Here, in order to minimize the formation of dimples and voids during via hole H filling plating, I.sub.1 may be 2 to 5 ASD, I.sub.2 may be 1 to 2 ASD, I.sub.3 may be 1 to 2 ASD, and I.sub.4 may be 3 to 10 ASD. Also, t.sub.1, t.sub.2, and the may each be 10 to 80 ms (specifically, 30 to 50 ms), and t.sub.3, t.sub.4, and t.sub.5 may each be 1 to 5 ms (specifically, 2 to 4 ms).

(37) In this way, as the current density is applied as a step-by-step pulse-reverse waveform representing the cycle of t.sub.1+t.sub.2+t.sub.3+t.sub.4+t.sub.5+t.sub.6 during the electrolytic plating, the electrolytic plating can be done in a relatively short time (specifically 20 to 40 minutes) while minimizing the formation of dimples and voids.

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

Example 1

(39) As a first amine (A1), 1,2-bis(2-aminoethoxy) ethane was mixed with water and then completely dissolved at a temperature of 80 C. After dissolution was completed, 1,3-dibromo benzene, which is a first alkylation agent (R1), was added and reacted for 8 hours. After the reaction was completed, 1-chloropropane, which is a second alkylation agent (R2), was added and reacted for 8 hours to synthesize a leveler compound (Formula 4). In this case, the weight ratio of A1 and R1 was set to 1:3, and the weight ratio of A1 and R2 was set to 1:3.

Example 2

(40) As a first amine (A1), imidazole was mixed with ethanol and then completely dissolved at a temperature of 50 C. while refluxing. After dissolution was completed, 1,6-dichlorohexane, which is a first alkylation agent (R1), was added and reacted for 8 hours. After the reaction was completed, benzyl chloride, which is a second alkylation agent (R2), was added and reacted for 8 hours to synthesize a leveler compound (Formula 6). In this case, the weight ratio of A1 and R1 was set to 1:3, and the weight ratio of A1 and R2 was set to 1:3.

Example 3

(41) Imidazole as a first amine (A1) and pyrimidine as a second amine (A2) were mixed with ethylene glycol and then completely dissolved at a temperature of 120 C. After dissolution was completed, 1,6-dichlorohexane, which is a first alkylation agent (R1), was added and reacted for 8 hours to synthesize a leveler compound (Formula 12). In this case, the weight ratio of A1 and A2 was set to 1:5, and the weight ratio of A1 and R1 was set to 1:3.

Comparative Example 1

(42) 1,2-bis(2-aminoethoxy) ethane as a primary amine (A1) was mixed with water and then completely dissolved at a temperature of 80 C. After dissolution was completed, 1,3-dibromo benzene, which is a first alkylation agent (R1), was added and reacted for 8 hours to synthesize a leveler compound. In this case, the weight ratio of A1 and R1 was set to 1:3.

Comparative Example 2

(43) Pyrazine as a first amine (A1) and 2,4-bipyridyl as a second amine (A2) were mixed with ethylene glycol and then completely dissolved at a temperature of 120 C. After dissolution was completed, 1,2-bis(2-chloroethoxy) ethane, which is a first alkylation agent (R1), was added and reacted for 8 hours to synthesize a leveler compound. In this case, the weight ratio of A1 and A2 was set to 1:5, and the weight ratio of A1 and R1 was set to 1:3.

Comparative Example 3

(44) A known leveler (KBPA from Dicolloy company) was used.

Experimental Example 1

(45) An electroplating composition containing 200 g/L of copper sulfate pentahydrate, 100 g/L of sulfuric acid, 50 mg/L of hydrochloric acid, 0.005 ml/L of bis-(sodium sulfopropyl)-disulfide, 0.5 ml/L of the inhibitor and 10 ml/L of the leveler of Example 1 was prepared.

(46) Via holes with a diameter of 120 and 140 m and a depth of 100 m were formed on an epoxy resin substrate having a thickness of 200 m by laser processing. 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, electrolytic plating was performed with the electroplating composition containing the leveler prepared in Example 1 to fill the via holes. When plating with the electroplating composition, the plating conditions were set as follows: Electroplating composition temperature: 21 to 24 C. Stirring: 0.5 to 1.5 LPM/con. Electrode: Insoluble electrode Current density: 3ASD

(47) In this case, in order to confirm the effect of filling with time, via holes were filled with different plating times, and each cross section is shown in FIG. 3. As shown in FIG. 3, it was confirmed that even when using a general current, it was possible to fill the via hole within 45 minutes without forming a void, and the occurrence of dimples was also minimized.

Experimental Example 2

(48) An electroplating composition containing 200 g/L of copper sulfate pentahydrate, 100 g/L of sulfuric acid, 50 mg/L of hydrochloric acid, 0.005 ml/L of bis-(sodium sulfopropyl)-disulfide, 0.5 ml/L of the inhibitor and 10 ml/L of the leveler of Examples 1 to 3 and Comparative Example 1 to 3 was prepared.

(49) A via hole having a diameter of 90 m and a depth of 100 m was formed by laser processing on a substrate of an epoxy resin having a thickness of 200 m. Next, a substrate of an epoxy resin having via holes was put into the 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, electrolytic plating was performed using the electroplating composition comprising the levelers prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively, to fill the via hole. When plating with the electroplating composition, the plating conditions were set as follows: Temperature of the electroplating composition: 21 to 24 C. Stirring: 0.5 to 1.5 LPM/con. Electrode: Insoluble electrode Current density: applying the step-wise pulse-reverse waveform under the conditions of Table 1 below (see FIG. 4).

(50) TABLE-US-00001 TABLE 1 Current Average density Application time current I.sub.for I.sub.rev T.sub.for T.sub.rev T.sub.off Frequency I.sub.for, AVG I.sub.rev, AVG Duty (ASD) (ASD) (sec) (sec) (sec) (Hz) (ASD) (ASD) cycle 3.6 12 0.04 0.004 0.002 22 3.27 2.09 0.91

(51) After completing the via hole filling plating, the cross-section of the substrate was confirmed with an optical microscope, and the result is shown in FIGS. 5A-5F.

(52) As shown in FIGS. 5A-5F, in the case of Examples 1 to 3 of the present invention, it was possible to fill via holes without generating voids and dimples. However, in the case of Comparative Examples 1 to 3, the occurrence of dimples and voids was confirmed. That is, in the case of Examples of the present invention, high-speed plating was possible, when using the pulse reverse current waveform, but in the case of the Comparative Example, it was confirmed that occurrence of dimples and voids appears.

Experimental Example 3

(53) When plating with the electroplating composition in Example 1, in order to confirm the conditions for applying the current density, via hole filling plating was performed while adjusting as shown in Table 2 below. After filling plating was completed, it was evaluated whether dimples and voids were formed on the cross section of the substrate, and the results are shown in Table 3 below. In this case, a direct current (DC) waveform, not a step-wise pulse-reverse waveform, was applied as a comparison condition.

(54) TABLE-US-00002 TABLE 2 Current Average density Application time current I.sub.for I.sub.rev T.sub.for T.sub.rev T.sub.off Frequency I.sub.for, AVG I.sub.rev, AVG Duty Item (ASD) (ASD) (sec) (sec) (sec) (Hz) (ASD) (ASD) cycle Condition 3.6 12 0.04 0.004 0.002 22 3.27 2.09 0.91 1 Condition 3 6 0.04 0.002 0.002 23 2.86 2.45 0.95 2 Condition 3.6 8 0.04 0.004 0.002 22 3.27 2.43 0.91 3 Condition 3 5 0.04 0.002 0.002 23 2.86 2.50 0.95 4 Comparison 1.2 0 0 0 1 1.20 0.00 condition 1 Comparison 2.4 0 0 0 1 2.40 0.00 condition 2 Comparison 3.6 0 0 0 1 3.60 0.00 condition 3

(55) TABLE-US-00003 TABLE 3 Via hole filling Void generation Item plating time (min) Dimple (m) rate (%) Condition 1 35 0 0 Condition 2 29 5.3 1 Condition 3 30 0 1 Condition 4 29 7 0 Comparison 60 0 3 condition 1 Comparison 30 34 0 condition 2 Comparison 20 99 0 condition 3

(56) Referring to Table 3 above, it can be confirmed that when filling via holes with the electroplating composition according to the present invention, as a step-wise pulse-reverse waveform is applied, plating is performed well even if the plating time for via hole filling is relatively short, thereby minimizing the occurrence of dimples and voids. Whereas, it can be confirmed that when applying a DC waveform, the plating time for 60 minutes or more is required to prevent dimples and voids from occurring, and when plating is performed within 30 minutes, dimples are severely generated.

Examples 4 to 11 and Comparative Examples 4 to 12

(57) Experiments were conducted to confirm the occurrence of dimples and voids depending on the types of amine compounds (A1, A2) and alkylation agent compounds (R1, R2) used. Experiments were conducted using the combinations shown in Table 4 below, and levelers were synthesized using conditions similar to Examples 1 to 3 as each condition.

(58) TABLE-US-00004 TABLE 4 Mixing A1 A2 R1 R2 Solvent temperature Example 4 1,2-Bis(2- 1,3-Dibromobenzene 1-Chloropropane Water 80 aminoethoxy) ethane Example 5 Imidazole 1,6-Dichlorohexane Benzylchloride Ethanol 50 Example 6 Pyrazine 1,6-Dichlorohexane Benzylchloride Ethanol 50 Example 7 Piperazine 3-Chloropyridine 1,2-Bis(2- Dichloro- Ethanol 50 chloroethoxy) p-xylene ethane Example 8 Imidazole Pyrimidine 1,6-Dichlorohexane Ethylene 120 glycol Example 9 Imidazole 2-Aminoimidazole 1,2-Bis(2- Ethylene 120 chloroethoxy) glycol ethane Example 10 Pyrazine 1,6-Dichlorohexane Dichloro- Ethanol 50 p-xylene Example 11 Pyridazine Pyrimidine 1,2-Bis(2- Dichloro- Ethanol 50 chloroethoxy) m-xylene ethane Comparative 1,2-Bis(2- 1,4-Dibromobenzene Water 80 Example 4 aminoethoxy) ethane Comparative Imidazole 4-chloropyridine 1,6-Dichlorohexane Ethanol 50 Example 5 Comparative Pyrazine 4-chloropyridine 1,6-Dichlorohexane Ethanol 50 Example 6 Comparative Pyrazine 4-chloropyridine 1,2-Bis(2- Ethanol 50 Example 7 chloroethoxy) ethane Comparative Pyrazine 2,4- 1,2-Bis(2- Ethanol 50 Example 8 Bipyridyl chloroethoxy) ethane Comparative Pyrazine 4,4- Dichloro-p- Ethanol 50 Example 9 Bipyridyl xylene Comparative Piperazine Benzimidazole 1,6-Dichlorohexane Dichloro- Ethylene 120 Example 10 m-xylene glycol Comparative Piperazine 2,2- 1,2-Bis(2- Ethylene 120 Example 11 Bipyridyl chloroethoxy) glycol ethane Comparative Piperazine Dichloro-p- Ethylene 120 Example 12 xylene glycol

Experimental Example 4

(59) Experiments were conducted in the same manner as Experimental Example 1 using Examples 4 to 11 and Comparative Examples 4 to 12, respectively. After completion of plating for filling, it was evaluated whether dimples and voids were formed on the cross-section of the substrate, and the results are shown in Table 5 below.

(60) TABLE-US-00005 TABLE 5 Plating time for filling Void occurrence Item via hole (min) Dimple (m) rate (%) Example 4 35 0 0 Example 5 29 0 0 Example 6 34 1.1 0.3 Example 7 30 0 0.1 Example 8 28 0 0 Example 9 29 2.3 0 Example 10 31 0.8 0.1 Example 11 33 0 0.2 Comparative 44 1.4 5.9 Example 4 Comparative 42 5.7 6.4 Example 5 Comparative 46 5.9 3.8 Example 6 Comparative 38 7.4 3.8 Example 7 Comparative 64 5.8 3.5 Example 8 Comparative 48 11.8 2.9 Example 9 Comparative 50 6.7 4.8 Example 10 Comparative 34 5.4 5.4 Example 11 Comparative 32 1.1 6.8 Example 12

(61) As shown in Table 5, in the case of the combination of the Examples of the present invention, it was confirmed that the plating time of the via holes is reduced, and the height of the dimples is kept low. In addition, voids also rarely occur, indicating that it can be used for filling via holes. However, in the case of the combination of the Comparative Examples, it was found that as the plating time for filling was increased, the height of the dimples was increased, and the occurrence rate of voids was also increased.

Experimental Example 5

(62) Experiments were conducted to confirm whether the leveler of the present invention was applied to the through-hole plating. Electroplating solutions (same as Experimental Example 2) containing the levelers of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared, respectively, and then experiments were conducted to plate through-holes with a diameter of 200 m and a depth of 400 m. In this case, other conditions are the same as in Experimental Example 2 above.

(63) TABLE-US-00006 TABLE 6 Surface Inner wall Corner thickness thickness thickness (m) (m) (m) Example 1 16.6 17.2 14.1 Example 2 16.9 18.6 12.6 Example 3 16.0 18.7 13.1 Comparative Example 1 12.1 7.7 6.9 Comparative Example 2 16.5 8.3 6.0 Comparative Example 3 13.9 9.2 6.0

(64) As shown in Table 6 and FIGS. 6A-6F, in the case of Examples 1 to 3 of the present invention, it was possible to secure an appropriate plating thickness, but it was found that in the case of Comparative Examples, the thickness could not be secured under the same conditions. In particular, it was found that in the case of the Examples of the present invention, CPT (corner thickness/surface thickness) representing the effect of plating was able to secure 70% or more, but in the case of the Comparative Examples, it has less than 70%. In the case of TP (inner wall plating thickness/surface thickness), it was found that the Examples of the present invention showed more than 100%, whereas the Comparative Examples showed less than 100%, and thus the Examples of the present invention have better plating performance.

(65) In the above, although specific parts of the content of the present invention have been described in detail, it will be clear to those skilled in the art that these specific descriptions are merely preferred embodiments, and the scope of the present invention is not limited thereby. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

DESCRIPTION OF SYMBOL

(66) 201: Substrate 202: Electroless plating layer 203: Electrolytic plating layer 204: Middle plating layer