TW201807261A - Electrolytic nickel (alloy) plating solution - Google Patents

Abstract

An object of the present invention is to provide an electrolytic nickel (alloy) plating solution, which enables filling without generating defects such as voids and seams when filling a micropore or microscopic groove 14 in an electronic circuit part with nickel or nickel alloy 18, and a method for plating and filling nickel or nickel alloy using the electrolytic nickel (alloy) plating solution, and a method for manufacturing a micro three-dimensional structure. The above object is solved by filling the micropore or microscopic groove 14 with an electrolytic nickel (alloy) plating solution having a specific N-substituted carbonylpyridinium compound.

Description

Electrolytic nickel (alloy) plating solution

The present invention relates to an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution (hereinafter, also referred to as "electrolytic nickel (alloy) plating solution"), and more specifically, An electrolytic nickel (alloy) plating solution for plating a micro hole or a minute recess in an electronic circuit component.

Moreover, the present invention also relates to a plating filling method using minute holes or minute recesses of the electrolytic nickel (alloy) plating solution, and a method of manufacturing a minute three-dimensional structure.

An electronic circuit component typified by a semiconductor or a printed circuit board has minute holes or minute recesses such as vias, through holes, and trenches for forming wiring. When a plurality of circuit boards are stacked in the past to manufacture a multilayer printed circuit board, a staggered via structure is mainly used, and after the wall surface of the through hole is conformal copper plating (following plating), Connect to other layers in a staggered arrangement. However, with the miniaturization and high functionality of electronic devices in recent years, the space saving system due to the stacked via structure in which the through holes are filled by copper plating and directly connected to the other layers to form interlayers is used. Already necessary and indispensable.

The technique of filling by electrolytic copper plating is also suitable for use in semiconductor manufacturing technology, and a technology called damascene process or TSV (Through Silicon Via) is available, and can be plated with electrolytic copper. The through holes are filled to form a three-dimensional wiring structure.

The electrolytic copper plating solution for filling the minute holes or the minute recesses contains a plurality of kinds of additives, and the through holes are filled by controlling the concentration balance of these, but even if it is about several μm The filling of the macrovoid disappears, and there is still a problem of residual microvoids of nm level due to side effects of the additive. Copper is a metal (1083 ° C) whose melting point is not very high. It is known that recrystallization occurs when it is placed at room temperature after electrolytic copper plating. During this recrystallization process, there are problems in that micropores of the order of nm are aggregated to form large pores.

For example, in Non-Patent Document 1, a part of polyethylene glycol (PEG) which is an additive is infiltrated into a copper film, and a micro-hole of a nm grade is generated in the copper film, and is placed in the process of recrystallization of copper. Large pores up to 70 nm in diameter are formed at room temperature.

Therefore, in the copper filling method using the electrolytic copper plating solution, there is such a problem that when the wiring is continuously finer, the void growth or the hole movement accompanying the aggregation of the micropores is caused. The reduction in wiring reliability has been significantly reduced.

Therefore, the inventors speculated that even if micropores caused by plating additives remain, high-melting metals which are not easily recrystallized at room temperature, especially nickel which is generally plated as electronic parts (melting point) : 1455 ° C), to fill tiny holes or tiny recesses, you can get holes is not easy Highly reliable wiring for agglutination.

Attempts have been made to fill the recesses with electrolytic nickel plating.

Non-Patent Document 2 investigates the filling property in a deep groove when various additives are added to an electrolytic nickel plating solution, and the micro-recesses (deep grooves) are filled by adding thiourea.

However, according to the additional test (the example described later) of the present inventors, the filling property of the electrolytic nickel plating solution described in Non-Patent Document 2 is not sufficient, and the occurrence of voids cannot be suppressed, and precipitates are generated. Cracks are not good as structures.

In the related art, the filling of microscopic holes and minute recesses is not sufficient, and it is desired to develop a nickel filling method which does not cause defects such as holes or cracks.

[Previous Technical Literature] [Non-patent literature]

Non-Patent Document 1: Surface Technology Vol. 52, No. 1, pp. 34-38 (2001)

Non-Patent Document 2: Electronics Society Institute Vol. 17, No. 2, pp. 143-148 (2014)

The present invention has been made in view of the above prior art, and an object thereof is to provide an electrolytic nickel (alloy) plating solution which is based on nickel or When the nickel alloy is filled with minute holes or minute recesses in the electronic circuit component, the filler can be filled in such a manner that no defects such as holes or gaps are formed; and nickel or the electrolytic nickel (alloy) plating solution is also provided. Nickel alloy plating filling method and manufacturing method of minute three-dimensional structure.

In order to solve the above problems, the inventors of the present invention have found that by electroplating using an electrolytic nickel (alloy) plating solution containing a specific N-substituted carbonyl pyridinium compound, it is possible to prevent defects such as voids. The present invention has been completed by filling nickel into minute holes or minute recesses.

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 buffering agent, and an N-substituted carbonylpyridinium compound represented by the following formula (A); [In the formula (A), m is 0 or 1; -R ¹ is -R ^1a or -NR ^1b R ^1c (R ^1a is an alkyl group having 1 to 6 carbon atoms; R ^1b is a hydrogen atom or a carbon number of 1 to 6 alkyl; R ^1c is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an amine group (-NH ₂ )); -R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; X ^- is any Anion].

Moreover, the present invention also provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, comprising: a nickel salt, a pH buffering agent, and an N-substituted carbonylpyridinium compound represented by the following formula (B); [In the formula (B), m is 0 or 1; -R ¹ is -R ^1a or -NR ^1b R ^1c (R ^1a is an alkyl group having 1 to 6 carbon atoms; R ^1b is a hydrogen atom or a carbon number of 1 to An alkyl group of 6; R ^1c is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an amine group (-NH ₂ )). -R ³ is -R ^3a -SO ₃ ^- (R ^3a is an alkylene group having 1 to 6 carbon atoms)].

Moreover, the present invention also provides a nickel or nickel alloy plating filling method for applying a seed layer for electrolytic plating to a surface of a minute hole or a minute recess formed in an electronic circuit component, and then the electronic circuit The part is immersed in the above-mentioned electrolytic nickel plating solution or electrolytic nickel alloy plating solution, and electrolytic plating is performed using an external power source.

Moreover, the present invention also provides a method of manufacturing a minute three-dimensional structure, comprising the step of plating a micro hole or a minute recess by a nickel or nickel alloy plating filling method.

According to the invention, by using nickel plating or nickel alloy plating Covering, it can fill tiny holes or tiny recesses in electronic circuit components without creating holes or gaps.

Moreover, in the present invention, it is possible to fill the minute holes or the minute recesses with nickel having a high melting point and which is not easily recrystallized at room temperature. Therefore, even if the wiring is further miniaturized, the problem of agglomeration due to the holes is less likely to occur. It can be widely used for three-dimensional wiring formation or three-dimensional MEMS (Micro Electro Mechanical Systems) parts that continue to progress in miniaturization.

1‧‧‧Printing substrate for evaluation

10‧‧‧The periphery of the plated part

11‧‧‧Substrate

12‧‧‧Stacked resin

13‧‧‧ copper foil

14‧‧‧Blind hole

15‧‧‧ seed layer

16‧‧‧Dry film photoresist

17‧‧‧ solder pads

18‧‧‧Precipitation of nickel

V‧‧‧ hole

Fig. 1 is a schematic view showing a cross section of the periphery of a portion to be plated of the printed circuit board for evaluation used in the examples.

Fig. 2 is a photograph of a wiring pattern of the surface of the printed circuit board for evaluation used in the examples.

Fig. 3 is a photomicrograph of a cross section of a substrate after plating and plating (Example 1).

Fig. 4 is a photomicrograph of a cross section of a substrate after plating and plating (Example 2).

Fig. 5 is a photomicrograph of a cross section of a substrate after plating (Example 3).

Fig. 6 is a photomicrograph of a cross section of a substrate after plating (Example 4).

Fig. 7 is a photomicrograph of a cross section of a substrate after plating (Comparative Example 1).

Fig. 8 is a photomicrograph of a cross section of a substrate after plating (Comparative Example 2).

Fig. 9 is a photomicrograph of a cross section of a substrate after plating (Comparative Example 3).

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

<Electrolyzed Nickel (Alloy) Plating Solution>

The electrolytic nickel (alloy) plating solution of the present invention (hereinafter also referred to simply as "the plating liquid of the present invention") contains a nickel salt, a pH buffer, and the following formula (A) or An N-substituted carbonylpyridinium compound represented by the general formula (B); [In the formula (A), m is 0 or 1. -R ¹ is -R ^1a or -NR ^1b R ^1c (R ^1a is an alkyl group having 1 to 6 carbon atoms; R ^1b is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ^1c is a hydrogen atom, carbon number 1 An alkyl group of 6 or an amine group (-NH ₂ )). -R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X ^- is an arbitrary anion]

[In the formula (B), m is 0 or 1. -R ¹ is -R ^1a or -NR ^1b R ^1c (R ^1a is an alkyl group having 1 to 6 carbon atoms; R ^1b is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ^1c is a hydrogen atom, carbon number 1 An alkyl group of 6 or an amine group (-NH ₂ )). -R ³ is -R ^3a -SO ₃ ^- (R ^3a is an alkylene group having 1 to 6 carbon atoms)].

The nickel salt contained in the plating solution of the present invention may be considered from the viewpoints of water solubility and filling properties, and examples thereof include nickel sulfate, nickel sulfonate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, and the like. Nickel acetate, nickel citrate, nickel fluoroborate or the like, but is not limited thereto.

These may be used alone or in combination of two or more.

The total content of the above 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.

Within the above range, the precipitation rate of nickel can be made sufficient, and fine holes or minute pits can be filled without generating voids.

The pH buffer contained in the plating solution of the present invention may, for example, be boric acid, metaboric acid, acetic acid, tartaric acid, citric acid or the like, but is not limited thereto.

These may be used alone or in combination of two or more.

The 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.

When it is in the above range, it is difficult to hinder the N-substituted carbonylpyridinium compound represented by the above formula (A) or (B) (hereinafter, also referred to as "specific N-substituted carbonylpyridinium compound") The effect of the present invention can be maintained.

The plating solution of the present invention contains a specific N-substituted carbonyl pyridinium compound.

By the action of a specific N-substituted carbonylpyridinium compound, the plating solution of the present invention can fill minute holes or minute pits without generating voids.

When R ^1a , R ^1b , R ^1c and R ² of the above formula (A) and the above formula (B) are an alkyl group having 1 to 6 carbon atoms, the R ^1a , R ^1b , R ^1c and R ^{2 are} Any one may preferably be an alkyl group having a carbon number of 1 to 4, more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably an alkyl group having 1 or 2 carbon atoms.

Further, when R ^3a of the above formula (B) is an alkylene group having 1 to 6 carbon atoms, it is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. Particularly preferred is an alkylene group having 1 or 2 carbon atoms.

In the above formula (A), specific examples of -R ¹ include, for example, -CH ₃ , -CH ₂ CH ₃ , -NH ₂ , -N(CH ₃ ) ₂ , -N(C ₂ H ₅ ) ₂ , -NHNH ₂ and so on.

Specific examples of -R ² include -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ and the like.

Specific examples of X ^- may, for example, be halide ions (chloride ions, bromide ions, iodide ions).

Specific examples of the specific N-substituted carbonylpyridinium compound represented by the above formula (A) include 1-aminopyridinium pyridinium, 1-(aminomethylmethylmethyl)pyridinium, and 1-(dimethyl group). Aminomethylpyridinium pyridinium, 1-(diethylamine-mercapto)pyridinium, 1-(decylcarbonylmethyl)pyridinium, and 1-acetonepyridinium halide (chloride, bromide) , iodide) and so on.

In the above formula (B), a specific example of -R ¹ may, for example, be the same as in the case of the formula (A).

Specific examples of -R ³ include -C ₂ H ₄ -SO ₃ ^- , -C ₃ H ₆ -SO ₃ ^-, and the like.

Specific examples of the specific N-substituted carbonylpyridinium compound represented by the above formula (B) include, for example, 1-(aminomercaptomethyl)-4-(2-sulfoethyl)pyridinium hydroxide. Inner salt, 1-(aminomercaptomethyl)-4-(2-sulfonylpropyl)pyridinium chloride intramolecular salt, 1-(aminomercapto)-4-(2-sulfonate) Intramolecular salt of acid ethyl)pyridinium, intramolecular salt of 1-(aminomercapto)-4-(2-sulfopropyl)pyridinium hydroxide, 1-(dimethylamineformamidine hydroxide) Intramolecular salt of 4-(2-sulfonic acid ethyl)pyridinium, intramolecular salt of 1-(dimethylaminocarbamimido)-4-(2-sulfopropyl)pyridinium hydroxide Wait.

The specific N-substituted carbonyl pyridinium compound may be used singly or in combination of two or more.

Further, the total content of the specific N-substituted carbonylpyridinium 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.

In the above range, the amount of nickel deposition outside the minute holes or the minute recesses can be increased, and the minute holes or minute recesses can be filled without generating holes.

The plating solution of the present invention contains a nickel salt, a pH buffering agent, 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, during storage, it is possible to store only an optional component of the above-mentioned essential components in an aqueous solution of water, and when used, it is possible to prepare a plating of the present invention containing all necessary components by adding other components. liquid.

When the plating liquid of the present invention is an electrolytic nickel alloy plating solution, examples of the metal ion for the alloy with nickel include tungsten, molybdenum, cobalt, iron, zinc, tin, copper, palladium, gold, and the like. A well-known compound can be used for such a metal source.

Further, in the nickel or nickel alloy film, carbon, sulfur, nitrogen, phosphorus, boron, chlorine, bromine or the like which is not a metal may be contained.

In the plating liquid of the present invention, an anti-cavity agent, a primary brightener, a secondary brightener, a surfactant, or the like may be added as needed within a range not inhibiting the effects of the present invention.

The plating solution of the present invention is suitable for filling tiny holes or minute recesses formed in electronic circuit components. As shown in the examples to be described later, when the minute holes or the minute recesses are filled with the plating solution of the present invention, the amount of precipitation inside the minute holes or the minute recesses becomes more than the amount of precipitation outside the minute holes or the minute recesses. Nickel (or nickel alloy) can be sufficiently buried in tiny holes or tiny recesses. Further, holes (holes) or slits (grooves) are less likely to be generated inside the minute holes or the minute recesses.

Therefore, due to the high melting point of nickel, the plating solution of the present invention can be expected. Electronic circuit parts that fill tiny holes or tiny recesses are highly reliable.

<Nickel (alloy) plating filling method, manufacturing method of minute three-dimensional structure>

In the nickel or nickel alloy plating filling method of the present invention, the seed layer for electrolytic plating is applied to the surface of the minute hole or the minute recess formed in the electronic circuit component, and the electronic circuit component is immersed in the foregoing. Electrolytic plating is performed using an external power source in the electrolytic nickel (alloy) plating solution.

Moreover, the method for producing a minute three-dimensional structure according to the present invention includes the step of plating and filling a minute hole or a minute recess by the nickel or nickel alloy plating and filling method.

The term "microscopic holes or minute recesses" refers to minute recesses such as through holes, through holes, and deep grooves formed in electronic circuit components such as semiconductors and printed boards, and is formed by electrolytic plating or the like by filling metal. The shape of the wiring portion is not limited as long as it is viewed from above. In addition, the "micro-holes" may be through or not.

In the practice of the present invention, minute holes or minute recesses must be formed on 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 which is often used as an electronic circuit component, and BT (Bismaleimide-triazine, Bismaleimide-Triazine). Resin materials, polypropylene materials, polyamidene materials, ceramic materials, coffins, metal materials, glass materials, and the like.

The method of forming minute holes or minute recesses in the substrate to be plated is not limited, and a well-known method can be suitably used. Thunder In the method of laser processing or ion etching, the micro recesses can be formed with an opening of 100 μm or less and an aspect ratio of 0.5 or more.

Then, a pattern can be formed on the surface of the substrate to be plated by a photoresist or the like as needed.

When the substrate to be plated on which the minute recesses are formed is an insulating base material, a seed layer for electrolytic plating is formed on the inner surface of the base material and the inner surface of the minute recess. The method for forming the seed layer is not particularly limited, and specific examples thereof include metal deposition by electroplating or electroless plating.

The metal constituting the seed layer is not particularly limited, and examples thereof include copper, nickel, and palladium.

After the seed layer for electrolytic plating is formed, 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 micropores or minute recesses are formed. Filled with nickel or nickel alloy.

Further, when the substrate to be plated which has been once dried after the formation of the seed layer is plated, it is subjected to degreasing and acid washing in accordance with a general method, and then plating may be carried out using the plating solution of the present invention.

According to the method of "plating filling of minute holes or minute recesses by the nickel or nickel alloy plating filling method of the present invention", it is possible to manufacture minute three-dimensional circuit wiring filled with minute holes or minute recesses by nickel or nickel alloy. Or tiny three-dimensional structures.

The plating temperature is preferably 30 ° C or higher, and particularly preferably 40 ° C or higher. Further, it is preferably 70 ° C or lower, and particularly preferably 60 ° C or lower.

If it is within the above range, the filling of tiny holes or tiny recesses is excellent. Different, it is also advantageous in terms of cost.

The current density at the time of plating is preferably 0.1 A/dm ² or more, and particularly preferably 1 A/dm ² or more. Further, it is preferably 10 A/dm ² or less, and particularly preferably 5 A/dm ² or less.

In the above range, the filling property of the minute holes or the minute recesses is excellent, and it is also advantageous in terms of cost.

Further, the current density may be kept constant or not fixed in the plating filling (for example, the initial current density is low, and the current density is gradually increased; pulse current, etc.).

The current density is preferably kept constant during plating filling (or most of the time during plating filling), since it can be easily filled without causing holes.

The plating time is preferably 5 minutes or more, and more preferably 10 minutes or more. Further, it is preferably 360 minutes or less, and preferably 60 minutes or less.

In the above range, the filling property of the minute holes or the minute recesses is excellent, and it is also advantageous in terms of cost.

[Examples]

In the following, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the examples and comparative examples as long as the scope of the invention is not exceeded.

Examples 1 to 4 and Comparative Examples 1 to 3

For the model of the tiny recess, the system uses an aspect ratio of 0.88 ( Printed substrate (manufactured by Nippon CIRCUIT Co., Ltd.) for evaluation of a 12 mm square of a laser hole of 45 μm × 40 μm D).

The cross section of the periphery 10 of the plated portion is shown in Fig. 1. BT (Bismaleimide-triazine, double-maleimide-three) with a thickness of 0.4 mm a through-hole forming portion of the substrate 11 to be bonded to a copper foil 13 having a thickness of 12 μm, on which a prepreg type build-up resin 12 having a thickness of 60 μm is laminated thereon Laser production Blind via hole of 45 μm and depth of 40 μm (hereinafter, also referred to as "via hole" or "via") 14 on the outer surface of the substrate (stacked resin 12) The inner surface of the through hole 14 and the inner wall surface of the through hole 14 are plated with electroless copper to form a seed layer 15 of about 1 μm.

Further, a wiring pattern shown in FIG. 2 is formed by a dry film resist (DFR) 16 to form a pad (opening) 17 having a through hole 14 ( The opening was 190 μm), and this was used as the printed circuit board 1 for evaluation.

In Fig. 2, the white portion is a copper plated portion, and the black portion is a dry film photoresist portion. Among the white portions, the largest circular portion connected by the wiring corresponds to the circular pad 17 of FIG. 1 ( 190 μm). A through hole 14 belonging to the micro recessed portion shown in Fig. 1 is formed on the entire circular pad 17.

<Modulation of Electrolytic Nickel Plating Solution>

The electrolytic nickel plating solution was prepared by dissolving in a deionized water so that nickel sulfonate is 600 g/L, nickel chloride is 10 g/L, and boric acid is 30 g/L.

For the above-mentioned electrolytic nickel plating solution, add the table in the amount shown in Table 1. The additive shown in 1 is dissolved.

Next, an appropriate amount of an aqueous solution of 100 g/L of an amine sulfonic acid was added to adjust the pH to 3.6 to prepare an electrolytic nickel plating solution of the invention.

<filling through holes by electrolytic nickel plating>

The printed circuit board 1 for evaluation described above was subjected to electrolytic nickel plating in the procedure shown in Table 2. To an electroless nickel plating step, an external power supply and a current density of 1.0A / dm ^2.

Further, 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.

<plating filling evaluation test>

The plated substrate was embedded in a resin for polishing, and then subjected to cross-section polishing to observe the filling of the through holes with a metal microscope.

In the state of the filling property, when the amount of precipitation inside the through hole is larger than the amount of precipitation outside the through hole, when the hole (hole) or the slit (ditch) is not observed inside the through hole, it is "○", and in other cases, "X".

Further, it was observed whether cracks (cracks) were formed outside the through holes.

When the filling property was "○" and no crack occurred, the evaluation was "good", and the other cases were evaluated as "poor".

A micrograph of the cross section of the substrate after plating is shown in Figs. 3 to 9. Further, the evaluation results are shown in Table 3.

In the first to fourth embodiments, as for the amount of the deposited nickel 18, the number of through holes belonging to the minute recesses is larger than the outside of the through holes, and the holes or the gaps can be well filled. Further, no crack was observed on the outside of the through hole.

In Comparative Example 1, conformal plating (following plating) in which the amount of nickel 18 was deposited to the same extent inside and outside the through hole was poor, and the filling property was poor.

In Comparative Example 2, there was a hole V inside the through hole, and the filling property was poor.

In Comparative Example 3, there was no pore in the inside of the through hole, and the filling property was good, but the precipitated portion was very weak and cracked, and the nickel 18 deposited on the upper portion of the through hole after the polishing showed significant peeling. Therefore, it is not preferable as a minute three-dimensional structure.

As shown in the results of Examples 1 to 4 and Comparative Examples 1 to 3, By electrolytic plating with an electrolytic nickel plating solution containing an N-substituted carbonylpyridinium compound represented by the general formula (A) or the general formula (B), it is possible to satisfactorily fill the minute pores formed in the electronic component with nickel. It can make tiny three-dimensional structures.

[Industrial availability]

The electrolytic nickel (alloy) plating solution containing a specific N-substituted carbonyl pyridinium compound of the present invention can fill minute holes or minute recesses in electronic circuit components with high reliability, and can be widely applied in consideration of further miniaturization of wiring. Formed in three-dimensional wiring or three-dimensional MEMS parts.

Claims (10)

An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, comprising: a nickel salt, a pH buffering agent, and an N-substituted carbonyl pyridinium compound represented by the following formula (A); In the formula (A), m is 0 or 1; -R ¹ is -R ^1a or -NR ^1b R ^1c , R ^1a is an alkyl group having 1 to 6 carbon atoms, and R ^1b is a hydrogen atom or a carbon number of 1 to 6 The alkyl group, R ^1c is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an amine group (-NH ₂ ); -R ² is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; and X ^- is an anion. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to claim 1, wherein X ^- is a halide ion. An electrolytic nickel plating solution or an electrolytic nickel alloy plating solution, comprising: a nickel salt, a pH buffering agent, and an N-substituted carbonyl pyridinium compound represented by the following formula (B); In the formula (B), m is 0 or 1; -R ¹ is -R ^1a or -NR ^1b R ^1c , R ^1a is an alkyl group having 1 to 6 carbon atoms, and R ^1b is a hydrogen atom or a carbon number of 1 to 6 An alkyl group, R ^1c is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an amine group (-NH ₂ ); -R ³ is -R ^3a -SO ₃ ^- , and R ^3a is a carbon number of 1 to 6 alkyl. 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 selected from the group consisting of nickel sulfate, nickel amine sulfonate, nickel chloride, and bromine. One or more of the group consisting of nickel, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, nickel citrate, and nickel fluoroborate. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 4, wherein the pH buffering agent is selected from the group consisting of boric acid, metaboric acid, acetic acid, tartaric acid, and citric acid. And one or more of the group consisting of such salts. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 2, 4 or 5, wherein the N-substituted carbonyl pyridinium compound represented by the formula (A) is selected from the group consisting of Halide of 1-aminopyridinium pyridinium, halide of 1-(aminomethylmethylmethyl)pyridinium, halide of 1-(dimethylammonium)pyridinium, 1-(diethyl A compound of one or more of the group consisting of a halide of an amidomethyl pyridinium, a halide of 1-(fluorenylcarbonylmethyl)pyridinium, and a halide of 1-acetonylpyridinium. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 3 to 5, wherein the N-substituted carbonyl pyridinium compound represented by the formula (B) is selected from the group consisting of hydrogen peroxide. 1-(Aminomethylmethyl)-4-(2-sulfoethyl)pyridinium intramolecular salt, 1-(aminomethylmethylmethyl)-4-(2-sulfonate) Pyridinium intramolecular salt, hydroxide 1-(Aminomethyl)-4-(2-sulfoethyl)pyridinium intramolecular salt, 1-(aminomercapto)-4-(2-sulfopropyl)pyridinium hydroxide Intramolecular salt, intramolecular salt of 1-(dimethylaminocarbamimido)-4-(2-sulfoethyl)pyridinium hydroxide and 1-(dimethylaminocarbamimidyl)-4 hydroxide One or more compounds of the group consisting of -(2-sulfonylpropyl)pyridinium intramolecular salt. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 7 is a filling for a minute hole or a minute recess formed in an electronic circuit component. A nickel or nickel alloy plating filling method is a method in which a seed layer for electrolytic plating is applied to a surface of a micro hole or a minute recess formed in an electronic circuit component, and the electronic circuit component is immersed in the patent application scope. The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of items 1 to 8 is electrolytically plated using an external power source. A method for manufacturing a microscopic three-dimensional structure, comprising: a step of plating a micro hole or a micro recess by a nickel or nickel alloy plating filling method according to claim 9 of the patent application.