JP7021781B2 - Electrolytic nickel (alloy) plating solution - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention may be an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution (hereinafter, these may be collectively referred to as "electrolytic nickel (alloy) plating solution". Further, by using an electrolytic nickel (alloy) plating solution. The “nickel or nickel alloy” that precipitates may be referred to as “nickel (alloy)”). The present invention relates to an electrolytic nickel (alloy) plating solution particularly suitable for plating and filling of minute gaps generated at the time.
The present invention also relates to a method for plating and filling minute pores and minute recesses using such an electrolytic nickel (alloy) plating solution, a method for manufacturing a minute three-dimensional structure, an electronic component joint and a method for manufacturing the same.

Electronic circuit components typified by semiconductors and printed circuit boards (hereinafter, may be simply referred to as "electronic components") have minute holes and minute recesses such as vias, through holes, and trenches for forming wiring. .. Conventionally, in the manufacture of a multilayer printed circuit board in which a plurality of circuit boards are laminated, a staggered via structure in which the wall surface of the via is subjected to conformal copper plating (follow-up plating) and then connected to other layers in a staggered arrangement has been the mainstream. However, with the recent miniaturization and higher functionality of electronic devices, it is indispensable to save space by a stack via structure in which vias are filled with copper plating and other layers are layered and connected as they are.

Filling technology by electrolytic copper plating is also applied to semiconductor manufacturing technology, and technology called damascene process and through silicon via (TSV: Through Silicon Via) has appeared, and vias are filled with electrolytic copper plating to create a three-dimensional wiring structure. It has become possible to form.

The electrolytic copper plating solution for filling micropores and microrecesses contains multiple additives and fills vias by optimally controlling the concentration balance between them, but there are no macrovoids of about several μm. Even if it could be filled, there was a problem that microvoids on the order of nm remained as a side effect of the additive. Copper is a metal whose melting point is not so high (1083 ° C.), and it is well known that recrystallization occurs even when it is left at room temperature after electrolytic copper plating. As a result of the aggregation of nm-order microvoids in this recrystallization process, there is a problem that macrovoids are formed.
For example, in Non-Patent Document 1, polyethylene glycol (PEG), which is an additive, is partially incorporated into a copper film, and nm-order microvoids are generated in the copper film, which is left at room temperature in the copper recrystallization process. , Forming large voids up to 70 nm in diameter.

Therefore, the copper filling method using the electrolytic copper plating solution potentially has such a problem, and when the wiring is further miniaturized, the void growth and the void movement due to the microvoid aggregation As a result, the deterioration of wiring reliability may become apparent.

Therefore, even if microvoids caused by the plating additive remain, the micropores and recesses are filled with a refractory metal that is unlikely to recrystallize at room temperature, especially nickel (melting point: 1455 ° C.), which is common as a base plating for electronic components. The present inventor speculates that if this can be done, void aggregation will not occur and the wiring can be highly reliable.

Attempts to fill the recesses with electrolytic nickel plating are also being considered.
In Non-Patent Document 2, the filling property in the trench when various additives are added to the electrolytic nickel plating solution is examined, and it is stated that the minute recesses (trench) are filled by adding thiourea.
However, according to a follow-up test by the present inventors (examples described later), the filling property with the electrolytic nickel plating solution described in Non-Patent Document 2 is still insufficient, the generation of voids cannot be suppressed, and the precipitate is formed. It was found that the structure was defective due to cracks in the structure.

The miniaturization of electronic circuits is progressing more and more, and it is desired to develop a nickel filling method in which the filling properties of micropores and recesses are insufficient with such known technology and defects such as voids and cracks do not occur. Was there.

Surface Technology Vol.52, No.1, pp.34-38 (2001) Journal of Electronics Packaging Society, Vol.17, No.2, pp.143-148 (2014)

The present invention has been made in view of the above background technique, and the problem thereof is that when the micropores and microrecesses in the electronic circuit parts are filled with nickel or a nickel alloy, defects such as voids and seams are not generated. The present invention is to provide an electrolytic nickel (alloy) plating solution that can be filled, and also to provide a nickel or nickel alloy plating filling method using such an electrolytic nickel (alloy) plating solution, and a method for manufacturing a micro three-dimensional structure. To provide.
Further, an object of the present invention is an electrolytic nickel (alloy) plating solution capable of filling minute gaps generated when two or more electronic components are overlapped with each other and firmly joining the electronic components to each other. , To provide a method for manufacturing an electronic component junction using it.

As a result of diligent studies to solve the above problems, the present inventor has performed electrolytic plating using an electrolytic nickel plating solution containing a specific N-substituted pyridinium compound in micropores and microrecesses. , And have found that nickel can be filled 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, which comprises a nickel salt, a pH buffer, and an N-substituted pyridinium compound represented by the following general formula (A). It is a thing.

[In the general formula (A), -R ¹ is an alkyl group having 1 to 6 carbon atoms, an alkylamino group or a cyanoalkyl group, an amino group (-NH ₂ ) or a cyano group. -R ² is a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms, a vinyl group, a methoxycarbonyl group (-CO-O-CH ₃ ), a carbamoyl group (-CO-NH ₂ ), and a dimethylcarbamoyloxy. It is a group (-O-CO-N (CH ₃ ) ₂ ) or an aldoxime group (-CH = NOH). X ^- is any anion. ]

The present invention also provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, which comprises a nickel salt, a pH buffer, and an N-substituted pyridinium compound represented by the following general formula (B). It is a thing.

[In the general formula (B), -R ³ is a hydrogen atom or a hydroxyl group (-OH). -R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a vinyl group or a carbamoyl group (-CO-NH ₂ ). m is 0, 1 or 2. ]

The present invention also provides a method for producing a nickel precipitate or a nickel alloy precipitate, which comprises performing electrolytic plating using the above-mentioned electrolytic nickel plating solution or electrolytic nickel alloy plating solution.

Further, the present invention is characterized in that electrolytic plating is performed using the above-mentioned electrolytic nickel plating solution or electrolytic nickel alloy plating solution, and the micropores or microrecesses are filled with nickel precipitates or nickel alloy precipitates. It provides a method for manufacturing electronic parts.

Further, in the present invention, after a seed layer for electrolytic plating is previously applied to the surface of micropores or microrecesses formed in an electronic component, the electronic component is immersed in the above-mentioned electrolytic nickel plating solution or electrolytic nickel alloy plating solution. Further, the present invention provides a method for manufacturing an electronic component in which a nickel precipitate or a nickel alloy precipitate is filled in a micropore or a microrecess, which is characterized by electrolytic plating using an external power source.

The present invention also provides a method for manufacturing micro-three-dimensional structures, which comprises a step of plating and filling micropores or microrecesses by the above-mentioned manufacturing method.

Further, in the present invention, in a state where two or more electronic parts are stacked and a minute gap is formed between the electronic parts, the two or more electronic parts are subjected to the above-mentioned electrolytic nickel plating solution or electrolytic nickel alloy. The present invention provides a method for manufacturing an electronic component bonded body, which comprises immersing in a plating solution and electrolytically plating using an external power source to fill the minute gaps.

Further, the present invention is an electronic component joint in which two or more electronic components are joined by nickel or a nickel alloy, and the vicinity of the minute gap formed between the electronic components is larger than that of other portions. Also provides an electronic component junction characterized by the precipitation of a large amount of nickel or nickel alloy.

Further, the present invention is a terminal for joining electronic components made of nickel or a nickel alloy, which is contained in a base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. A plug portion embedded so as not to penetrate the base material and a cap portion having an outer diameter larger than the outer diameter of the plug portion and in contact with the plug portion are provided, and the outer diameter of the cap portion is 200 μm or less. The cap portion provides a terminal for joining electronic components on one side, which is characterized in that the cap portion has a shape protruding from the base material surface of the base material.

Further, the present invention is a terminal for joining electronic components made of nickel or a nickel alloy, which is contained in a base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. The two cap portions are provided with a plug portion embedded so as to penetrate the base material and two cap portions having an outer diameter larger than the outer diameter of the plug portion and in contact with both ends of the plug portion. Both have an outer diameter of 200 μm or less, and the two cap portions provide terminals for joining electronic components on both sides, which are characterized in that the two cap portions have a shape protruding from the respective substrate surfaces of the substrate. be.

Further, the present invention is a terminal for joining electronic components made of nickel or a nickel alloy, which is contained in a base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. It comprises a plug portion embedded so as not to penetrate the base material, and provides a single-sided electronic component joining terminal characterized in that the outer diameter of the plug portion is 100 μm or less.

Further, the present invention is a terminal for joining electronic components made of nickel or a nickel alloy, which is contained in a base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. It comprises a plug portion embedded so as to penetrate a base material, and provides a terminal for joining electronic components on both sides, characterized in that the outer diameter of the plug portion is 100 μm or less.

According to the present invention, by using nickel plating or nickel alloy plating, it is possible to fill micropores or microrecesses in an electronic circuit component without causing defects such as voids and seams.

In the present invention, since nickel having a high melting point and difficult to recrystallize at room temperature can be filled with micropores and microrecesses, even if the wiring is further miniaturized, problems due to the aggregation of voids are less likely to occur and the miniaturization progresses. It can be widely applied to 3D wiring formation and 3D MEMS (Micro Electro Mechanical Systems) parts.

Further, in the present invention, since nickel can be deposited in the minute portion, the amount of nickel deposited in the minute gap portion generated when the electronic parts are overlapped with each other can be increased, and the electronic parts can be firmly bonded to each other. Can be done.

It is a schematic diagram which shows the cross section around the plated part of the evaluation printed circuit board used in an Example. It is a photograph of the wiring pattern of the surface of the evaluation printed circuit board used in the Example. It is a schematic diagram which shows the cross section before joining of the electronic component for evaluation (copper wire and copper plate) used in an Example. It is a micrograph of the cross section of a substrate after plating filling (Example 1). It is a micrograph of the cross section of a substrate after plating filling (Example 2). It is a micrograph of the cross section of a substrate after plating filling (Example 3). It is a micrograph of the cross section of a substrate after plating filling (Example 4). It is a micrograph of the cross section of a substrate after plating filling (Example 5). It is a micrograph of the cross section of a substrate after plating filling (Example 6). It is a micrograph of the cross section of a substrate after plating filling (Comparative Example 1). It is a micrograph of the cross section of the substrate after plating filling (Comparative Example 2). It is a micrograph of the cross section of a substrate after plating filling (Comparative Example 3). It is a micrograph of the cross section of a copper wire and a copper plate after plating filling (Example 7). It is a micrograph of the cross section of a copper wire and a copper plate after plating filling (Example 8). It is a micrograph of a cross section of a copper wire and a copper plate after plating filling (Comparative Example 4). It is a schematic diagram of the cross section of a base material at the time of filling a nickel (alloy) precipitate in a micropore or a microrecess by the method of this invention. It is a schematic diagram which shows an example of the terminal for joining an electronic component on one side of this invention. It is a schematic diagram which shows an example of the terminal for joining electronic parts on both sides of this invention. It is a schematic diagram which shows an example of the terminal for joining an electronic component on one side of this invention. It is a schematic diagram which shows an example of the terminal for joining electronic parts on both sides of this invention.

Hereinafter, the present invention will be described, but the present invention is not limited to the following embodiments, and can be arbitrarily modified and carried out.

<Electrolytic nickel (alloy) plating solution>
The electrolytic nickel (alloy) plating solution of the present invention (hereinafter, may be simply abbreviated as "plating solution of the present invention") includes a nickel salt, a pH buffer, and the following general formula (A) or the following general formula. It contains an N-substituted pyridinium compound represented by (B).

[In the general formula (A), -R ¹ is an alkyl group having 1 to 6 carbon atoms, an alkylamino group or a cyanoalkyl group, an amino group (-NH ₂ ) or a cyano group. -R ² is a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms, a vinyl group, a methoxycarbonyl group (-CO-O-CH ₃ ), a carbamoyl group (-CO-NH ₂ ), and a dimethylcarbamoyloxy. It is a group (-O-CO-N (CH ₃ ) ₂ ) or an aldoxime group (-CH = NOH). X ^- is any anion. ]

[In the general formula (B), -R ³ is a hydrogen atom or a hydroxyl group (-OH). -R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a vinyl group or a carbamoyl group (-CO-NH ₂ ). m is 0, 1 or 2. ]

The nickel salt contained in the plating solution of the present invention includes nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, and citric acid from the viewpoint of water solubility and filling property. Examples thereof include nickel and nickel borofluoride, but the present invention is not limited thereto.
These may be used individually by 1 type, or may be used by mixing 2 or more types.

The total content of the nickel salts is preferably 10 g / L or more and 180 g / L or less, and particularly preferably 50 g / L or more and 130 g / L or less as nickel ions.
Within the above range, the precipitation rate of nickel can be made sufficient, and micropores and recesses can be filled without generating voids.

Examples of the pH buffering agent 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 may be used individually by 1 type, or may be used by mixing 2 or more types.

The total content of the pH buffer is preferably 1 g / L or more and 100 g / L or less, and particularly preferably 5 g / L or more and 50 g / L or less.
Within the above range, the action of the N-substituted pyridinium compound represented by the general formula (A) or the general formula (B) (hereinafter, may be referred to as “specific N-substituted pyridinium compound”) is less likely to be inhibited. The effect of the present invention is maintained.

The plating solution of the present invention contains a specific N-substituted pyridinium compound.
Due to the action of the specific N-substituted pyridinium compound, the plating solution of the present invention can fill micropores and microrecesses without generating voids.

When R ¹ , R ² , and R ⁴ of the general formula (A) and the general formula (B) are an alkyl group, an alkylamino group, a cyanoalkyl group, or a hydroxyalkyl group having 1 to 6 carbon atoms, the said. R ¹ , R ² , and R ⁴ may be different from each other. The carbon number of R ¹ , R ² , and R ⁴ is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 or 2.

In the above general formula (A), specific examples of -R ¹ include -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CN and the like.
Specific examples of -R ² include -H, -CH ₃ , -C ₂ H ₅ , -CH ₂ OH, -CH = CH ₂ , -CONH ₂ , -CH = NOH and the like.
Specific examples of X ⁻ include halide ions (chloride ion, bromide ion, iodide ion) and the like.

Specific examples of the specific N-substituted pyridinium compound represented by the above general formula (A) include 1-methylpyridinium, 1-ethylpyridinium, 1-propylpyridinium, 1-butylpyridinium, 1-pentylpyridinium, and 1-hexylpyridinium. , 1-Ethyl-3- (hydroxymethyl) pyridinium, 1-ethyl-4- (methoxycarbonyl) pyridinium, 1-butyl-4-methylpyridinium, 1-butyl-3-methylpyridinium, 1-methylpyridinium-2- Examples thereof include halides (chloride, bromide, iodide) such as aldoxime, 3-carbamoyl-1-methylpyridinium, 3- (dimethylcarbamoyloxy) -1-methylpyridinium (pyridostigmin), 1- (cyanomethyl) pyridinium. ..

In the above general formula (B), as a specific example of ^−R4 , the same as that of ^−R2 can be mentioned.

Specific examples of the specific N-substituted pyridinium compound represented by the above general formula (B) include 1- (3-sulfonatepropyl) pyridinium, 1- (2-sulfonateethyl) pyridinium, and 1- (4-sulfonatebutyl). Pyridinium, 2-vinyl-1- (3-sulfonatopropyl) pyridinium, 3-vinyl-1- (3-sulfonatopropyl) pyridinium, 4-vinyl-1- (3-sulfonatepropyl) pyridinium, 2-methyl -1- (3-Sulphonatopropyl) pyridinium, 3-methyl-1- (3-sulfonatepropyl) pyridinium, 4-methyl-1- (3-sulfonatepropyl) pyridinium, 2-ethyl-1- (3) -Sulfonatopropyl) pyridinium, 3-ethyl-1- (3-sulfonatepropyl) pyridinium, 4-ethyl-1- (3-sulfonatepropyl) pyridinium, 2-vinyl-1- (4-sulfonatebutyl) pyridinium, 3-Vinyl-1- (4-sulfonatebutyl) pyridinium, 4-vinyl-1- (4-sulfonatebutyl) pyridinium, 2-methyl-1- (4-sulfonatebutyl) pyridinium, 3-methyl-1- (4-sulfonatebutyl) Pyridinium, 4-Methyl-1- (4-sulfonatebutyl) pyridinium, 2-ethyl-1- (4-sulfonatebutyl) pyridinium, 3-ethyl-1- (4-sulfonatebutyl) pyridinium, 4-ethyl-1- (4-ethyl-1- (4-) Sulfonatobutyl) pyridinium, 4-tert-butyl-1- (3-sulfonatopropyl) pyridinium, 2,6-dimethyl-1- (3-sulfonatopropyl) pyridinium, 3- (aminocarbonyl) -1- (3-) Sulfonatopropyl) pyridinium, 1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 2-vinyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 3-vinyl-1- (2-hydroxy) -3-Sulphonatopropyl) pyridinium, 4-vinyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 2-methyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 3-methyl -1- (2-Hydroxy-3-sulfonatopropyl) pyridinium, 4-methyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 2-ethyl-1- (2-hydroxy-3-sulfonato) Propyl) pyridinium, 3-ethyl-1- (2-hydroxy-3-sulfonato) Examples thereof include propyl) pyridinium and 4-ethyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium.

"1- (3-Sulphonatopropyl) pyridinium" is a compound in the general formula (B) in which -R ³ is a hydrogen atom, -R ⁴ is a hydrogen atom, and m is 1. There are other names such as "propyl) pyridinium hydroxide intramolecular salt", "1- (3-sulfopropyl) pyridinium", and "PPS".
"2-Vinyl-1- (3-sulfonatopropyl) pyridinium" is a compound in the general formula (B) in which -R ³ is a hydrogen atom, -R ⁴ is a vinyl group bonded to the ortho position, and m is 1. There are other names such as "1- (3-sulfopropyl) -2-vinylpyridinium hydroxide intramolecular salt", "1- (3-sulfopropyl) -2-vinylpyridinium betaine", and "PPV".
"1- (2-Hydroxy-3-sulfonatopropyl) pyridinium" is a compound in the general formula (B) in which -R ³ is a hydroxyl group, -R ⁴ is a hydrogen atom, and m is 1. There are other names such as (2-hydroxy-3-sulfonatopropyl) pyridinium hydroxide intramolecular salt, "1- (2-hydroxy-3-sulfopropyl) pyridinium betaine", and "PPSOH".

The specific N-substituted pyridinium compound may be used alone or in combination of two or more.
The total content of the specific N-substituted pyridinium compound in the plating solution of the present invention is preferably 0.01 g / L or more and 100 g / L or less, and particularly preferably 0.1 g / L or more and 10 g / L or less.
Within the above range, the amount of nickel deposited outside the micropores and microrecesses can be increased, and the micropores and microrecesses can be filled without generating voids.

When the plating solution of the present invention is an electrolytic nickel alloy plating solution, the metal ions for alloying with nickel include, for example, tungsten, molybdenum, cobalt, manganese, iron, zinc, tin, copper, palladium, gold and the like. Can be mentioned. Known compounds can be used as these metal sources.
Further, although it is not a metal, carbon, sulfur, nitrogen, phosphorus, boron, chlorine, bromine and the like may be contained in the nickel or nickel alloy film.

A pit inhibitor, a primary brightener, a secondary brightener, a surfactant and the like can be added to the plating solution of the present invention as necessary, as long as the effects of the present invention are not impaired.

The plating solution of the present invention is particularly suitable for use in filling micropores or microdents formed in electronic circuit components, but is also used for producing ordinary nickel (alloy) precipitates. Can be done.
That is, the present invention also relates to a method for producing a nickel precipitate or a nickel alloy precipitate, which comprises performing electrolytic plating using the above-mentioned electrolytic nickel plating solution or electrolytic nickel alloy plating solution.

When the micropores and microrecesses are filled with the plating solution of the present invention as in the examples described later, the amount of precipitation inside the micropores and microrecesses is larger than the amount of precipitation outside the micropores and microrecesses. Therefore, nickel (or nickel alloy) can be sufficiently embedded in the micropores and the microrecesses. In addition, voids (holes) and seams (grooves) are less likely to occur inside the micropores and recesses.
Therefore, in combination with the high melting point of nickel, it is expected that the electronic circuit component in which the micropores and the microrecesses are filled with the plating solution of the present invention has high reliability.

<Manufacturing method of nickel (alloy) filled electronic parts / Manufacturing method of micro-three-dimensional structure>
The present invention is characterized in that electrolytic plating is performed using the electrolytic nickel plating solution or the electrolytic nickel alloy plating solution, wherein the micropores or microrecesses are filled with nickel precipitates or nickel alloy precipitates. It also relates to a method of manufacturing parts (ie, a method of filling nickel precipitates or nickel alloy precipitates).
Further, in the present invention, after a seed layer for electrolytic plating is previously applied to the surface of micropores or microrecesses formed in an electronic component, the electronic component is immersed in the electrolytic nickel (alloy) plating solution to the outside. It is also a method for manufacturing an electronic component in which nickel precipitates or nickel alloy precipitates are filled in micropores or recesses, which is characterized by electrolytic plating using a power source.
Further, the present invention is also a method for manufacturing micro-three-dimensional structures, which comprises a step of plating and filling micropores or microrecesses by the above-mentioned manufacturing method.

The "micropores or microrecesses" are minute recessed portions such as vias, through holes, and trenches formed in electronic circuit parts such as semiconductors and printed circuit boards, and are filled with metal by electrolytic plating or the like. As a result, it refers to a part that functions as a wiring part, and the shape seen from above is not limited. Further, the "micropores" may or may not penetrate.

In order to carry out the present invention, it is necessary to form minute holes and minute recesses on the substrate to be plated in the electronic circuit component.

The base material to be plated is not particularly limited, and specifically, glass epoxy material, BT (Bismaleimide-Triazine) resin material, polypropylene material, polyimide material, ceramic material, silicon material, metal material, and glass, which are often used as electronic circuit parts. Materials and the like can be mentioned.

There is no limitation on the method of forming micropores or microrecesses on the substrate to be plated, and a known method can be appropriately used. For example, a method by laser processing or ion etching can be mentioned, and a minute recess can be formed at a depth of 100 μm or less and an aspect ratio of 0.5 or more.
Then, if necessary, a pattern is formed on the surface of the substrate to be plated with a photoresist or the like.

When the base material to be plated on which the micro-recesses are formed is an insulating base material, a seed layer for electrolytic plating is formed on the surface of the base material and the inner surface of the micro-recesses. The method for forming the seed layer is not limited, and specific examples thereof include metal deposition by sputtering and electroless plating.
The metal constituting the seed layer is not particularly limited, and copper, nickel, palladium and the like can be exemplified.

After forming the seed layer for electrolytic plating, the base material 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 to form micropores and concave portions. , Nickel or nickel alloy.
When plating the substrate to be plated once dried after forming the seed layer, it may be subjected to degreasing and pickling according to a conventional method, and then electroplated using the plating solution of the present invention.

Here, "filling" of micropores and microrecesses means embedding micropores and microrecesses without forming large voids (holes), but when the micropores and microrecesses are not completely filled. (For example, as shown in FIGS. 16 (b) and 19 (c), nickel (alloy) is deposited in the micropores and the microrecesses, but there is a recessed portion) or the micropores. The case where nickel or nickel alloy is deposited even on the outer peripheral edge of the micro-recess (in the case of FIG. 16A or the like) is also included in "filling".

In the filling method of the present invention, when electrolytic plating is performed using an external power source, the minimum plating cross-sectional thickness inside the micropores or microrecesses 30 (X2 in _FIG . 16) is outside the micropores or microrecesses 30. It is possible to make the peripheral portion 31 larger than the maximum plating cross _- sectional thickness (X1 in FIG. 16).
That is, in the filling method of the present invention, it is possible to increase the amount of nickel (alloy) deposited in the micropores or the microrecesses 30.

When nickel (alloy) is filled inside the micropores or microrecesses 30 by the filling method of the present invention, as shown in FIG. 16A, the micropores or microrecesses 30 are completely made of nickel (alloy). It may be buried, or as shown in FIG. 16B, it may not be partially buried (it may have an inverted convex shape).

By the method including the step of plating and filling the micropores or the microrecesses by the nickel or nickel alloy plating filling method of the present invention, the micropores or the microrecesses are filled with nickel or nickel alloy. The structure can be manufactured.

The plating temperature is preferably 30 ° C. or higher, and particularly preferably 40 ° C. or higher. Further, 70 ° C. or lower is preferable, and 60 ° C. or lower is particularly preferable.
When it is within the above range, the filling property of the minute holes and the minute recesses is excellent, and it is advantageous in terms of cost.

The current density during plating is preferably 0.1 A / dm ² or more, and particularly preferably 1 A / dm ² or more. Further, 10 A / dm ² or less is preferable, and 5 A / dm ² or less is particularly preferable.
When it is within the above range, the filling property of the minute holes and the minute recesses is excellent, and it is advantageous in terms of cost.

Further, the current density may or may not be constant during plating filling (for example, the initial current density is lowered and the current density is gradually increased; the pulse current is used; etc.). ).
It is preferable that the current density is always constant during plating filling (or constant during most of the plating filling) because it is easy to fill without forming voids.

The plating time is preferably 5 minutes or more, and particularly preferably 10 minutes or more. Further, 360 minutes or less is preferable, and 60 minutes or less is particularly preferable.
When it is within the above range, the filling property of the minute holes and the minute recesses is excellent, and it is advantageous in terms of cost.

<Electronic component joints and their manufacturing methods>
In the present invention, two or more electronic components are stacked, and the two or more electronic components are immersed in the electrolytic nickel (alloy) plating solution in a state where a minute gap is formed between the electronic components. It is also a method for manufacturing an electronic component joint, which is characterized in that the minute gaps are filled by electrolytic plating using an external power source.

"Electronic component" means a component that is surface-mounted on an electronic circuit. The "electronic component joint" means a body in which two or more electronic components are joined and integrated.

When the surface of an electronic component is plated and a plurality of electronic components are joined (to produce an electronic component joint), if the plating grows uniformly, the strength is insufficient in the vicinity of the minute gap between the electronic components. And may cause problems.

When plated with the electrolytic nickel (alloy) plating solution of the present invention, the amount of nickel or nickel alloy deposited increases in the vicinity of such minute gaps.
That is, according to the present invention, it is an electronic component junction in which two or more electronic components are joined by nickel or a nickel alloy, and another electronic component is formed in the vicinity of a minute gap formed between the electronic components. It is possible to obtain an electronic component junction characterized by the precipitation of more nickel or nickel alloy than the site.

Since the electronic component joint of the present invention has a large amount of nickel or nickel alloy deposited in the vicinity of the minute gap, it has sufficient strength and high reliability at the junction between the electronic components.

According to the present invention, the plating temperature at the time of manufacturing the electronic component joint is preferably 30 ° C. or higher, and particularly preferably 40 ° C. or higher. Further, 70 ° C. or lower is preferable, and 60 ° C. or lower is particularly preferable.
Within the above range, the amount of nickel or nickel alloy deposited in the vicinity of the minute gaps is sufficient, and the bonding strength is likely to be improved.

According to the present invention, the current density when manufacturing the electronic component joint is preferably 0.1 A / dm ² or more, and particularly preferably 1 A / dm ² or more. Further, 10 A / dm ² or less is preferable, and 5 A / dm ² or less is particularly preferable.
Within the above range, the amount of nickel or nickel alloy deposited in the vicinity of the minute gaps is sufficient, and the bonding strength is likely to be improved.

Further, the current density may or may not be constant during plating filling (for example, the initial current density is lowered and the current density is gradually increased; the pulse current is used; etc.). ).
It is preferable that the current density is always constant during plating filling (or constant during most of the plating filling) from the viewpoint of bonding strength.

The plating time is preferably 5 minutes or more, and particularly preferably 10 minutes or more. Further, 360 minutes or less is preferable, and 60 minutes or less is particularly preferable.
When it is within the above range, the bonding strength is excellent and it is advantageous in terms of cost.

<Terminal for joining electronic components>
In the present invention, electrons having few voids (holes) are embedded in a base material having micropores or microrecesses in a direction substantially perpendicular to the base material surface of the base material 11 (60 ° to 90 ° direction). It is also related to the terminals for joining parts.

The terminal 40 for joining electronic components of the present invention is made of nickel or a nickel alloy. By using the electrolytic nickel (alloy) plating solution of the present invention described above, it is easy to form the terminal for joining electronic components of the present invention.

The terminal 40 for joining electronic components of the present invention is embedded in a base material 11 having a thickness of 1 mm or less.
The electronic component joining terminal 40 may be a single-sided (not penetrating the base material 11) electronic component joining terminal as shown in FIGS. 17 and 19, or both sides as shown in FIGS. 18 and 20. It may be a terminal for joining electronic components (penetrating the base material 11).

FIG. 17 shows a plug portion 41 embedded so as not to penetrate the base material 11 in a direction substantially perpendicular to the base material surface of the base material 11, and a cap portion 42 in contact with the plug portion 41. It is a single-sided electronic component joining terminal 40 provided.
The cap portion 42 has a shape protruding from the substrate surface of the substrate 11, and its outer diameter is larger than the outer diameter of the plug portion 41 and is 200 μm or less.
The cross section of the plug portion 41 and the cap portion 42 parallel to the base material surface is usually circular, but when it is not circular, the "outer diameter" means the outer diameter of a circle having an equal area (hereinafter referred to as "outer diameter"). The same applies to the terminal 40 for joining electronic parts shown in FIGS. 18 to 20).

FIG. 18 shows a plug portion 41 embedded so as to penetrate the base material 11 in a direction substantially perpendicular to the base material surface of the base material 11, and two portions in contact with both ends of the plug portion 41. A terminal 40 for joining electronic components on both sides provided with a cap portion 42.
Each of the two cap portions 42 has a shape protruding from the surface of each base material of the base material 11. The outer diameters of the two cap portions 42 are both larger than the outer diameter of the plug portion 41 and 200 μm or less.

FIG. 19 shows a single-sided electronic component joining terminal 40 composed of a plug portion 41 embedded so as not to penetrate the base material 11 in a direction substantially perpendicular to the base material surface of the base material 11. The outer diameter of the plug portion 41 is 100 μm or less.
The end portion of the plug portion 41 may protrude from the base material surface of the base material 11 as shown in FIG. 19 (a), or may be the same as the base material surface of the base material 11 as shown in FIG. 19 (b). It may be at a height, or may be buried in the base material surface of the base material 11 as shown in FIG. 19 (c).

FIG. 20 shows a terminal 40 for joining electronic components on both sides, which is composed of a plug portion 41 embedded so as to penetrate the base material 11 in a direction substantially perpendicular to the base material surface of the base material 11. The outer diameter of the plug portion 41 is 100 μm or less.
The end portion of the plug portion 41 may protrude from the base material surface of the base material 11 as shown in FIG. 20 (a), or may be the same as the base material surface of the base material 11 as shown in FIG. 20 (b). It may be at a height, or may be buried in the base material surface of the base material 11 as shown in FIG. 20 (c).

A nickel (alloy) electronic component joining terminal with a size of 100 μm or less in the outer diameter of the plug portion 41 or 200 μm or less in the outer diameter of the cap portion 42 embedded in a base material having a thickness of 1 mm or less. It was impossible to manufacture with conventional technology. By performing plating using the electrolytic nickel (alloy) plating solution of the present invention described above, the generation of voids in the nickel (alloy) precipitate is suppressed, and the terminal for joining electronic parts of such a size has a good yield. Can be manufactured.

When manufacturing terminals for joining electronic components using the electrolytic nickel (alloy) plating solution of the present invention, terminals for joining electronic components can be used on thinner substrates of 0.8 mm or less and thinner substrates of 0.5 mm or less. Easy to embed.
Further, an electronic component joining terminal having a plug portion having a smaller outer diameter of 70 μm or less and a smaller outer diameter of 50 μm or less, and an electron having a cap portion having a smaller outer diameter of 150 μm or less and a smaller outer diameter of 100 μm or less. Easy to manufacture terminals for joining parts.

It is preferable that there is no void having a maximum width of more than 10 μm in the plug portion 41 of the terminal 40 for joining electronic components.
By using the electrolytic nickel (alloy) plating solution of the present invention described above, it is easy to form a plug portion without such a large void.

Preferred conditions (plating temperature, current density, etc.) for manufacturing the above-mentioned terminal for joining electronic parts by performing plating using the electrolytic nickel (alloy) plating solution of the present invention are the above-mentioned <nickel (alloy) filling. The conditions are almost the same as those described in the section of "Manufacturing method of electronic parts / Manufacturing method of micro three-dimensional structure>".

Hereinafter, the present invention will be described in more detail 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 thereof is not exceeded.

[Filling of minute recesses]
Examples 1 to 6, Comparative Examples 1 to 3
As a model of the minute recess, a 12 mm square evaluation printed circuit board (manufactured by Nippon Circuit Co., Ltd.) having a laser via with an aspect ratio of 0.88 (φ45 μm × 40 μm D) was used.

FIG. 1 shows a cross-sectional view of the area around the portion to be plated 10. A copper foil 13 having a thickness of 12 μm is attached to a via hole forming portion of a base material 11 made of BT (Bismaleimide-Triazine) having a thickness of 0.4 mm, and a prepreg type build-up resin 12 having a thickness of 60 μm is laminated. A blind via hole (hereinafter, may be simply abbreviated as "via hole" or "via") 14 having a diameter of 45 μm and a depth of 40 μm is created by a laser, and the outer surface of the substrate (the surface of the build-up resin 12) and the inside of the via 14 are created. A seed layer 15 was formed on the wall surface by electroless copper plating in an amount of about 1 μm.
Further, a printed circuit board 1 for evaluation is obtained by forming the wiring pattern shown in FIG. 2 with a dry film resist (DFR) 16 having a thickness of 25 μm and opening a pad (opening) 17 (φ190 μm) having a via 14. And said.

In FIG. 2, the white portion is the copper-plated portion and the black portion is the dry film resist portion. Of the white portions, the largest circular portion to which the wiring is connected corresponds to the circular pad 17 (φ190 μm) in FIG. 1. Via holes 14, which are minute recesses shown in FIG. 1, are formed in all of the circular pads 17.

<Preparation of electrolytic nickel plating solution>
An electrolytic nickel plating solution was prepared by dissolving nickel sulfamate at 600 g / L, nickel chloride at 10 g / L, and boric acid at 30 g / L in deionized water.
The additives shown in Table 1 were added to the electrolytic nickel plating solution in the amount shown in Table 1 and dissolved.
Next, an appropriate amount of 100 g / L of a sulfamic acid aqueous solution was added to adjust the pH to 3.6 to prepare the electrolytic nickel plating solution of the present invention.

<filling of vias by electrolytic nickel plating>
The evaluation printed circuit board 1 was subjected to electrolytic nickel plating in the steps shown in Table 2. In the electrolytic nickel plating step, an external power source was used to achieve a current density of 1.0 A / dm ² .
The plating area was calculated as the surface area including the side surface of the via 14.

<Plating fillability evaluation test>
The substrate after plating was embedded and fixed in a resin for polishing, and then the cross section was polished, and the filling condition of vias was observed with a metallurgical microscope.
Regarding the filling property, when the amount of precipitation inside the via hole is larger than the amount of precipitation outside the via hole, no voids (holes) or seams (grooves) are observed inside the via hole, "○", otherwise "×". And said.
In addition, the presence or absence of cracks outside the via hole was observed.
When the filling property was "◯" and no cracks were generated, it was evaluated as "good", and when it was not, it was evaluated as "poor".

Micrographs of the cross section of the substrate after plating filling are shown in FIGS. 4 to 12. The evaluation results are shown in Table 3.

In Examples 1 to 6, the amount of precipitated nickel 18 was larger in the inside of the via hole, which is a minute recess, than in the outside of the via hole, and was well filled without voids or seams. No cracks were observed outside the via hole.

In Comparative Example 1, conformal plating (follow-up plating) in which the amount of precipitated nickel 18 was about the same inside and outside the via hole, and the filling property was poor.

In Comparative Example 2, there was a void V having a maximum width of 14 μm inside the via, and the filling property was poor.

In Comparative Example 3, there were no voids inside the via and the filling property was good, but the precipitated portion was very brittle and cracks were generated, and remarkable peeling of the precipitated nickel 18 was observed at the upper part of the via after polishing. .. Therefore, it was poor as a micro-three-dimensional structure.

As the results of Examples 1 to 6 and Comparative Examples 1 to 3 show, by electrolytic plating with an electrolytic nickel plating solution containing an N-substituted pyridinium compound represented by the general formula (A) or the general formula (B). , The micropores formed in the electronic component could be satisfactorily filled with nickel, and it became possible to create a microthree-dimensional structure.

[Joining electronic components]
Examples 7-8, Comparative Example 4
As a model of the electronic component to be joined, a copper wire (φ0.9 mm) and a copper plate (20 mm × 20 mm × 0.3 mmt) with a masked back surface were used.

As shown in FIG. 3, two copper plates 22 whose back surface side is masked with the masking material 22a are prepared, and the copper wire 21 is sandwiched between the two unmasked surfaces of the copper plates 22 and fixed by the jig 23. , An electronic component sample 20 in which a minute gap portion 24 was formed between the copper wire 21 and the copper plate 22 was produced.

<Preparation of electrolytic nickel plating solution>
An electrolytic nickel plating solution was prepared by dissolving nickel sulfamate at 600 g / L, nickel chloride at 10 g / L, and boric acid at 30 g / L in deionized water.
The additives shown in Table 4 were added to the electrolytic nickel plating solution in the amount shown in Table 4 and dissolved.
Next, an appropriate amount of 100 g / L of a sulfamic acid aqueous solution was added to adjust the pH to 3.6 to prepare the electrolytic nickel plating solution of the present invention.

<Joining copper wire and copper plate by electrolytic nickel plating>
The electronic component sample was immersed in the electrolytic nickel plating solution so that the line direction of the copper wire 21 and the plating solution surface were perpendicular to each other, and electrolytic nickel plating was performed in the process shown in Table 5. One nickel anode was opposed to the outside of the masking material 22a. In the electrolytic nickel plating step, an external power source was used to achieve a current density of 1.0 A / dm ² .
The plating area was only the surface area of the copper plate 22.

<Joinability evaluation test>
The plated electronic component sample (bonded body) was embedded and fixed in a resin for polishing, and then the cross section was polished, and the bonded state of the copper wire 21 and the copper plate 22 was observed with a metallurgical microscope.
Regarding the bondability, the case where the nickel plating thickness of the minute gap portion 24 where the copper wire 21 and the copper plate 22 are in contact is thicker than the other portions is marked with “◯”, and the other cases are marked with “x”.

Micrographs of cross sections of electronic component samples (joints) after plating filling are shown in FIGS. 13 to 15. The evaluation results are shown in Table 6.

In Examples 7 to 8, the amount of the precipitated nickel 18 was such that the minute gap portion 24 in which the copper wire 21 and the copper plate 22 were in contact was larger than the other portions, and the bonded nickel 18 was more firmly bonded.

In Comparative Example 4, the plating had a substantially uniform thickness at all the sites, and the bondability was poor.

As the results of Examples 7 to 8 and Comparative Example 4 show, microscopic plating is performed with an electrolytic nickel plating solution containing an N-substituted pyridinium compound represented by the general formula (A) or the general formula (B). The joints of the parts are plated with thicker nickel, making it possible to join more firmly.

The electrolytic nickel (alloy) plating solution containing the specific N-substituted pyridinium compound of the present invention can reliably fill micropores or microrecesses in electronic circuit components, and firmly joins electronic components to each other. Since it can be used, it can be widely applied to three-dimensional wiring formation, three-dimensional MEMS parts, and the like because it can cope with further miniaturization of wiring.

1 Printed circuit board for evaluation 10 Peripheral area to be plated 11 Base material 12 Build-up resin 13 Copper foil 14 Blind via hole 15 Seed layer 16 Dry film resist 17 Pad 18 Precipitated nickel (alloy)
V-void 20 Electronic component sample 21 Copper wire 22 Copper plate 22a Masking material 23 Jig 24 Micro gap 30 Micro hole / micro recess 31 Peripheral 40 Electronic component joining terminal 41 Plug 42 Cap

Claims (23)

An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, which comprises a nickel salt, a pH buffer, and an N-substituted pyridinium compound represented by the following general formula (A).

[In the general formula (A), -R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkylamino group or a cyanoalkyl group, an amino group (-NH ₂ ) or a cyano group. -R ² is a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 6 carbon atoms, a vinyl group, a methoxycarbonyl group (-CO-O-CH ₃ ), a carbamoyl group (-CO-NH ₂ ), and a dimethylcarbamoyloxy. It is a group (-O-CO-N (CH ₃ ) ₂ ) or an aldoxime group (-CH = NOH). X ^- is any anion. ]
(However, this excludes the case where the general formula (A) is the following formula (A1) and the case where the following formula (A2) is used.)

The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to claim 1, wherein X ⁻ is a halide ion. The N-substituted pyridinium compound represented by the general formula (A) is a halide of 1-methylpyridinium, a halide of 1-ethylpyridinium, a halide of 1-propylpyridinium, a halide of 1-butylpyridinium, or 1 -ethyl. -3- (Hydroxymethyl) pyridinium halide, 1-ethyl-4- (methoxycarbonyl) pyridinium halide, 1-butyl-4-methylpyridinium halide, 1-butyl-3-methylpyridinium halide , 1-Methylpyridinium-2-aldoxime halide, 3-carbamoyl-1-methylpyridinium halide, 3- (dimethylcarbamoyloxy) -1-methylpyridinium halide and 1- (cyanomethyl) pyridinium halide The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to claim 2, which is one or more compounds selected from the group consisting of. An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution (provided as nickel-cobalt-boron ) containing a nickel salt, a pH buffer, and an N-substituted pyridinium compound represented by the following general formula (B). (Except when it is an electrolytic nickel alloy plating solution for the original alloy) .

[In the general formula (B), -R ³ is a hydrogen atom or a hydroxyl group (-OH). -R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a vinyl group or a carbamoyl group (-CO-NH ₂ ). m is 0, 1 or 2. ] An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution containing a nickel salt, a pH buffer, and an N-substituted pyridinium compound represented by the following general formula (B), in the case of an electrolytic nickel alloy plating solution, nickel. An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, wherein the metal ion for alloying with is tungsten, molybdenum, manganese, iron, zinc, tin, copper, palladium or gold .

[In the general formula (B), -R ³ is a hydrogen atom or a hydroxyl group (-OH). -R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a vinyl group or a carbamoyl group (-CO-NH ₂ ). m is 0, 1 or 2. ] The N-substituted pyridinium compound represented by the general formula (B) is 1- (3-sulfonatepropyl) pyridinium, 1- (2-sulfonateethyl) pyridinium, 1- (4-sulfonatebutyl) pyridinium, 2-vinyl- 1- (3-Sulphonatopropyl) pyridinium, 3-vinyl-1- (3-sulfonatepropyl) pyridinium, 4-vinyl-1- (3-sulfonatepropyl) pyridinium, 2-methyl-1- (3-) Sulfonatopropyl) pyridinium, 3-methyl-1- (3-sulfonatopropyl) pyridinium, 4-methyl-1- (3-sulfonatepropyl) pyridinium, 2-ethyl-1- (3-sulfonatepropyl) pyridinium , 3-Ethyl-1- (3-sulfonatopropyl) pyridinium, 4-ethyl-1- (3-sulfonatepropyl) pyridinium, 2-vinyl-1- (4-sulfonatebutyl) pyridinium, 3-vinyl-1- (4-Sulfonatobutyl) pyridinium, 4-vinyl-1- (4-sulfonatebutyl) pyridinium, 2-methyl-1- (4-sulfonatebutyl) pyridinium, 3-methyl-1- (4-sulfonatebutyl) pyridinium, 4-methyl- 1- (4-sulfonatebutyl) pyridinium, 2-ethyl-1- (4-sulfonatebutyl) pyridinium, 3-ethyl-1- (4-sulfonatebutyl) pyridinium, 4-ethyl-1- (4-sulfonatebutyl) pyridinium, 4- tert-butyl-1- (3-sulfonatopropyl) pyridinium, 2,6-dimethyl-1- (3-sulfonatepropyl) pyridinium, 3- (aminocarbonyl) -1- (3-sulfonatopropyl) pyridinium, 1- (2-Hydroxy-3-sulfonatopropyl) pyridinium, 2-vinyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 3-vinyl-1- (2-hydroxy-3-sulfonatopropyl) ) Pyridinium, 4-vinyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 2-methyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 3-methyl-1- (2-) Hydroxy-3-sulfonatopropyl) pyridinium, 4-methyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 2-ethyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium, 3- Ethyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium The electrolytic nickel plating solution or electrolytic nickel according to claim 4 or 5, which is one or more compounds selected from the group consisting of 4-ethyl-1- (2-hydroxy-3-sulfonatopropyl) pyridinium. Alloy plating solution. 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 borofluoride. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 6 . The invention according to any one of claims 1 to 7 , wherein the pH buffering agent is at least one selected from the group consisting of boric acid, metaboric acid, acetic acid, tartaric acid and citric acid, and salts thereof. Electrolytic nickel plating solution or electrolytic nickel alloy plating solution. The electrolytic nickel plating according to any one of claims 1 to 8 , which is for filling micropores or recesses formed in electronic parts or microgaps generated when electronic parts are overlapped with each other. Liquid or electrolytic nickel alloy plating liquid. A method for producing a nickel precipitate or a nickel alloy precipitate, which comprises performing electrolytic plating using the electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 9 . .. Nickel precipitates or nickel precipitates in micropores or recesses, characterized in that electrolytic plating is performed using the electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 9 . A method for manufacturing electronic parts filled with nickel alloy precipitates. The electrolytic nickel plating solution according to any one of claims 1 to 9, wherein a seed layer for electrolytic plating is previously applied to the surface of micropores or microrecesses formed in the electronic component, and then the electronic component is subjected to the electrolytic nickel plating solution according to any one of claims 1 to 9 . Alternatively, a method for manufacturing an electronic component in which a nickel precipitate or a nickel alloy precipitate is filled in a micropore or a microrecess, which comprises immersing in an electrolytic nickel alloy plating solution and performing electrolytic plating using an external power source. .. When electrolytic plating is performed using an external power source, the minimum plating cross-sectional thickness X ₂ inside the micropores or microrecesses becomes larger than the maximum plating cross _- sectional thickness X1 at the outer peripheral edge of the micropores or microrecesses. The method for manufacturing an electronic component, wherein the micropores or the microrecesses according to claim 12 are filled with nickel precipitates or nickel alloy precipitates. A method for manufacturing micro-three-dimensional structures, which comprises a step of plating and filling micropores or microrecesses by the manufacturing method according to any one of claims 11 to 13 . The claim according to any one of claims 1 to 9 , wherein the two or more electronic components are stacked and a minute gap is formed between the electronic components. A method for manufacturing an electronic component bonded body, which comprises immersing in an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution and electrolytically plating using an external power source to fill the minute gaps. An electronic component junction in which two or more electronic components are joined by nickel or a nickel alloy, and the vicinity of the minute gap formed between the linear electronic component and the plate-shaped electronic component is the other. An electronic component junction characterized in that more nickel or nickel alloy is deposited than the site of. The electronic component joint according to claim 15, wherein the linear electronic component is a copper wire and the plate-shaped electronic component is a copper plate. A terminal for joining electronic components made of nickel or nickel alloy so that the base material does not penetrate the base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. It is provided with a plug portion embedded in the plug portion and a cap portion having an outer diameter larger than the outer diameter of the plug portion and in contact with the plug portion, and the outer diameter of the cap portion is 200 μm or less, and the cap portion is provided. Is a single-sided electronic component joining terminal characterized in that it has a shape protruding from the base material surface of the base material. A terminal for joining electronic components made of nickel or nickel alloy, which penetrates the base material in a base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. It is provided with a plug portion embedded in the plug and two cap portions having an outer diameter larger than the outer diameter of the plug portion and in contact with both ends of the plug portion, and the outer diameters of the two cap portions are both. A terminal for joining electronic components on both sides, which is 200 μm or less and has a shape in which the two cap portions protrude from the respective substrate surfaces of the substrate. A terminal for joining electronic components made of nickel or nickel alloy so that the base material does not penetrate the base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. A terminal for joining electronic components on one side, which is composed of a plug portion embedded in the plug portion and has an outer diameter of 100 μm or less. A terminal for joining electronic components made of nickel or nickel alloy, which penetrates the base material in a base material having a thickness of 1 mm or less in a direction substantially perpendicular to the base material surface of the base material. A terminal for joining electronic components on both sides, which comprises a plug portion embedded in the plug portion and has an outer diameter of 100 μm or less. The terminal for joining electronic components according to any one of claims 18 to 21 , wherein no void having a maximum width of more than 10 μm is present in the plug portion. The claim according to any one of claims 18 to 22 , which is formed by using the electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 9 . Terminal for joining electronic components.

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