CN109154093B - Electrolytic nickel (alloy) plating solution - Google Patents
Electrolytic nickel (alloy) plating solution Download PDFInfo
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- CN109154093B CN109154093B CN201780030115.7A CN201780030115A CN109154093B CN 109154093 B CN109154093 B CN 109154093B CN 201780030115 A CN201780030115 A CN 201780030115A CN 109154093 B CN109154093 B CN 109154093B
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- plating solution
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- electrolytic nickel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
Abstract
The invention provides an electrolytic nickel (alloy) plating solution, a nickel or nickel alloy plating filling method using the same, and a method for manufacturing a three-dimensional microstructure, wherein the electrolytic nickel (alloy) plating solution can fill minute holes or minute recesses (14) in electronic circuit components with nickel or nickel alloy (18) without causing defects such as holes or gaps. The present invention also solves the above-mentioned problems by filling the minute holes or minute recesses (14) with an electrolytic nickel (alloy) plating solution containing a specific N-substituted carbonylpyridinium compound.
Description
Technical Field
The present invention relates to an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution (hereinafter, these solutions may be collectively referred to as "electrolytic nickel (alloy) plating solution"), and more particularly, to an electrolytic nickel (alloy) plating solution suitable for plating and filling minute holes or minute recesses in electronic circuit components.
The present invention also relates to a method for plating and filling minute holes or minute recesses using the electrolytic nickel (alloy) plating solution, and a method for producing a three-dimensional microstructure.
Background
Electronic circuit components represented by semiconductors and printed boards have minute holes or minute recesses such as through holes (via), through holes (through holes), and deep trenches (trenches) for forming wiring. In the conventional production of a multilayer printed circuit board by laminating a plurality of circuit boards, a Staggered via (Staggered via) structure has been mainly used, in which the wall surfaces of via holes are subjected to conformal copper plating (follow-up plating), and then connected to other layers in a Staggered arrangement. However, with the recent miniaturization and higher functionality of electronic devices, space saving by a Stacked via (Stacked via) structure in which a via hole is filled by copper plating and directly Stacked on another layer to connect layers has become necessary and indispensable.
The technique of filling by electrolytic copper plating is also suitable for use in semiconductor manufacturing techniques, and a technique called damascene process (damascene process) or Through Silicon Via (TSV) has been developed, so that a three-dimensional wiring structure can be formed by filling a Via hole by electrolytic copper plating.
The electrolytic copper plating solution for filling the micro holes or the micro recesses contains various additives, and fills the through holes by controlling the concentration balance thereof in an optimum state, but even if filling is completed so that large holes (macro) of about several μm disappear, there is a problem that micro holes (microvoids) of the nm order remain due to the side effect of the additives. Copper is a metal whose melting point is not very high (1083 c) and is known to recrystallize after electrolytic copper plating when left at room temperature. In this recrystallization, there is a problem that micropores in the order of nm are aggregated to form large pores.
For example, non-patent document 1 describes that polyethylene glycol (PEG) as an additive partially penetrates into a copper film to form nm-sized micropores in the copper film, and that large pores having a diameter of 70nm are formed by standing at room temperature during recrystallization of copper.
Therefore, in the copper filling method using the electrolytic copper plating solution, there is a potential problem that, when the wiring is continuously further miniaturized, the deterioration of the wiring reliability may be conspicuous due to void (void) growth or void movement accompanied by the aggregation of the micro-voids.
Therefore, the present inventors speculate that even if micro-voids due to the plating additive remain, if the micro-voids or the micro-recesses can be filled with a high-melting-point metal that is not easily recrystallized at room temperature, particularly nickel (melting point: 1455 ℃) that is generally used as a primer for electronic parts, a highly reliable wiring in which the voids are not easily aggregated can be obtained.
Attempts have been made to fill the recesses by electrolytic nickel plating.
Non-patent document 2 discusses the filling property of deep trenches when various additives are added to an electrolytic nickel plating solution, in which thiourea is added to fill fine recesses (deep trenches).
However, according to additional tests (examples described later) by the present inventors, it was found that the electrolytic nickel plating solution described in non-patent document 2 has insufficient filling property and is not capable of suppressing the generation of voids, and cracks are generated in precipitates, resulting in a defective structure.
While miniaturization of electronic circuits is actively progressing, in the related known art, the filling property of micro holes and micro recesses is not sufficient, and development of a nickel filling method that does not generate defects such as holes or cracks is desired.
[ Prior art documents ]
[ non-patent document ]
Non-patent document 1: surface technology Vol.52, No.1, pp.34-38(2001)
Non-patent document 2: journal of electronics Assembly society, Vol.17, No.2, pp.143-148 (2014).
Disclosure of Invention
(problems to be solved by the invention)
The present invention has been made in view of the above-mentioned background art, and an object thereof is to provide an electrolytic nickel (alloy) plating solution which can fill minute holes or minute recesses in electronic circuit parts with nickel or a nickel alloy without causing defects such as holes or gaps; also disclosed are a nickel or nickel alloy plating and filling method using the electrolytic nickel (alloy) plating solution, and a method for producing a three-dimensional microstructure.
(means for solving the problem)
As a result of diligent research directed toward solving the above problems, the present inventors have found that by electroplating using an electrolytic nickel (alloy) plating solution containing a specific N-substituted carbonylpyridinium compound, nickel can be filled in the minute holes or minute recesses without causing defects such as voids, and have completed the present invention.
That is, the present invention provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, comprising: a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (A);
[ in the general formula (A), m is 0 or 1; -R1is-R1aor-NR1bR1c(R1aIs an alkyl group having 1 to 6 carbon atoms; r1bIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; r1cIs hydrogen atom, alkyl group having 1 to 6 carbon atoms, or amino group (-NH)2))；-R2Is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; x-Is an arbitrary anion]。
In addition, the present invention provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, comprising: a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (B);
[ in the general formula (B), m is 0 or 1; -R1is-R1aor-NR1bR1c(R1aIs an alkyl group having 1 to 6 carbon atoms; r1bIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; r1cIs hydrogen atom, alkyl group having 1 to 6 carbon atoms, or amino group (-NH)2))。-R3is-R3a-SO3 -(R3aAlkylene group having 1 to 6 carbon atoms)]。
In addition, the present invention provides a method for plating and filling a nickel or nickel alloy, wherein a seed layer for electrolytic plating is applied in advance to the surface of a fine hole or a fine recess formed in an electronic circuit part, and then the electronic circuit part is immersed in the electrolytic nickel plating solution or the electrolytic nickel alloy plating solution and electrolytic plating is performed using an external power source.
Further, the present invention provides a method for producing a three-dimensional microstructure, comprising: and plating and filling the micro holes or the micro concave parts by the nickel or nickel alloy plating and filling method.
[ Effect of the invention ]
According to the present invention, by using nickel plating or nickel alloy plating, it is possible to fill minute holes or minute recesses in electronic circuit parts without generating holes or gaps.
In addition, in the present invention, since the fine pores or the fine recesses can be filled with nickel having a high melting point and not easily recrystallized at room temperature, even if the wiring is further miniaturized, defects associated with aggregation of the pores are not easily generated, and thus the present invention can be widely used for three-dimensional wiring formation, three-dimensional MEMS (Micro Electro Mechanical Systems) parts, and the like in which miniaturization is continuously advanced.
Drawings
Fig. 1 is a schematic view showing a cross section around a plated portion of a printed board for evaluation used in the examples.
FIG. 2 is a photograph of a wiring pattern on the surface of the evaluation printed board used in the example.
FIG. 3 is a photomicrograph of a cross-section of the substrate after plating and filling (example 1).
FIG. 4 is a photomicrograph of a cross-section of the substrate after plating and filling (example 2).
FIG. 5 is a photomicrograph of a cross-section of the substrate after plating and filling (example 3).
FIG. 6 is a photomicrograph of a cross-section of the substrate after plating and filling (example 4).
FIG. 7 is a photomicrograph of a cross-section of the substrate after plating and filling (comparative example 1).
FIG. 8 is a photomicrograph of a cross-section of the substrate after plating and filling (comparative example 2).
FIG. 9 is a photomicrograph of a cross-section of the substrate after plating and filling (comparative example 3).
Detailed Description
The present invention will be described below, but the present invention is not limited to the following embodiments, and can be implemented in various modifications.
< electrolytic nickel (alloy) plating solution >
The electrolytic nickel (alloy) plating solution of the present invention (hereinafter, also simply referred to as "plating solution of the present invention") contains: a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (A) or the following general formula (B);
[ in the general formula (A), m is 0 or 1. -R1is-R1aor-NR1bR1c(R1aIs an alkyl group having 1 to 6 carbon atoms; r1bIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; r1cIs hydrogen atom, alkyl group having 1 to 6 carbon atoms, or amino group (-NH)2))。-R2Is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X-Is an arbitrary anion]
[ in the general formula (B), m is 0 or 1. -R1is-R1aor-NR1bR1c(R1aIs an alkyl group having 1 to 6 carbon atoms; r1bIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; r1cIs hydrogen atom, alkyl group having 1 to 6 carbon atoms, or amino group (-NH)2))。-R3is-R3a-SO3 -(R3aAlkylene group having 1 to 6 carbon atoms)]。
The nickel salt contained in the plating solution of the present invention is not limited to nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, nickel citrate, nickel fluoroborate, and the like, from the viewpoint of water solubility and filling property.
These can be used alone in 1 kind, also can be mixed with more than 2 kinds of use.
The total content of the nickel salts is preferably 10g/L to 180g/L, and particularly preferably 50g/L to 130g/L, in terms of nickel ions.
Within the above range, the precipitation rate of nickel becomes sufficient, and in addition, the minute holes or minute recesses can be filled in such a manner that no holes are generated.
Examples of the pH buffer contained in the plating solution of the present invention include, but are not limited to, boric acid, metaboric acid, acetic acid, tartaric acid, citric acid, and salts thereof.
These can be used alone in 1 kind, also can be mixed with more than 2 kinds of use.
The content of the pH buffer is preferably 1g/L to 100g/L, and particularly preferably 5g/L to 50 g/L.
When the amount is within the above range, the action of the N-substituted carbonylpyridinium compound represented by the general formula (a) or the general formula (B) (hereinafter, also referred to as "specific N-substituted carbonylpyridinium compound") is not easily inhibited, and the effects of the present invention can be maintained.
The plating solution of the present invention contains a specific N-substituted carbonylpyridinium compound.
By the action of the specific N-substituted carbonylpyridinium compound, the plating solution of the present invention can fill micro holes or micro pits without causing holes.
When R in the above general formula (A) and the above general formula (B)1a、R1b、R1c、R2When it is C1-6 alkyl, R1a、R1b、R1c、R2Each of the above groups may be an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms.
In addition, when R of the above general formula (B)3aIn the case of an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 4 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and an alkylene group having 1 or 2 carbon atoms is particularly preferable.
In the above general formula (A), -R1Specific examples of (2) include, for example, -CH3、-CH2CH3、-NH2、-N(CH3)2、-N(C2H5)2、-NHNH2And the like.
-R2Specific examples of (3) include, for example, -H and-CH3、-C2H5、-C3H7And the like.
X-Specific examples of (2) include halide ions (chloride ion)Seed, bromide ion, iodide ion), and the like.
Specific examples of the specific N-substituted carbonylpyridinium compound represented by the general formula (A) include, for example, halides (chloride, bromide, iodide) of 1-carbamoylpyridinium, 1- (carbamoylmethyl) pyridinium, 1- (dimethylcarbamoyl) pyridinium, 1- (diethylcarbamoyl) pyridinium, 1- (hydrazinocarbonylmethyl) pyridinium, and 1-acetonylpyridinium.
In the above general formula (B), -R1Specific examples of (A) include the same ones as in the case of the general formula (A).
-R3Specific examples of (1) include, for example, -C2H4-SO3 -、-C3H6-SO3 -And the like.
Specific examples of the specific N-substituted carbonylpyridinium compound represented by the general formula (B), examples thereof include 1- (carbamoylmethyl) -4- (2-sulfoethyl) pyridinium hydroxide intramolecular salt, 1- (carbamoylmethyl) -4- (2-sulfopropyl) pyridinium hydroxide intramolecular salt, 1- (carbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide intramolecular salt, 1- (carbamoyl) -4- (2-sulfopropyl) pyridinium hydroxide intramolecular salt, 1- (dimethylcarbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide intramolecular salt, and 1- (dimethylcarbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide intramolecular salt.
The specific N-substituted carbonylpyridinium compound may be used alone in 1 kind or in combination of 2 or more kinds.
The total content of the specific N-substituted carbonylpyridinium compounds in the plating solution of the present invention is preferably 0.01g/L to 100g/L, and particularly preferably 0.1g/L to 10 g/L.
Within the above range, the amount of nickel deposited on the outside of the micro-holes or micro-recesses can be increased, and the micro-holes or micro-recesses can be filled without causing holes.
The plating solution of the present invention contains a nickel salt, a pH buffer and a specific N-substituted carbonylpyridinium compound as essential components.
In preparing the plating solution of the present invention, the above-mentioned essential components may be added to water in any order. Further, the plating solution of the present invention can be prepared by dissolving only any one of the above-mentioned essential components in an aqueous solution of water during storage, and adding other components during use.
When the plating solution of the present invention is an electrolytic nickel alloy plating solution, examples of the metal ion for alloying with nickel include tungsten, molybdenum, cobalt, iron, zinc, tin, copper, palladium, gold, and the like. As the metal source, a known compound can be used.
The nickel or nickel alloy coating may contain non-metallic carbon, sulfur, nitrogen, phosphorus, boron, chlorine, bromine, or the like.
The plating solution of the present invention may contain an anti-dishing agent, a primary brightening agent, a secondary brightening agent, a surfactant, and the like as necessary within a range not to impair the effects of the present invention.
The plating solution of the present invention is suitable for filling minute holes or minute recesses formed in electronic circuit parts. As shown in examples described later, when the fine holes or the fine recesses are filled with the plating solution of the present invention, the amount of deposition inside the fine holes or the fine recesses becomes larger than the amount of deposition outside the fine holes or the fine recesses, and nickel (or a nickel alloy) can be sufficiently embedded in the fine holes or the fine recesses. In addition, holes (holes) or slits (grooves) are not easily formed inside the minute holes or minute recesses.
Therefore, also because of the high melting point of nickel, it is expected that electronic circuit components having minute holes or minute recesses filled with the plating solution of the present invention will have high reliability.
< method for plating and filling nickel (alloy), method for manufacturing three-dimensional microstructure >
The nickel or nickel alloy plating filling method of the present invention is a method of plating and filling a surface of a fine hole or a fine recess formed in an electronic circuit part with a seed layer for electrolytic plating in advance, immersing the electronic circuit part in the electrolytic nickel (alloy) plating solution, and performing electrolytic plating using an external power source.
Further, a method for producing a three-dimensional microstructure according to the present invention includes: and a step of plating and filling the micro holes or the micro recesses by the nickel or nickel alloy plating and filling method.
The "minute hole or minute recess" refers to a minute recessed portion such as a through hole, or a deep trench formed in an electronic circuit component such as a semiconductor or a printed board, and is a portion that functions as a wiring portion by being filled with a metal by electrolytic plating or the like, and the shape when viewed from above is not limited. In addition, the "micro holes" may be through holes or may be non-through holes.
In the practice of the present invention, it is necessary to form minute holes or minute recesses in the substrate to be plated in the electronic circuit component.
The substrate to be plated is not particularly limited, and specific examples thereof include a glass epoxy material, a BT (Bismaleimide triazine) resin material, a polypropylene material, a polyimide material, a ceramic material, a silicon material, a metal material, a glass material, and the like, which are commonly used as electronic circuit components.
The method for forming the minute holes or minute recesses in the substrate to be plated is not limited, and a known method can be suitably used. For example, the method using laser processing or ion etching can form the fine recessed portions with a depth of the opening portion of 100 μm or less and an aspect ratio of 0.5 or more.
Then, a pattern (pattern) is formed on the surface of the substrate to be plated with a resist or the like as necessary.
When the substrate to be plated on which the fine recessed portions are formed is an insulating substrate, a seed layer for electrolytic plating is formed on the surface of the substrate and the inner surfaces of the fine recessed portions. The method of forming the seed layer is not particularly limited, and specifically, metal deposition by sputtering, electroless plating, or the like can be given as examples.
The metal constituting the seed layer is not particularly limited, and examples thereof include copper, nickel, palladium, and the like.
After the formation of the seed layer for electrolytic plating, the substrate to be plated is immersed in the electrolytic nickel (alloy) plating solution of the present invention, and electrolytic nickel (alloy) plating is performed using an external power source, and the minute holes or minute recesses are filled with nickel or a nickel alloy.
In the case of plating a substrate to be plated which is obtained by drying immediately after forming a seed layer, degreasing and cleaning with an acid are performed by a general method, and then plating is performed using the plating solution of the present invention.
According to the method including the step of plating and filling the minute holes or minute recesses by the nickel or nickel alloy plating and filling method of the present invention, minute three-dimensional circuit wirings or minute three-dimensional structures in which the minute holes or minute recesses are filled with nickel or nickel alloy can be manufactured.
The plating temperature is preferably 30 ℃ or higher, and particularly preferably 40 ℃ or higher. Further, it is preferably 70 ℃ or lower, and particularly preferably 60 ℃ or lower.
When the amount is within the above range, the filling property of the fine pores or the fine recesses is excellent, and the cost is also advantageous.
The current density at the time of plating is preferably 0.1A/dm2Above, 1A/dm is particularly preferable2The above. Further, it is preferably 10A/dm2Hereinafter, it is particularly preferably 5A/dm2The following.
When the amount is within the above range, the filling property of the fine pores or the fine recesses is excellent, and the cost is also advantageous.
The current density may be kept constant or not during the plating filling (for example, the current density is gradually increased by lowering the initial current density, or the current density is set to a pulse current).
The current density is preferably kept constant during the plating filling (or constant for most of the time during the plating filling) because the filling can be easily performed without causing voids.
The plating time is preferably 5 minutes or more, and particularly preferably 10 minutes or more. Further, it is preferably 360 minutes or less, and particularly preferably 60 minutes or less.
When the amount is within the above range, the filling property of the fine pores or the fine recesses is excellent, and the cost is also advantageous.
[ examples ]
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples as long as the gist of the present invention is not exceeded.
Examples 1 to 4 and comparative examples 1 to 3
For the model of the minute recessed portion, a 12mm square evaluation printed board (manufactured by CIRCUIT corporation, Japan) having a laser hole with an aspect ratio of 0.88(φ 45 μm × 40 μm D) was used.
Fig. 1 shows a cross-sectional view of the periphery 10 of the plated portion. After a copper foil 13 having a thickness of 12 μm was bonded to a through-hole forming portion of a BT (Bismaleimide-triazine) substrate 11 having a thickness of 0.4mm, a laminated resin (build-up) 12 having a thickness of 60 μm and a prepreg type (pre) was laminated thereon, a blind via (hereinafter, also referred to simply as "via hole") 14 having a diameter of 45 μm and a depth of 40 μm was formed by a laser, and a seed layer 15 having a thickness of about 1 μm was formed on the outer surface of the substrate (the surface of the laminated resin 12) and the inner wall surface of the through-hole 14 by electroless copper plating.
Further, a wiring pattern shown in fig. 2 was formed with a Dry Film Resist (DFR) 16, and a pad (opening portion) 17(Φ 190 μm) having a through hole 14 was opened to be used as the evaluation printed board 1.
In fig. 2, the white portion is a copper plating portion and the black portion is a dry film resist portion. Of the white portions, the circular portion having the largest size to which the wiring is connected corresponds to the circular pad 17 (phi 190 μm) of fig. 1. The through hole 14 belonging to the minute recess shown in fig. 1 is formed in the entire circular pad 17.
< preparation of electrolytic Nickel plating solution >
An electrolytic nickel plating solution was prepared by dissolving 600g/L nickel sulfamate, 10g/L nickel chloride and 30g/L boric acid in deionized water.
The additives shown in table 1 were added to and dissolved in the electrolytic nickel plating solution in the amounts shown in table 1.
Then, an appropriate amount of 100g/L aqueous solution of sulfamic acid was added to adjust the pH to 3.6, thereby preparing an electrolytic nickel plating solution of the present invention.
[ Table 1]
Filling of through-holes by electrolytic nickel plating
The evaluation printed board 1 was subjected to electrolytic nickel plating according to the procedure shown in table 2. In the electrolytic nickel plating step, an external power source was used and the current density was set to 1.0A/dm2。
Note that the plating area does not include the surface area of the side surface of the through hole 14, but only the area of the plane of the opening (pad) 17 is calculated.
[ Table 2]
< evaluation test of plating filling Property >
The plated substrate was embedded and fixed in a resin for polishing, and then cross-section polishing was performed to observe the filling of the through-hole with a metal microscope.
Regarding the filling property, when the amount of deposition inside the through-hole was larger than the amount of deposition outside the through-hole, the hole (hole) or the gap (groove) was observed inside the through-hole, the hole was "o", and in other cases, the hole was "x".
Further, the outside of the through-hole was observed for the presence or absence of cracks (fissures).
When the filling property was "good" and no crack was generated, the evaluation was "good", and in other cases, the evaluation was "poor".
The microphotographs of the cross-section of the substrate after plating and filling are shown in fig. 3 to 9. The evaluation results are shown in table 3.
[ Table 3]
In examples 1 to 4, the amount of deposited nickel 18 was more excellent in filling the through-holes belonging to the minute recessed portions than outside the through-holes so as to eliminate voids and gaps. In addition, no cracks were observed outside the through-hole.
In comparative example 1, conformal plating (follow-up plating) was performed in which the amount of deposited nickel 18 was the same between the inside and outside of the through-hole, and the filling property was poor.
In comparative example 2, the hole V was formed in the through hole, and the filling property was poor.
In comparative example 3, although there was no void inside the through-hole and the filling property was good, the deposited portion was very brittle and cracked, and significant peeling was observed in the nickel 18 deposited on the upper portion of the through-hole after polishing. Therefore, the microstructure is not satisfactory.
As shown in examples 1 to 4 and comparative examples 1 to 3, when electrolytic plating was performed using an electrolytic nickel plating solution containing an N-substituted carbonylpyridinium compound represented by general formula (a) or general formula (B), the minute pores formed in the electronic component could be satisfactorily filled with nickel, and a minute three-dimensional structure could be produced.
[ industrial applicability ]
The electrolytic nickel (alloy) plating solution containing the specific N-substituted carbonylpyridinium compound of the present invention can fill minute holes or minute recesses in electronic circuit components with high reliability, and can cope with further miniaturization of wiring, and thus can be widely applied to three-dimensional wiring formation, three-dimensional MEMS components, and the like.
[ description of reference numerals ]
1 evaluation printed substrate
10 around the portion to be plated
11 base material
12 Stack resin
13 copper foil
14 blind hole
15 seed layer
16 dry film photoresist
17 pad
18 precipitation of nickel
And (4) V holes.
Claims (10)
1. An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, comprising: a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (A);
in the general formula (A), m is 0 or 1; -R1is-R1aor-NR1bR1c，R1aIs alkyl of 1 to 6 carbon atoms, R1bIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R1cIs hydrogen atom, alkyl group having 1 to 6 carbon atoms, or amino group (-NH)2)；-R2Is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; x-Is any anion.
2. The electrolytic nickel or nickel alloy plating solution according to claim 1, wherein X-Is a halide ion.
3. An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, comprising: a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (B);
in the general formula (B), m is 0 or 1; -R1is-R1aor-NR1bR1c，R1aIs alkyl of 1 to 6 carbon atoms, R1bIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R1cIs hydrogen atom, alkyl group having 1 to 6 carbon atoms, or amino group (-NH)2)；-R3is-R3a-SO3 -，R3aIs an alkylene group having 1 to 6 carbon atoms.
4. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 3, wherein the nickel salt is at least one selected from the group consisting of nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, nickel citrate, and nickel fluoroborate.
5. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 3, wherein the pH buffer is one or more selected from the group consisting of boric acid, metaboric acid, acetic acid, tartaric acid, citric acid, and salts thereof.
6. An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution according to claim 2, wherein the N-substituted carbonylpyridinium compound represented by the general formula (a) is one or more compounds selected from the group consisting of a halide of 1-carbamoylpyridinium, a halide of 1- (carbamoylmethyl) pyridinium, a halide of 1- (dimethylcarbamoyl) pyridinium, a halide of 1- (diethylcarbamoyl) pyridinium, a halide of 1- (hydrazinocarbonylmethyl) pyridinium, and a halide of 1-acetonylpyridinium.
7. An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution according to claim 3, wherein the N-substituted carbonylpyridinium compound represented by the general formula (B) is selected from the group consisting of 1- (carbamoylmethyl) -4- (2-sulfoethyl) pyridinium hydroxide intramolecular salt, 1- (carbamoylmethyl) -4- (2-sulfopropyl) pyridinium hydroxide intramolecular salt, 1- (carbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide intramolecular salt, 1- (carbamoyl) -4- (2-sulfopropyl) pyridinium hydroxide intramolecular salt, 1- (dimethylcarbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide intramolecular salt, and 1- (dimethylcarbamoyl) -4- (2-sulfopropyl) pyridinium hydroxide intramolecular salt Yl) pyridinium intramolecular salt.
8. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 3, for filling minute holes or minute recesses formed in electronic circuit parts.
9. A method for plating and filling a nickel or nickel alloy, wherein a seed layer for electrolytic plating is applied in advance to the surface of a fine hole or a fine recess formed in an electronic circuit part, and then the electronic circuit part is immersed in the electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 8, and electrolytic plating is performed using an external power source.
10. A method for manufacturing a micro three-dimensional structure, comprising: the step of plating and filling the minute hole or the minute recess by the nickel or nickel alloy plating and filling method according to claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016099184 | 2016-05-18 | ||
| JP2016-099184 | 2016-05-18 | ||
| PCT/JP2017/017832 WO2017199835A1 (en) | 2016-05-18 | 2017-05-11 | Electrolytic nickel (alloy) plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109154093A CN109154093A (en) | 2019-01-04 |
| CN109154093B true CN109154093B (en) | 2020-11-27 |
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| CN201780030115.7A Active CN109154093B (en) | 2016-05-18 | 2017-05-11 | Electrolytic nickel (alloy) plating solution |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6860933B2 (en) |
| KR (1) | KR102354192B1 (en) |
| CN (1) | CN109154093B (en) |
| TW (1) | TWI726101B (en) |
| WO (1) | WO2017199835A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383073A (en) * | 1981-08-20 | 1983-05-10 | The Dow Chemical Company | Cationic resin curable with acid catalyzed cross-linkers |
| US5547832A (en) * | 1992-07-07 | 1996-08-20 | Eastman Kodak Company | Method for hardening photographic materials |
| CN101918618A (en) * | 2008-02-29 | 2010-12-15 | 阿托特德国有限公司 | Pyrophosphate-based bath for plating on tin alloy layers |
| CN104285000A (en) * | 2013-05-08 | 2015-01-14 | 德国艾托特克公司 | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or nickel alloy |
| JP2015101751A (en) * | 2013-11-25 | 2015-06-04 | 日本高純度化学株式会社 | Electrolytic gold plating solution and gold film produced using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014204620A1 (en) * | 2013-06-17 | 2014-12-24 | Applied Materials, Inc. | Method for copper plating through silicon vias using wet wafer back contact |
-
2017
- 2017-05-11 KR KR1020187032988A patent/KR102354192B1/en active IP Right Grant
- 2017-05-11 WO PCT/JP2017/017832 patent/WO2017199835A1/en active Application Filing
- 2017-05-11 CN CN201780030115.7A patent/CN109154093B/en active Active
- 2017-05-11 JP JP2018518251A patent/JP6860933B2/en active Active
- 2017-05-16 TW TW106116109A patent/TWI726101B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383073A (en) * | 1981-08-20 | 1983-05-10 | The Dow Chemical Company | Cationic resin curable with acid catalyzed cross-linkers |
| US5547832A (en) * | 1992-07-07 | 1996-08-20 | Eastman Kodak Company | Method for hardening photographic materials |
| CN101918618A (en) * | 2008-02-29 | 2010-12-15 | 阿托特德国有限公司 | Pyrophosphate-based bath for plating on tin alloy layers |
| CN104285000A (en) * | 2013-05-08 | 2015-01-14 | 德国艾托特克公司 | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or nickel alloy |
| JP2015101751A (en) * | 2013-11-25 | 2015-06-04 | 日本高純度化学株式会社 | Electrolytic gold plating solution and gold film produced using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190008232A (en) | 2019-01-23 |
| JPWO2017199835A1 (en) | 2019-03-14 |
| TW201807261A (en) | 2018-03-01 |
| JP6860933B2 (en) | 2021-04-21 |
| KR102354192B1 (en) | 2022-01-20 |
| TWI726101B (en) | 2021-05-01 |
| WO2017199835A1 (en) | 2017-11-23 |
| CN109154093A (en) | 2019-01-04 |
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