WO2017199835A1 - Electrolytic nickel (alloy) plating solution - Google Patents
Electrolytic nickel (alloy) plating solution Download PDFInfo
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- WO2017199835A1 WO2017199835A1 PCT/JP2017/017832 JP2017017832W WO2017199835A1 WO 2017199835 A1 WO2017199835 A1 WO 2017199835A1 JP 2017017832 W JP2017017832 W JP 2017017832W WO 2017199835 A1 WO2017199835 A1 WO 2017199835A1
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- Prior art keywords
- nickel
- plating solution
- electrolytic
- electrolytic nickel
- plating
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- 0 CC*[N+](C(C)C)[O-] Chemical compound CC*[N+](C(C)C)[O-] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
Definitions
- the present invention relates to an electrolytic nickel plating solution and an electrolytic nickel alloy plating solution (hereinafter, these may be collectively referred to as “electrolytic nickel (alloy) plating solution”).
- the present invention relates to an electrolytic nickel (alloy) plating solution suitable for filling a minute recess.
- the present invention also relates to a method for plating and filling minute holes and minute recesses using such electrolytic nickel (alloy) plating solution, and a method for producing a minute three-dimensional structure.
- Electronic circuit components typified by semiconductors and printed circuit boards have minute holes and minute recesses such as vias, through holes, and trenches for wiring formation.
- minute holes and minute recesses such as vias, through holes, and trenches for wiring formation.
- a staggered via structure in which via walls are conformally copper-plated (follow-up plating) and then connected to other layers in a staggered arrangement has been the mainstream.
- TSV through silicon via
- Electrolytic copper plating solution for filling micropores and microrecesses contains multiple additives and fills vias by optimally controlling their concentration balance, but there are no macrovoids of several ⁇ m. Even if it could be filled, there was a problem that micro-voids 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 left at room temperature after electrolytic copper plating. As a result of the aggregation of nano-order microvoids in this recrystallization process, there is a problem that macrovoids are formed.
- Non-Patent Document 1 polyethylene glycol (PEG), which is an additive, is partly incorporated into a copper film, resulting in nano-order microvoids in the copper film. The formation of large voids reaching a diameter of 70 nm is described.
- PEG polyethylene glycol
- the copper filling method using an electrolytic copper plating solution potentially has such problems, and when the wiring is further miniaturized, void growth and void movement accompanying microvoid aggregation occur. As a result, a decrease in wiring reliability may become apparent.
- Non-Patent Document 2 the filling properties in the trenches when various additives are added to the electrolytic nickel plating solution are examined, and the addition of thiourea fills the fine recesses (trench).
- the filling property with the electrolytic nickel plating solution described in Non-Patent Document 2 is still insufficient, and generation of voids cannot be suppressed. It was found that the structure was defective as a crack.
- the present invention has been made in view of the above-mentioned background art, and its problem is that, when a minute hole or minute recess in an electronic circuit component is filled with nickel or a nickel alloy, a defect such as a void or a seam is not generated.
- an electrolytic nickel (alloy) plating solution that can be filled, and to provide a nickel or nickel alloy plating filling method using such an electrolytic nickel (alloy) plating solution and a method of manufacturing a micro three-dimensional structure. It is to provide.
- the present inventor conducted electroplating using an electrolytic nickel plating solution containing a specific N-substituted carbonylpyridinium compound, so that the inside of micropores or microrecesses was obtained.
- the present inventors have found that nickel can be filled without generating defects such as voids, and the present invention has been completed.
- the present invention provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution comprising a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (A): To do.
- 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )).
- —R 2 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
- X ⁇ is any anion.
- the present invention also provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution comprising a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (B): To do.
- 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )).
- R 3 is —R 3a —SO 3 — (R 3a is an alkylene group having 1 to 6 carbon atoms).
- the present invention provides an electrolytic plating seed layer or an electrolytic nickel alloy plating solution after applying a seed layer for electrolytic plating in advance to the surface of a minute hole or minute recess formed in the electronic circuit component. And a nickel or nickel alloy plating filling method, characterized in that the plating is performed using an external power source.
- the present invention also provides a method for producing a micro three-dimensional structure, comprising the step of plating and filling micropores or microrecesses by the nickel or nickel alloy plating filling method described above.
- the present invention by using nickel plating or nickel alloy plating, it is possible to fill the minute holes or minute recesses in the electronic circuit component without generating defects such as voids and seams.
- the melting point is low and room temperature recrystallization is difficult to be filled with nickel, microholes and microcavities can be filled, so even if the wiring is further miniaturized, defects associated with the aggregation of voids are unlikely to occur. It can be widely applied to 3D wiring formation, 3D MEMS (Micro Electro Mechanical Systems) parts, etc. that are progressing.
- 3D MEMS Micro Electro Mechanical Systems
- the electrolytic nickel (alloy) plating solution of the present invention (hereinafter sometimes simply referred to as “the plating solution of the present invention”) is a nickel salt, a pH buffer, the following general formula (A) or the following general formula.
- An N-substituted carbonylpyridinium compound represented by (B) is contained.
- 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )).
- —R 2 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
- X ⁇ is any anion.
- 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )).
- R 3 is —R 3a —SO 3 — (R 3a is an alkylene group having 1 to 6 carbon atoms).
- nickel salt to be contained in the plating solution of the present invention from the viewpoint of water solubility and filling properties, nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, citric acid Although nickel, nickel borofluoride, etc. are mentioned, it is not limited to these. These may be used alone or in combination of two or more.
- the total content of the nickel salt 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 nickel deposition rate can be made sufficient, and the micropores and microrecesses can be filled without generating voids.
- pH buffering agent examples include, but are not limited to, boric acid, metaboric acid, acetic acid, tartaric acid, citric acid, and salts thereof. These may be used alone or in combination of two or more.
- the total content of the pH buffering agent is preferably 1 g / L or more and 100 g / L or less, particularly preferably 5 g / L or more and 50 g / L or less.
- the action of the N-substituted carbonylpyridinium compound represented by the general formula (A) or the general formula (B) (hereinafter sometimes referred to as “specific N-substituted carbonylpyridinium compound”) is inhibited. It is hard to maintain the effect of the present invention.
- the plating solution of the present invention contains a specific N-substituted carbonylpyridinium compound. Due to the action of the specific N-substituted carbonylpyridinium compound, the plating solution of the present invention can fill micropores and microrecesses without generating voids.
- R 1a , R 1b , R 1c and R 2 in the general formula (A) and the general formula (B) are each an alkyl group having 1 to 6 carbon atoms
- the R 1a , R 1b , R 1c , R 2 is preferably an alkyl group having 1 to 4 carbon atoms which may be different, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms.
- R 3a in the general formula (B) is an alkylene group having 1 to 6 carbon atoms
- an alkylene group having 1 to 4 carbon atoms is preferable
- an alkylene group having 1 to 3 carbon atoms is more preferable
- Particularly preferred are 1 or 2 alkylene groups.
- —R 1 examples include —CH 3 , —CH 2 CH 3 , —NH 2 , —N (CH 3 ) 2 , —N (C 2 H 5 ) 2 , — NHNH 2, and the like.
- —R 2 examples include —H, —CH 3 , —C 2 H 5 , —C 3 H 7 and the like.
- X ⁇ include halide ions (chloride ions, bromide ions, iodide ions) and the like.
- Specific examples of the specific N-substituted carbonylpyridinium compound represented by the general formula (A) include 1-carbamoylpyridinium, 1- (carbamoylmethyl) pyridinium, 1- (dimethylcarbamoyl) pyridinium, 1- (diethylcarbamoyl) pyridinium. 1- (hydrazinocarbonylmethyl) pyridinium, and 1-acetonylpyridinium halides (chloride, bromide, iodide), and the like.
- —R 1 examples include the same as those in the general formula (A).
- —R 3 examples 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 general formula (B) include 1- (carbamoylmethyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (carbamoylmethyl)- 4- (2-sulfopropyl) pyridinium hydroxide inner salt, 1- (carbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (carbamoyl) -4- (2-sulfopropyl) pyridinium Hydroxide inner salt, 1- (dimethylcarbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (dimethylcarbamoyl) -4- (2-sulfopropyl) pyridinium hydroxide inner salt, etc. Can be mentioned.
- the specific N-substituted carbonylpyridinium compound may be used alone 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, 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 microholes and microrecesses can be filled without generating voids.
- the plating solution of the present invention contains a nickel salt, a pH buffer, and a specific N-substituted carbonylpyridinium compound as essential components.
- the above essential components may be added to water in any order.
- the plating solution of the invention may be prepared.
- the plating solution of the present invention is an electrolytic nickel alloy plating solution
- metal ions for alloying with nickel include tungsten, molybdenum, cobalt, iron, zinc, tin, copper, palladium, and gold.
- known compounds can be used.
- the nickel or nickel alloy film may contain carbon, sulfur, nitrogen, phosphorus, boron, chlorine, bromine or the like.
- a pit inhibitor, a primary brightener, a secondary brightener, a surfactant, and the like can be added as necessary within a range that does not impair the effects of the present invention.
- the plating solution of the present invention is suitable for use in filling minute holes or minute recesses formed in an electronic circuit component.
- the amount of precipitation inside the micropores or microrecesses is larger than the amount of precipitation outside the micropores or microrecesses.
- nickel or a nickel alloy
- voids (holes) and seams (grooves) are less likely to be generated inside the minute holes and the minute recesses. For this reason, in combination with the high melting point of nickel, it is expected that an electronic circuit component filled with micropores or microrecesses with the plating solution of the present invention has high reliability.
- an electroplating seed layer is applied in advance to the surface of a minute hole or minute recess formed in an electronic circuit component, and then the electronic component is immersed in the electrolytic nickel (alloy) plating solution, It is also a nickel or nickel alloy plating filling method characterized in that electrolytic plating is performed using.
- the present invention is also a method for manufacturing a micro three-dimensional structure characterized by including a step of plating and filling micropores or microrecesses by such nickel or nickel alloy plating filling method.
- Microholes or microrecesses are microscopic recesses such as vias, through-holes, and trenches formed in electronic circuit components such as semiconductors and printed boards, and are filled with metal by electrolytic plating or the like. Therefore, the portion functioning as the wiring portion is referred to, and the shape seen from above is not limited. In addition, “micropores” may or may not penetrate.
- the substrate to be plated there are no particular restrictions on the substrate to be plated. Specifically, glass epoxy materials, BT (Bismaleimide-Triazine) resin materials, polypropylene materials, polyimide materials, ceramic materials, silicon materials, metal materials, glass, which are frequently used as electronic circuit components. Materials and the like.
- a well-known method can be used suitably.
- a method by laser processing or ion etching can be used, and minute recesses can be formed with a depth of 100 ⁇ m or less and an aspect ratio of 0.5 or more.
- a pattern is formed on the surface of the substrate to be plated with a photoresist or the like.
- the seed layer for electrolytic plating is formed in the base material surface and the inner surface of a micro recessed part.
- the metal deposition by sputtering, an electroless-plating method, etc. are mentioned.
- a metal which comprises a seed layer Copper, nickel, palladium etc. can be illustrated.
- 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. Fill with nickel or nickel alloy.
- electroplating may be performed using the plating solution of the present invention after degreasing and acid cleaning according to a conventional method.
- a structure can be manufactured.
- the plating temperature is preferably 30 ° C. or higher, and particularly preferably 40 ° C. or higher. Moreover, 70 degrees C or less is preferable and 60 degrees C or less is especially preferable. Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
- the current density during plating is preferably 0.1 A / dm 2 or more, particularly preferably 1 A / dm 2 or more. Moreover, 10 A / dm 2 or less is preferable and 5 A / dm 2 or less is particularly preferable. Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
- the current density may or may not always 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 for most of the time during plating filling) because filling is easy without generating voids.
- the plating time is preferably 5 minutes or longer, particularly preferably 10 minutes or longer. Moreover, 360 minutes or less are preferable and 60 minutes or less are especially preferable. Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
- Examples 1 to 4 and Comparative Examples 1 to 3 A 12 mm square printed circuit board for evaluation (manufactured by Nippon Circuit Co., Ltd.) having a laser via with an aspect ratio of 0.88 ( ⁇ 45 ⁇ m ⁇ 40 ⁇ mD) was used as a model of the minute recess.
- FIG. 10 A cross-sectional view around the portion to be plated 10 is shown in FIG.
- a prepreg type buildup resin 12 having a thickness of 60 ⁇ m is laminated
- a blind via hole (hereinafter sometimes simply referred to as “via hole” or “via”) 14 having a diameter of 45 ⁇ m and a depth of 40 ⁇ m is created by a laser, and the substrate outer surface (the surface of the buildup resin 12) and the inside of the via 14
- About 1 ⁇ m of seed layer 15 was formed on the wall surface by electroless copper plating.
- the evaluation printed circuit board 1 was formed by forming the wiring pattern shown in FIG. 2 with a dry film resist (DFR) 16 and opening a pad (opening) 17 ( ⁇ 190 ⁇ m) having a via 14.
- DFR dry film resist
- the white part is the copper plating part and the black part is the dry film resist part.
- the largest circular portion to which the wiring is connected corresponds to the circular pad 17 ( ⁇ 190 ⁇ m) in FIG.
- a via hole 14 that is a minute recess shown in FIG. 1 is formed in all of the circular pads 17.
- An electrolytic nickel plating solution was prepared by dissolving in deionized water so that nickel sulfamate was 600 g / L, nickel chloride was 10 g / L, and boric acid was 30 g / L.
- the additives shown in Table 1 were added to the electrolytic nickel plating solution so as to have the addition amount shown in Table 1 and dissolved.
- an appropriate amount of 100 g / L sulfamic acid aqueous solution was added to adjust the pH to 3.6 to prepare the electrolytic nickel plating solution of the present invention.
- Electrolytic nickel plating was performed on the evaluation printed circuit board 1 in the steps shown in Table 2.
- the electroless nickel plating step was made to be a current density of 1.0A / dm 2 using an external power source.
- the plating area was calculated not as a surface area including the side surface of the via 14 but as an area of only the plane of the opening (pad) 17.
- ⁇ Plating fillability evaluation test> The substrate after plating was buried and fixed in a polishing resin, and the cross-section was polished. The via filling state was observed with a metal microscope.
- filling properties “ ⁇ ” indicates that no voids (holes) or seams (grooves) are observed inside the via hole when the amount of precipitation inside the via hole is greater than the amount deposited outside the via hole, and “ ⁇ ” otherwise. It was. In addition, the occurrence of cracks (cracks) outside the via hole was observed. The case where the filling property was “ ⁇ ” and no crack was generated was evaluated as “good”, and the other cases were evaluated as “bad”.
- the amount of precipitated nickel 18 was greater in via holes that are minute recesses than outside the via holes, and was well filled without voids or seams. Further, no cracks were observed outside the via hole.
- Comparative Example 1 was conformal plating (follow-up plating) in which the amount of deposited nickel 18 was the same inside and outside the via hole, and the filling property was poor.
- Comparative Example 3 there was no void inside the via and the filling property was good, but the deposited part was very brittle and cracks occurred, and after the polishing, the deposited nickel 18 was remarkably peeled at the upper part of the via. . Therefore, it was a poor micro three-dimensional structure.
- the electrolytic nickel (alloy) plating solution containing the specific N-substituted carbonylpyridinium compound of the present invention can reliably fill minute holes or minute recesses in electronic circuit components, and can cope with further miniaturization of wiring. Therefore, it can be widely applied to 3D wiring formation, 3D MEMS parts, and the like.
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Abstract
The present invention addresses the problem of providing: an electrolytic nickel (alloy) plating solution which is able to fill micro holes or micro recesses 14 within an electronic circuit component with nickel or nickel alloy 18 without the generation of defects such as voids and seams; a nickel or nickel alloy plating/filling method which uses this electrolytic nickel (alloy) plating solution; and a method for producing a three-dimensional microstructure. The above-described problem has been solved by filling the micro holes or micro recesses 14 with use of an electrolytic nickel (alloy) plating solution which contains a specific N-substituted carbonyl pyridinium compound.
Description
本発明は、電解ニッケルめっき液や電解ニッケル合金めっき液（以下、これらを総称して「電解ニッケル（合金）めっき液」という場合がある。）に関し、更に詳しくは、電子部品内の微小孔や微小凹部のめっき充填用に適した電解ニッケル（合金）めっき液に関する。
また、本発明は、かかる電解ニッケル（合金）めっき液を使用した微小孔や微小凹部のめっき充填方法や、微小三次元構造体の製造方法に関する。 The present invention relates to an electrolytic nickel plating solution and an electrolytic nickel alloy plating solution (hereinafter, these may be collectively referred to as “electrolytic nickel (alloy) plating solution”). The present invention relates to an electrolytic nickel (alloy) plating solution suitable for filling a minute recess.
The present invention also relates to a method for plating and filling minute holes and minute recesses using such electrolytic nickel (alloy) plating solution, and a method for producing a minute three-dimensional structure.
また、本発明は、かかる電解ニッケル（合金）めっき液を使用した微小孔や微小凹部のめっき充填方法や、微小三次元構造体の製造方法に関する。 The present invention relates to an electrolytic nickel plating solution and an electrolytic nickel alloy plating solution (hereinafter, these may be collectively referred to as “electrolytic nickel (alloy) plating solution”). The present invention relates to an electrolytic nickel (alloy) plating solution suitable for filling a minute recess.
The present invention also relates to a method for plating and filling minute holes and minute recesses using such electrolytic nickel (alloy) plating solution, and a method for producing a minute three-dimensional structure.
半導体やプリント基板に代表される電子回路部品は、配線形成のためのビア、スルーホール、トレンチ等の微小孔や微小凹部を有している。従来複数の回路基板を積層させた多層プリント基板の製造においては、ビアの壁面をコンフォーマル銅めっき（追従めっき）した後に、食い違い配列で他層と接続させるスタガードビア構造が主流であった。しかし、近年の電子機器の小型化、高機能化に伴い、ビアを銅めっきで充填し、そのまま他層を重ねて層間接続させるスタックビア構造による省スペース化が必要不可欠なものとなっている。
Electronic circuit components typified by semiconductors and printed circuit boards have minute holes and minute recesses such as vias, through holes, and trenches for wiring formation. Conventionally, in the manufacture of multilayer printed circuit boards in which a plurality of circuit boards are laminated, a staggered via structure in which via walls are conformally copper-plated (follow-up plating) and then connected to other layers in a staggered arrangement has been the mainstream. However, with recent downsizing and higher functionality of electronic devices, it is indispensable to save space with a stacked via structure in which vias are filled with copper plating, and other layers are stacked as they are and connected to each other.
電解銅めっきによる充填技術は半導体製造技術にも適用され、ダマシンプロセスやシリコン貫通電極（ＴＳＶ：Ｔｈｒｏｕｇｈ Ｓｉｌｉｃｏｎ Ｖｉａ）と呼ばれる技術が登場し、ビアを電解銅めっきで充填させて三次元的に配線構造を形成することが可能となってきている。
Filling technology by electrolytic copper plating is also applied to semiconductor manufacturing technology, and a technology called damascene process or through silicon via (TSV) has appeared, and vias are filled with electrolytic copper plating to provide a three-dimensional wiring structure. Can be formed.
微小孔や微小凹部の充填用の電解銅めっき液は、複数の添加剤を含有させ、それらの濃度バランスを最適にコントロールすることでビアを充填しているが、数μｍ程度のマクロボイドがなく充填できたとしても、添加剤の副作用としてｎｍオーダーのマイクロボイドが残留するという問題があった。銅は融点がそれほど高くない金属であり（１０８３℃）、電解銅めっき後の室温放置においても再結晶が起こることは良く知られている。この再結晶過程においてｎｍオーダーのマイクロボイドが凝集した結果、マクロなボイドを形成してしまうという問題があった。
例えば、非特許文献１には、添加剤であるポリエチレングリコール（ＰＥＧ）が銅皮膜中に一部取り込まれ、銅皮膜中にｎｍオーダーのマイクロボイドが生じ、銅の再結晶過程において、室温放置により、直径７０ｎｍに達する大きなボイドを形成することが記載されている。 Electrolytic copper plating solution for filling micropores and microrecesses contains multiple additives and fills vias by optimally controlling their concentration balance, but there are no macrovoids of several μm. Even if it could be filled, there was a problem that micro-voids 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 left at room temperature after electrolytic copper plating. As a result of the aggregation of nano-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 partly incorporated into a copper film, resulting in nano-order microvoids in the copper film. The formation of large voids reaching a diameter of 70 nm is described.
例えば、非特許文献１には、添加剤であるポリエチレングリコール（ＰＥＧ）が銅皮膜中に一部取り込まれ、銅皮膜中にｎｍオーダーのマイクロボイドが生じ、銅の再結晶過程において、室温放置により、直径７０ｎｍに達する大きなボイドを形成することが記載されている。 Electrolytic copper plating solution for filling micropores and microrecesses contains multiple additives and fills vias by optimally controlling their concentration balance, but there are no macrovoids of several μm. Even if it could be filled, there was a problem that micro-voids 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 left at room temperature after electrolytic copper plating. As a result of the aggregation of nano-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 partly incorporated into a copper film, resulting in nano-order microvoids in the copper film. The formation of large voids reaching a diameter of 70 nm is described.
従って、電解銅めっき液を使用した銅充填方法ではこのような課題を潜在的に抱えていることになり、配線の更なる微細化が進んだ際にはマイクロボイド凝集に伴うボイド成長やボイド移動により、配線信頼性の低下が顕在化するおそれがある。
Therefore, the copper filling method using an electrolytic copper plating solution potentially has such problems, and when the wiring is further miniaturized, void growth and void movement accompanying microvoid aggregation occur. As a result, a decrease in wiring reliability may become apparent.
そこで、めっき添加剤起因のマイクロボイドが残留したとしても、室温再結晶が起こりにくい高融点金属、特に電子部品の下地めっきとして一般的なニッケル（融点：１４５５℃）で微小孔や微小凹部を充填することができれば、ボイドの凝集が起きず信頼性の高い配線になり得ると本発明者は推測した。
Therefore, even if microvoids due to plating additives remain, filling micropores and microrecesses with refractory metals that are unlikely to recrystallize at room temperature, especially nickel (melting point: 1455 ° C), which is commonly used as the base plating for electronic components If this can be done, the present inventor speculated that void aggregation does not occur and a highly reliable wiring can be obtained.
電解ニッケルめっきで凹部を充填する試みも検討はされている。
非特許文献２では、電解ニッケルめっき液に、様々な添加剤を加えた場合のトレンチ内の充填性を検討し、チオ尿素を添加することで微小凹部（トレンチ）が充填されるとしている。
しかしながら、本発明者らの追試（後述の実施例）によると、非特許文献２に記載の電解ニッケルめっき液での充填性は未だ不十分でありボイドの発生を抑制できず、また、析出物にクラックが入り、構造体として不良であることが判明した。 Attempts have also been made to fill recesses with electrolytic nickel plating.
In Non-Patent Document 2, the filling properties in the trenches when various additives are added to the electrolytic nickel plating solution are examined, and the addition of thiourea fills the fine recesses (trench).
However, according to the follow-up test by the present inventors (examples to be described later), the filling property with the electrolytic nickel plating solution described in Non-Patent Document 2 is still insufficient, and generation of voids cannot be suppressed. It was found that the structure was defective as a crack.
非特許文献２では、電解ニッケルめっき液に、様々な添加剤を加えた場合のトレンチ内の充填性を検討し、チオ尿素を添加することで微小凹部（トレンチ）が充填されるとしている。
しかしながら、本発明者らの追試（後述の実施例）によると、非特許文献２に記載の電解ニッケルめっき液での充填性は未だ不十分でありボイドの発生を抑制できず、また、析出物にクラックが入り、構造体として不良であることが判明した。 Attempts have also been made to fill recesses with electrolytic nickel plating.
In Non-Patent Document 2, the filling properties in the trenches when various additives are added to the electrolytic nickel plating solution are examined, and the addition of thiourea fills the fine recesses (trench).
However, according to the follow-up test by the present inventors (examples to be described later), the filling property with the electrolytic nickel plating solution described in Non-Patent Document 2 is still insufficient, and generation of voids cannot be suppressed. It was found that the structure was defective as a crack.
電子回路の微細化は、益々進行しており、かかる公知技術では、微小孔・微小凹部の充填性が不十分であり、ボイド等の欠陥やクラック等が発生しないニッケル充填方法の開発が望まれていた。
The miniaturization of electronic circuits is progressing more and more, and with such known techniques, the filling of micropores and microrecesses is insufficient, and it is desired to develop a nickel filling method that does not cause defects such as voids or cracks. It was.
本発明は上記背景技術に鑑みてなされたものであり、その課題は、電子回路部品内の微小孔や微小凹部をニッケル又はニッケル合金で充填するに際し、ボイドやシーム等の欠陥を発生させることなく充填することのできる電解ニッケル（合金）めっき液を提供することにあり、また、かかる電解ニッケル（合金）めっき液を用いたニッケル又はニッケル合金めっき充填方法や、微小三次元構造体の製造方法を提供することにある。
The present invention has been made in view of the above-mentioned background art, and its problem is that, when a minute hole or minute recess in an electronic circuit component is filled with nickel or a nickel alloy, a defect such as a void or a seam is not generated. To provide an electrolytic nickel (alloy) plating solution that can be filled, and to provide a nickel or nickel alloy plating filling method using such an electrolytic nickel (alloy) plating solution and a method of manufacturing a micro three-dimensional structure. It is to provide.
本発明者は、上記の課題を解決すべく鋭意検討を重ねた結果、特定のＮ置換カルボニルピリジニウム化合物を含有させた電解ニッケルめっき液を使用して電気めっきすることによって、微小孔や微小凹部内に、ボイド等の欠陥を発生させることなくニッケルを充填することができることを見出し、本発明を完成するに至った。
As a result of intensive studies to solve the above problems, the present inventor conducted electroplating using an electrolytic nickel plating solution containing a specific N-substituted carbonylpyridinium compound, so that the inside of micropores or microrecesses was obtained. In addition, the present inventors have found that nickel can be filled without generating defects such as voids, and the present invention has been completed.
すなわち、本発明は、ニッケル塩と、ｐＨ緩衝剤と、下記一般式（Ａ）で表されるＮ置換カルボニルピリジニウム化合物を含有することを特徴とする電解ニッケルめっき液又は電解ニッケル合金めっき液を提供するものである。
That is, the present invention provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution comprising a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (A): To do.
［一般式（Ａ）において、ｍは０又は１である。－Ｒ１は－Ｒ１ａ又は－ＮＲ１ｂＲ１ｃである（Ｒ１ａは炭素数１～６のアルキル基；Ｒ１ｂは水素原子又は炭素数１～６のアルキル基；Ｒ１ｃは水素原子、炭素数１～６のアルキル基、又はアミノ基（－ＮＨ２））。－Ｒ２は水素原子又は炭素数１～６の炭化水素基である。Ｘ－は任意の陰イオンである。］
[In General 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )). —R 2 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X − is any anion. ]
また、本発明は、ニッケル塩と、ｐＨ緩衝剤と、下記一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物を含有することを特徴とする電解ニッケルめっき液又は電解ニッケル合金めっき液を提供するものである。
The present invention also provides an electrolytic nickel plating solution or an electrolytic nickel alloy plating solution comprising a nickel salt, a pH buffer, and an N-substituted carbonylpyridinium compound represented by the following general formula (B): To do.
［一般式（Ｂ）において、ｍは０又は１である。－Ｒ１は－Ｒ１ａ又は－ＮＲ１ｂＲ１ｃである（Ｒ１ａは炭素数１～６のアルキル基；Ｒ１ｂは水素原子又は炭素数１～６のアルキル基；Ｒ１ｃは水素原子、炭素数１～６のアルキル基、又はアミノ基（－ＮＨ２））。－Ｒ３は－Ｒ３ａ－ＳＯ３
－（Ｒ３ａは炭素数１～６のアルキレン基）である。］
[In General 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )). —R 3 is —R 3a —SO 3 — (R 3a is an alkylene group having 1 to 6 carbon atoms). ]
また、本発明は、電子回路部品内に形成された微小孔又は微小凹部の表面に予め電解めっき用シード層を施した後、該電子回路部品を上記の電解ニッケルめっき液又は電解ニッケル合金めっき液に浸漬し、外部電源を使用して電解めっきをすることを特徴とするニッケル又はニッケル合金めっき充填方法を提供するものである。
Further, the present invention provides an electrolytic plating seed layer or an electrolytic nickel alloy plating solution after applying a seed layer for electrolytic plating in advance to the surface of a minute hole or minute recess formed in the electronic circuit component. And a nickel or nickel alloy plating filling method, characterized in that the plating is performed using an external power source.
また、本発明は、上記のニッケル又はニッケル合金めっき充填方法により微小孔又は微小凹部にめっき充填する工程を含むことを特徴とする微小三次元構造体の製造方法を提供するものである。
The present invention also provides a method for producing a micro three-dimensional structure, comprising the step of plating and filling micropores or microrecesses by the nickel or nickel alloy plating filling method described above.
本発明によれば、ニッケルめっき又はニッケル合金めっきを使用することにより、電子回路部品内の微小孔又は微小凹部を、ボイドやシーム等の欠陥を発生させることなく充填することができる。
According to the present invention, by using nickel plating or nickel alloy plating, it is possible to fill the minute holes or minute recesses in the electronic circuit component without generating defects such as voids and seams.
また、本発明では、融点が高く、室温再結晶が起こりにくいニッケルで微小孔や微小凹部を充填できるので、配線の更なる微細化が進んでも、ボイドの凝集に伴う不具合が起こりにくく、微細化が進んでいる三次元配線形成や三次元ＭＥＭＳ（Micro Electro Mechanical Systems）部品等に広く応用することができる。
In addition, in the present invention, since the melting point is low and room temperature recrystallization is difficult to be filled with nickel, microholes and microcavities can be filled, so even if the wiring is further miniaturized, defects associated with the aggregation of voids are unlikely to occur. It can be widely applied to 3D wiring formation, 3D MEMS (Micro Electro Mechanical Systems) parts, etc. that are progressing.
以下、本発明について説明するが、本発明は以下の実施の形態に限定されるものではなく、任意に変形して実施することができる。
Hereinafter, the present invention will be described, but the present invention is not limited to the following embodiments, and can be implemented with arbitrary modifications.
＜電解ニッケル（合金）めっき液＞
本発明の電解ニッケル（合金）めっき液（以下、単に「本発明のめっき液」と略記する場合がある。）は、ニッケル塩と、ｐＨ緩衝剤と、下記一般式（Ａ）又は下記一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物を含有する。 <Electrolytic nickel (alloy) plating solution>
The electrolytic nickel (alloy) plating solution of the present invention (hereinafter sometimes simply referred to as “the plating solution of the present invention”) is a nickel salt, a pH buffer, the following general formula (A) or the following general formula. An N-substituted carbonylpyridinium compound represented by (B) is contained.
本発明の電解ニッケル（合金）めっき液（以下、単に「本発明のめっき液」と略記する場合がある。）は、ニッケル塩と、ｐＨ緩衝剤と、下記一般式（Ａ）又は下記一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物を含有する。 <Electrolytic nickel (alloy) plating solution>
The electrolytic nickel (alloy) plating solution of the present invention (hereinafter sometimes simply referred to as “the plating solution of the present invention”) is a nickel salt, a pH buffer, the following general formula (A) or the following general formula. An N-substituted carbonylpyridinium compound represented by (B) is contained.
［一般式（Ａ）において、ｍは０又は１である。－Ｒ１は－Ｒ１ａ又は－ＮＲ１ｂＲ１ｃである（Ｒ１ａは炭素数１～６のアルキル基；Ｒ１ｂは水素原子又は炭素数１～６のアルキル基；Ｒ１ｃは水素原子、炭素数１～６のアルキル基、又はアミノ基（－ＮＨ２））。－Ｒ２は水素原子又は炭素数１～６の炭化水素基である。Ｘ－は任意の陰イオンである。］
[In General 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )). —R 2 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X − is any anion. ]
［一般式（Ｂ）において、ｍは０又は１である。－Ｒ１は－Ｒ１ａ又は－ＮＲ１ｂＲ１ｃである（Ｒ１ａは炭素数１～６のアルキル基；Ｒ１ｂは水素原子又は炭素数１～６のアルキル基；Ｒ１ｃは水素原子、炭素数１～６のアルキル基、又はアミノ基（－ＮＨ２））。－Ｒ３は－Ｒ３ａ－ＳＯ３
－（Ｒ３ａは炭素数１～６のアルキレン基）である。］
[In General 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 An alkyl group of the number 1 to 6 or an amino group (—NH 2 )). —R 3 is —R 3a —SO 3 — (R 3a is an alkylene group having 1 to 6 carbon atoms). ]
本発明のめっき液に含有させるニッケル塩としては、水溶性や充填性の観点から、硫酸ニッケル、スルファミン酸ニッケル、塩化ニッケル、臭化ニッケル、炭酸ニッケル、硝酸ニッケル、ギ酸ニッケル、酢酸ニッケル、クエン酸ニッケル、ホウフッ化ニッケル等が挙げられるが、これらに限定されるものではない。
これらは、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 As the nickel salt to be contained in the plating solution of the present invention, from the viewpoint of water solubility and filling properties, nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, citric acid Although nickel, nickel borofluoride, etc. are mentioned, it is not limited to these.
These may be used alone or in combination of two or more.
これらは、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 As the nickel salt to be contained in the plating solution of the present invention, from the viewpoint of water solubility and filling properties, nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, citric acid Although nickel, nickel borofluoride, etc. are mentioned, it is not limited to these.
These may be used alone or in combination of two or more.
上記ニッケル塩の合計含有量は、ニッケルイオンとして、１０ｇ／Ｌ以上１８０ｇ／Ｌ以下が好ましく、５０ｇ／Ｌ以上１３０ｇ／Ｌ以下が特に好ましい。
上記範囲内であると、ニッケルの析出速度を十分にすることができ、また、ボイドを発生することなく微小孔や微小凹部を充填することができる。 The total content of the nickel salt 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 nickel deposition rate can be made sufficient, and the micropores and microrecesses can be filled without generating voids.
上記範囲内であると、ニッケルの析出速度を十分にすることができ、また、ボイドを発生することなく微小孔や微小凹部を充填することができる。 The total content of the nickel salt 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 nickel deposition rate can be made sufficient, and the micropores and microrecesses can be filled without generating voids.
本発明のめっき液に含有させるｐＨ緩衝剤としては、ホウ酸、メタホウ酸、酢酸、酒石酸、クエン酸や、それらの塩等が挙げられるが、これらに限定されるものではない。
これらは、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 Examples of the pH buffering agent to be 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 alone or in combination of two or more.
これらは、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 Examples of the pH buffering agent to be 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 alone or in combination of two or more.
ｐＨ緩衝剤の合計含有量は、１ｇ／Ｌ以上１００ｇ／Ｌ以下が好ましく、５ｇ／Ｌ以上５０ｇ／Ｌ以下が特に好ましい。
上記範囲内であると、上記一般式（Ａ）又は一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物（以下、「特定Ｎ置換カルボニルピリジニウム化合物」という場合がある。）の作用を阻害しにくく、本発明の効果が保たれる。 The total content of the pH buffering agent is preferably 1 g / L or more and 100 g / L or less, particularly preferably 5 g / L or more and 50 g / L or less.
Within the above range, the action of the N-substituted carbonylpyridinium compound represented by the general formula (A) or the general formula (B) (hereinafter sometimes referred to as “specific N-substituted carbonylpyridinium compound”) is inhibited. It is hard to maintain the effect of the present invention.
上記範囲内であると、上記一般式（Ａ）又は一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物（以下、「特定Ｎ置換カルボニルピリジニウム化合物」という場合がある。）の作用を阻害しにくく、本発明の効果が保たれる。 The total content of the pH buffering agent is preferably 1 g / L or more and 100 g / L or less, particularly preferably 5 g / L or more and 50 g / L or less.
Within the above range, the action of the N-substituted carbonylpyridinium compound represented by the general formula (A) or the general formula (B) (hereinafter sometimes referred to as “specific N-substituted carbonylpyridinium compound”) is inhibited. It is hard to maintain the effect of the present invention.
本発明のめっき液は、特定Ｎ置換カルボニルピリジニウム化合物を含有する。
特定Ｎ置換カルボニルピリジニウム化合物の作用により、本発明のめっき液は、微小孔や微小凹部をボイドの発生なく充填することができる。 The plating solution of the present invention contains a specific N-substituted carbonylpyridinium compound.
Due to the action of the specific N-substituted carbonylpyridinium compound, the plating solution of the present invention can fill micropores and microrecesses without generating voids.
特定Ｎ置換カルボニルピリジニウム化合物の作用により、本発明のめっき液は、微小孔や微小凹部をボイドの発生なく充填することができる。 The plating solution of the present invention contains a specific N-substituted carbonylpyridinium compound.
Due to the action of the specific N-substituted carbonylpyridinium compound, the plating solution of the present invention can fill micropores and microrecesses without generating voids.
上記一般式（Ａ）及び上記一般式（Ｂ）のＲ１ａ、Ｒ１ｂ、Ｒ１ｃ、Ｒ２が、炭素数１～６のアルキル基である場合は、該Ｒ１ａ、Ｒ１ｂ、Ｒ１ｃ、Ｒ２は何れも、異なっていてもよい炭素数１～４のアルキル基が好ましく、炭素数１～３のアルキル基がより好ましく、炭素数１又は２のアルキル基が特に好ましい。
また、上記一般式（Ｂ）のＲ３ａが炭素数１～６のアルキレン基である場合は、炭素数１～４のアルキレン基が好ましく、炭素数１～３のアルキレン基がより好ましく、炭素数１又は２のアルキレン基が特に好ましい。 When R 1a , R 1b , R 1c and R 2 in the general formula (A) and the general formula (B) are each an alkyl group having 1 to 6 carbon atoms, the R 1a , R 1b , R 1c , R 2 is preferably an alkyl group having 1 to 4 carbon atoms which may be different, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms.
Further, when R 3a in the general formula (B) is an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 4 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and Particularly preferred are 1 or 2 alkylene groups.
また、上記一般式（Ｂ）のＲ３ａが炭素数１～６のアルキレン基である場合は、炭素数１～４のアルキレン基が好ましく、炭素数１～３のアルキレン基がより好ましく、炭素数１又は２のアルキレン基が特に好ましい。 When R 1a , R 1b , R 1c and R 2 in the general formula (A) and the general formula (B) are each an alkyl group having 1 to 6 carbon atoms, the R 1a , R 1b , R 1c , R 2 is preferably an alkyl group having 1 to 4 carbon atoms which may be different, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms.
Further, when R 3a in the general formula (B) is an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 4 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and Particularly preferred are 1 or 2 alkylene groups.
上記一般式（Ａ）において、－Ｒ１の具体例としては、－ＣＨ３、－ＣＨ２ＣＨ３、－ＮＨ２、－Ｎ（ＣＨ３）２、－Ｎ（Ｃ２Ｈ５）２、－ＮＨＮＨ２等が挙げられる。
－Ｒ２の具体例としては、－Ｈ、－ＣＨ３、－Ｃ２Ｈ５、－Ｃ３Ｈ７等が挙げられる。
Ｘ－の具体例としては、ハロゲン化物イオン（塩化物イオン、臭化物イオン、ヨウ化物イオン）等が挙げられる。 In the general formula (A), specific examples of —R 1 include —CH 3 , —CH 2 CH 3 , —NH 2 , —N (CH 3 ) 2 , —N (C 2 H 5 ) 2 , — NHNH 2, and the like.
Specific examples of —R 2 include —H, —CH 3 , —C 2 H 5 , —C 3 H 7 and the like.
Specific examples of X − include halide ions (chloride ions, bromide ions, iodide ions) and the like.
－Ｒ２の具体例としては、－Ｈ、－ＣＨ３、－Ｃ２Ｈ５、－Ｃ３Ｈ７等が挙げられる。
Ｘ－の具体例としては、ハロゲン化物イオン（塩化物イオン、臭化物イオン、ヨウ化物イオン）等が挙げられる。 In the general formula (A), specific examples of —R 1 include —CH 3 , —CH 2 CH 3 , —NH 2 , —N (CH 3 ) 2 , —N (C 2 H 5 ) 2 , — NHNH 2, and the like.
Specific examples of —R 2 include —H, —CH 3 , —C 2 H 5 , —C 3 H 7 and the like.
Specific examples of X − include halide ions (chloride ions, bromide ions, iodide ions) and the like.
上記一般式（Ａ）で表される特定Ｎ置換カルボニルピリジニウム化合物の具体例としては、１－カルバモイルピリジニウム、１－（カルバモイルメチル）ピリジニウム、１－（ジメチルカルバモイル）ピリジニウム、１－（ジエチルカルバモイル）ピリジニウム、１－（ヒドラジノカルボニルメチル）ピリジニウム、及び、１－アセトニルピリジニウムのハロゲン化物（塩化物、臭化物、ヨウ化物）等が挙げられる。
Specific examples of the specific N-substituted carbonylpyridinium compound represented by the general formula (A) include 1-carbamoylpyridinium, 1- (carbamoylmethyl) pyridinium, 1- (dimethylcarbamoyl) pyridinium, 1- (diethylcarbamoyl) pyridinium. 1- (hydrazinocarbonylmethyl) pyridinium, and 1-acetonylpyridinium halides (chloride, bromide, iodide), and the like.
上記一般式（Ｂ）において、－Ｒ１の具体例としては、一般式（Ａ）の場合と同様のものが挙げられる。
－Ｒ３の具体例としては、－Ｃ２Ｈ４－ＳＯ３ －、－Ｃ３Ｈ６－ＳＯ３ －等が挙げられる。 In the general formula (B), specific examples of —R 1 include the same as those in the general formula (A).
Specific examples of —R 3 include —C 2 H 4 —SO 3 — , —C 3 H 6 —SO 3 —, and the like.
－Ｒ３の具体例としては、－Ｃ２Ｈ４－ＳＯ３ －、－Ｃ３Ｈ６－ＳＯ３ －等が挙げられる。 In the general formula (B), specific examples of —R 1 include the same as those in the general formula (A).
Specific examples of —R 3 include —C 2 H 4 —SO 3 — , —C 3 H 6 —SO 3 —, and the like.
上記一般式（Ｂ）で表される特定Ｎ置換カルボニルピリジニウム化合物の具体例としては、１－（カルバモイルメチル）－４－（２－スルホエチル）ピリジニウムヒドロキシド分子内塩、１－（カルバモイルメチル）－４－（２－スルホプロピル）ピリジニウムヒドロキシド分子内塩、１－（カルバモイル）－４－（２－スルホエチル）ピリジニウムヒドロキシド分子内塩、１－（カルバモイル）－４－（２－スルホプロピル）ピリジニウムヒドロキシド分子内塩、１－（ジメチルカルバモイル）－４－（２－スルホエチル）ピリジニウムヒドロキシド分子内塩、１－（ジメチルカルバモイル）－４－（２－スルホプロピル）ピリジニウムヒドロキシド分子内塩等が挙げられる。
Specific examples of the specific N-substituted carbonylpyridinium compound represented by the general formula (B) include 1- (carbamoylmethyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (carbamoylmethyl)- 4- (2-sulfopropyl) pyridinium hydroxide inner salt, 1- (carbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (carbamoyl) -4- (2-sulfopropyl) pyridinium Hydroxide inner salt, 1- (dimethylcarbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (dimethylcarbamoyl) -4- (2-sulfopropyl) pyridinium hydroxide inner salt, etc. Can be mentioned.
特定Ｎ置換カルボニルピリジニウム化合物は、１種単独で用いてもよいし、２種以上を混合して用いてもよい。
また、本発明のめっき液における特定Ｎ置換カルボニルピリジニウム化合物の合計含有量は、０．０１ｇ／Ｌ以上１００ｇ／Ｌ以下が好ましく、０．１ｇ／Ｌ以上１０ｇ／Ｌ以下が特に好ましい。
上記範囲内であると、微小孔や微小凹部の外部のニッケル析出量を多くすることができ、微小孔や微小凹部にボイドを発生させることなく充填することができる。 The specific N-substituted carbonylpyridinium compound may be used alone 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, 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 microholes and microrecesses can be filled without generating voids.
また、本発明のめっき液における特定Ｎ置換カルボニルピリジニウム化合物の合計含有量は、０．０１ｇ／Ｌ以上１００ｇ／Ｌ以下が好ましく、０．１ｇ／Ｌ以上１０ｇ／Ｌ以下が特に好ましい。
上記範囲内であると、微小孔や微小凹部の外部のニッケル析出量を多くすることができ、微小孔や微小凹部にボイドを発生させることなく充填することができる。 The specific N-substituted carbonylpyridinium compound may be used alone 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, 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 microholes and microrecesses can be filled without generating voids.
本発明のめっき液は、ニッケル塩と、ｐＨ緩衝剤と、特定Ｎ置換カルボニルピリジニウム化合物を必須成分として含有する。
本発明のめっき液を調製する際には、上記必須成分をどのような順序で水に添加してもよい。また、保管の際には、上記必須成分のうち、任意の成分のみを水に溶解した水溶液の状態で保管し、使用時に、他の成分を添加することにより、全ての必須成分を含有する本発明のめっき液を調製してもよい。 The plating solution of the present invention contains a nickel salt, a pH buffer, and a specific N-substituted carbonylpyridinium compound as essential components.
When preparing the plating solution of the present invention, the above essential components may be added to water in any order. In addition, when storing, store in the form of an aqueous solution in which only any of the above essential components is dissolved in water, and add other components at the time of use to contain all the essential components. The plating solution of the invention may be prepared.
本発明のめっき液を調製する際には、上記必須成分をどのような順序で水に添加してもよい。また、保管の際には、上記必須成分のうち、任意の成分のみを水に溶解した水溶液の状態で保管し、使用時に、他の成分を添加することにより、全ての必須成分を含有する本発明のめっき液を調製してもよい。 The plating solution of the present invention contains a nickel salt, a pH buffer, and a specific N-substituted carbonylpyridinium compound as essential components.
When preparing the plating solution of the present invention, the above essential components may be added to water in any order. In addition, when storing, store in the form of an aqueous solution in which only any of the above essential components is dissolved in water, and add other components at the time of use to contain all the essential components. The plating solution of the invention may be prepared.
本発明のめっき液が、電解ニッケル合金めっき液である場合、ニッケルとの合金用の金属イオンについては、例えば、タングステン、モリブデン、コバルト、鉄、亜鉛、錫、銅、パラジウム、金等が挙げられる。これらの金属源としては、公知の化合物を使用できる。
また、金属ではないものの、ニッケル又はニッケル合金皮膜に、炭素、硫黄、窒素、リン、ホウ素、塩素、臭素等を含有してもよい。 When the plating solution of the present invention is an electrolytic nickel alloy plating solution, examples of metal ions for alloying with nickel include tungsten, molybdenum, cobalt, iron, zinc, tin, copper, palladium, and gold. . As these metal sources, known compounds can be used.
Further, although not a metal, the nickel or nickel alloy film may contain carbon, sulfur, nitrogen, phosphorus, boron, chlorine, bromine or the like.
また、金属ではないものの、ニッケル又はニッケル合金皮膜に、炭素、硫黄、窒素、リン、ホウ素、塩素、臭素等を含有してもよい。 When the plating solution of the present invention is an electrolytic nickel alloy plating solution, examples of metal ions for alloying with nickel include tungsten, molybdenum, cobalt, iron, zinc, tin, copper, palladium, and gold. . As these metal sources, known compounds can be used.
Further, although not a metal, the nickel or nickel alloy film may contain carbon, sulfur, nitrogen, phosphorus, boron, chlorine, bromine or the like.
本発明のめっき液には、本発明の効果を阻害しない範囲内で、ピット防止剤、１次光沢剤、２次光沢剤、界面活性剤等を必要に応じて添加することができる。
In the plating solution of the present invention, a pit inhibitor, a primary brightener, a secondary brightener, a surfactant, and the like can be added as necessary within a range that does not impair the effects of the present invention.
本発明のめっき液は、電子回路部品内に形成された微小孔又は微小凹部の充填用として使用するのに適している。後述の実施例のように、本発明のめっき液により、微小孔や微小凹部を充填した場合、微小孔や微小凹部の内部の析出量が、微小孔や微小凹部の外部の析出量よりも多くなり、微小孔や微小凹部にニッケル（又はニッケル合金）を十分に埋め込むことができる。また、微小孔や微小凹部の内部にボイド（穴）やシーム（溝）が発生しにくい。
このため、ニッケルの融点の高さも相俟って、本発明のめっき液により微小孔や微小凹部を充填した電子回路部品は、高い信頼性を持つことが期待される。 The plating solution of the present invention is suitable for use in filling minute holes or minute recesses formed in an electronic circuit component. When the micropores or microrecesses are filled with the plating solution of the present invention as described later, the amount of precipitation inside the micropores or microrecesses is larger than the amount of precipitation outside the micropores or microrecesses. Thus, nickel (or a nickel alloy) can be sufficiently embedded in the minute holes and the minute recesses. In addition, voids (holes) and seams (grooves) are less likely to be generated inside the minute holes and the minute recesses.
For this reason, in combination with the high melting point of nickel, it is expected that an electronic circuit component filled with micropores or microrecesses with the plating solution of the present invention has high reliability.
このため、ニッケルの融点の高さも相俟って、本発明のめっき液により微小孔や微小凹部を充填した電子回路部品は、高い信頼性を持つことが期待される。 The plating solution of the present invention is suitable for use in filling minute holes or minute recesses formed in an electronic circuit component. When the micropores or microrecesses are filled with the plating solution of the present invention as described later, the amount of precipitation inside the micropores or microrecesses is larger than the amount of precipitation outside the micropores or microrecesses. Thus, nickel (or a nickel alloy) can be sufficiently embedded in the minute holes and the minute recesses. In addition, voids (holes) and seams (grooves) are less likely to be generated inside the minute holes and the minute recesses.
For this reason, in combination with the high melting point of nickel, it is expected that an electronic circuit component filled with micropores or microrecesses with the plating solution of the present invention has high reliability.
＜ニッケル（合金）めっき充填方法・微小三次元構造体の製造方法＞
本発明は、電子回路部品内に形成された微小孔又は微小凹部の表面に予め電解めっき用シード層を施した後、該電子部品を前記の電解ニッケル（合金）めっき液に浸漬し、外部電源を使用して電解めっきをすることを特徴とするニッケル又はニッケル合金めっき充填方法でもある。
また、本発明は、かかるニッケル又はニッケル合金めっき充填方法により微小孔又は微小凹部にめっき充填する工程を含むことを特徴とする微小三次元構造体の製造方法でもある。 <Nickel (alloy) plating filling method and manufacturing method of micro three-dimensional structure>
According to the present invention, an electroplating seed layer is applied in advance to the surface of a minute hole or minute recess formed in an electronic circuit component, and then the electronic component is immersed in the electrolytic nickel (alloy) plating solution, It is also a nickel or nickel alloy plating filling method characterized in that electrolytic plating is performed using.
The present invention is also a method for manufacturing a micro three-dimensional structure characterized by including a step of plating and filling micropores or microrecesses by such nickel or nickel alloy plating filling method.
本発明は、電子回路部品内に形成された微小孔又は微小凹部の表面に予め電解めっき用シード層を施した後、該電子部品を前記の電解ニッケル（合金）めっき液に浸漬し、外部電源を使用して電解めっきをすることを特徴とするニッケル又はニッケル合金めっき充填方法でもある。
また、本発明は、かかるニッケル又はニッケル合金めっき充填方法により微小孔又は微小凹部にめっき充填する工程を含むことを特徴とする微小三次元構造体の製造方法でもある。 <Nickel (alloy) plating filling method and manufacturing method of micro three-dimensional structure>
According to the present invention, an electroplating seed layer is applied in advance to the surface of a minute hole or minute recess formed in an electronic circuit component, and then the electronic component is immersed in the electrolytic nickel (alloy) plating solution, It is also a nickel or nickel alloy plating filling method characterized in that electrolytic plating is performed using.
The present invention is also a method for manufacturing a micro three-dimensional structure characterized by including a step of plating and filling micropores or microrecesses by such nickel or nickel alloy plating filling method.
「微小孔又は微小凹部」とは、半導体やプリント基板等の電子回路部品内に形成されたビア、スルーホール、トレンチ等の微小な窪んだ部分であり、電解めっき等により、金属を充填されることにより、配線部として機能する部分をいい、上から見た形状は限定されない。また、「微小孔」に関しては、貫通していてもいなくてもよい。
“Microholes or microrecesses” are microscopic recesses such as vias, through-holes, and trenches formed in electronic circuit components such as semiconductors and printed boards, and are filled with metal by electrolytic plating or the like. Therefore, the portion functioning as the wiring portion is referred to, and the shape seen from above is not limited. In addition, “micropores” may or may not penetrate.
本発明を実施するには、電子回路部品内の被めっき基板上に、微小孔や微小凹部を形成することが必要である。
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.
被めっき基材に特に制限はなく、具体的には電子回路部品として多用されるガラスエポキシ材、ＢＴ（Bismaleimide-Triazine）レジン材、ポリプロピレン材、ポリイミド材、セラミック材、シリコン材、金属材、ガラス材等が挙げられる。
There are no particular restrictions on the substrate to be plated. Specifically, glass epoxy materials, BT (Bismaleimide-Triazine) resin materials, polypropylene materials, polyimide materials, ceramic materials, silicon materials, metal materials, glass, which are frequently used as electronic circuit components. Materials and the like.
被めっき基材に微小孔や微小凹部を形成する方法に制限はなく、公知の方法が適宜使用できる。例えば、レーザー加工やイオンエッチングによる方法が挙げられ、開口部が１００μｍ以下、アスペクト比が０．５以上の深さで微小凹部を形成させることができる。
その後必要に応じてフォトレジスト等で被めっき基材表面にパターンを形成させる。 There is no restriction | limiting in the method of forming a micropore or a micro recessed part in a to-be-plated base material, A well-known method can be used suitably. For example, a method by laser processing or ion etching can be used, and minute recesses can be formed with a depth of 100 μm or less and an aspect ratio of 0.5 or more.
Thereafter, if necessary, a pattern is formed on the surface of the substrate to be plated with a photoresist or the like.
その後必要に応じてフォトレジスト等で被めっき基材表面にパターンを形成させる。 There is no restriction | limiting in the method of forming a micropore or a micro recessed part in a to-be-plated base material, A well-known method can be used suitably. For example, a method by laser processing or ion etching can be used, and minute recesses can be formed with a depth of 100 μm or less and an aspect ratio of 0.5 or more.
Thereafter, if necessary, a pattern is formed on the surface of the substrate to be plated with a photoresist or the like.
微小凹部を形成した被めっき基材が絶縁基材の場合には、基材表面と微小凹部の内表面に電解めっき用シード層を形成させる。シード層の形成方法に制限はないが、具体的にはスパッタリングによる金属堆積や無電解めっき法等が挙げられる。
シード層を構成する金属としては特に制限はなく、銅、ニッケル、パラジウム等が例示できる。 When the to-be-plated base material which formed the micro recessed part is an insulating base material, the seed layer for electrolytic plating is formed in the base material surface and the inner surface of a micro recessed part. Although there is no restriction | limiting in the formation method of a seed layer, Specifically, the metal deposition by sputtering, an electroless-plating method, etc. are mentioned.
There is no restriction | limiting in particular as a metal which comprises a seed layer, Copper, nickel, palladium etc. can be illustrated.
シード層を構成する金属としては特に制限はなく、銅、ニッケル、パラジウム等が例示できる。 When the to-be-plated base material which formed the micro recessed part is an insulating base material, the seed layer for electrolytic plating is formed in the base material surface and the inner surface of a micro recessed part. Although there is no restriction | limiting in the formation method of a seed layer, Specifically, the metal deposition by sputtering, an electroless-plating method, etc. are mentioned.
There is no restriction | limiting in particular as a metal which comprises a seed layer, Copper, nickel, palladium etc. can be illustrated.
電解めっき用シード層を形成した後に、本発明の電解ニッケル（合金）めっき液に被めっき基材を浸漬し、外部電源を用いて電解ニッケル（合金）めっきを実施し、微小孔や微小凹部に、ニッケル又はニッケル合金を充填する。
なお、シード層形成後に一度乾燥した被めっき基材にめっきする場合は、常法に従って脱脂、酸洗浄を行った後に、本発明のめっき液を用いて電気めっきすればよい。 After forming the seed layer for electrolytic plating, the substrate to be plated is immersed in the electrolytic nickel (alloy) plating solution of the present invention, and electrolytic nickel (alloy) plating is performed using an external power source. Fill with nickel or nickel alloy.
In addition, when plating on the substrate to be plated once after forming the seed layer, electroplating may be performed using the plating solution of the present invention after degreasing and acid cleaning according to a conventional method.
なお、シード層形成後に一度乾燥した被めっき基材にめっきする場合は、常法に従って脱脂、酸洗浄を行った後に、本発明のめっき液を用いて電気めっきすればよい。 After forming the seed layer for electrolytic plating, the substrate to be plated is immersed in the electrolytic nickel (alloy) plating solution of the present invention, and electrolytic nickel (alloy) plating is performed using an external power source. Fill with nickel or nickel alloy.
In addition, when plating on the substrate to be plated once after forming the seed layer, electroplating may be performed using the plating solution of the present invention after degreasing and acid cleaning according to a conventional method.
本発明のニッケル又はニッケル合金めっき充填方法により、微小孔又は微小凹部にめっき充填する工程を含む方法により、微小孔や微小凹部がニッケル又はニッケル合金で充填された微小三次元回路配線又は微小三次元構造体を製造することができる。
According to the nickel or nickel alloy plating filling method of the present invention, a micro three-dimensional circuit wiring or micro three dimensional in which micro holes or micro concave portions are filled with nickel or nickel alloy by a method including a step of plating and filling micro holes or micro concave portions. A structure can be manufactured.
めっき温度は、３０℃以上が好ましく、４０℃以上が特に好ましい。また、７０℃以下が好ましく、６０℃以下が特に好ましい。
上記範囲内であると、微小孔や微小凹部の充填性に優れ、コスト的にも有利である。 The plating temperature is preferably 30 ° C. or higher, and particularly preferably 40 ° C. or higher. Moreover, 70 degrees C or less is preferable and 60 degrees C or less is especially preferable.
Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
上記範囲内であると、微小孔や微小凹部の充填性に優れ、コスト的にも有利である。 The plating temperature is preferably 30 ° C. or higher, and particularly preferably 40 ° C. or higher. Moreover, 70 degrees C or less is preferable and 60 degrees C or less is especially preferable.
Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
めっきの際の電流密度は、０．１Ａ／ｄｍ２以上が好ましく、１Ａ／ｄｍ２以上が特に好ましい。また、１０Ａ／ｄｍ２以下が好ましく、５Ａ／ｄｍ２以下が特に好ましい。
上記範囲内であると、微小孔や微小凹部の充填性に優れ、コスト的にも有利である。 The current density during plating is preferably 0.1 A / dm 2 or more, particularly preferably 1 A / dm 2 or more. Moreover, 10 A / dm 2 or less is preferable and 5 A / dm 2 or less is particularly preferable.
Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
上記範囲内であると、微小孔や微小凹部の充填性に優れ、コスト的にも有利である。 The current density during plating is preferably 0.1 A / dm 2 or more, particularly preferably 1 A / dm 2 or more. Moreover, 10 A / dm 2 or less is preferable and 5 A / dm 2 or less is particularly preferable.
Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
また、電流密度は、めっき充填中に常に一定にしてもよいし、一定でなくてもよい（例えば、初期の電流密度を低くし、徐々に電流密度を上げていく；パルス電流とする；等）。
電流密度は、めっき充填中に常に一定（又は、めっき充填中の大半の時間において一定）とした方が、ボイドを生ずることなく充填しやすく、好ましい。 Also, the current density may or may not always 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 for most of the time during plating filling) because filling is easy without generating voids.
電流密度は、めっき充填中に常に一定（又は、めっき充填中の大半の時間において一定）とした方が、ボイドを生ずることなく充填しやすく、好ましい。 Also, the current density may or may not always 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 for most of the time during plating filling) because filling is easy without generating voids.
めっき時間は、５分以上が好ましく、１０分以上が特に好ましい。また、３６０分以下が好ましく、６０分以下が特に好ましい。
上記範囲内であると、微小孔や微小凹部の充填性に優れ、コスト的にも有利である。 The plating time is preferably 5 minutes or longer, particularly preferably 10 minutes or longer. Moreover, 360 minutes or less are preferable and 60 minutes or less are especially preferable.
Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
上記範囲内であると、微小孔や微小凹部の充填性に優れ、コスト的にも有利である。 The plating time is preferably 5 minutes or longer, particularly preferably 10 minutes or longer. Moreover, 360 minutes or less are preferable and 60 minutes or less are especially preferable.
Within the above range, the filling properties of the micropores and microrecesses are excellent, and the cost is advantageous.
以下に、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例及び比較例に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples and comparative examples as long as the gist thereof is not exceeded.
実施例１～４、比較例１～３
微小凹部のモデルとして、アスペクト比０．８８（φ４５μｍ×４０μｍＤ）のレーザービアを有した１２ｍｍ角の評価用プリント基板（日本サーキット株式会社製）を使用した。 Examples 1 to 4 and Comparative Examples 1 to 3
A 12 mm square printed circuit board for evaluation (manufactured by Nippon Circuit Co., Ltd.) having a laser via with an aspect ratio of 0.88 (φ45 μm × 40 μmD) was used as a model of the minute recess.
微小凹部のモデルとして、アスペクト比０．８８（φ４５μｍ×４０μｍＤ）のレーザービアを有した１２ｍｍ角の評価用プリント基板（日本サーキット株式会社製）を使用した。 Examples 1 to 4 and Comparative Examples 1 to 3
A 12 mm square printed circuit board for evaluation (manufactured by Nippon Circuit Co., Ltd.) having a laser via with an aspect ratio of 0.88 (φ45 μm × 40 μmD) was used as a model of the minute recess.
被めっき部周辺１０の断面図を図１に示す。厚さ０．４ｍｍのＢＴ（Bismaleimide-Triazine）製の基材１１のビアホール形成部分に厚さ１２μｍの銅箔１３を張り付けた上で、厚さ６０μｍのプリプレグタイプのビルドアップ樹脂１２を積層後、レーザーにてφ４５μｍ、深さ４０μｍのブラインドビアホール（以下、単に「ビアホール」又は「ビア」と略記する場合がある。）１４を作成し、基板外表面（ビルドアップ樹脂１２の表面）及びビア１４内壁面に、無電解銅めっきで、シード層１５を約１μｍ形成した。
更に、ドライフィルムレジスト（ＤＦＲ）１６にて、図２に示す配線パターンを形成し、ビア１４を有するパッド（開口部）１７（φ１９０μｍ）を開口させたものを評価用プリント基板１とした。 A cross-sectional view around the portion to be plated 10 is shown in FIG. After pasting a 12 μmthick copper foil 13 on a via hole forming portion of a base material 11 made of BT (Bismaleimide-Triazine) having a thickness of 0.4 mm, a prepreg type buildup resin 12 having a thickness of 60 μm is laminated, A blind via hole (hereinafter sometimes simply referred to 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 substrate outer surface (the surface of the buildup resin 12) and the inside of the via 14 About 1 μm of seed layer 15 was formed on the wall surface by electroless copper plating.
Further, the evaluation printed circuit board 1 was formed by forming the wiring pattern shown in FIG. 2 with a dry film resist (DFR) 16 and opening a pad (opening) 17 (φ190 μm) having a via 14.
更に、ドライフィルムレジスト（ＤＦＲ）１６にて、図２に示す配線パターンを形成し、ビア１４を有するパッド（開口部）１７（φ１９０μｍ）を開口させたものを評価用プリント基板１とした。 A cross-sectional view around the portion to be plated 10 is shown in FIG. After pasting a 12 μm
Further, the evaluation printed circuit board 1 was formed by forming the wiring pattern shown in FIG. 2 with a dry film resist (DFR) 16 and opening a pad (opening) 17 (φ190 μm) having a via 14.
図２において、白色部が銅めっき部で、黒色部がドライフィルムレジスト部である。白色部のうち、配線が接続されている最もサイズの大きい円形部分が図１の円形パッド１７（φ１９０μｍ）に相当する。円形パッド１７の全てに、図１に示した微小凹部であるビアホール１４が形成されている。
In FIG. 2, the white part is the copper plating part and the black part is the dry film resist part. Of the white portion, the largest circular portion to which the wiring is connected corresponds to the circular pad 17 (φ190 μm) in FIG. A via hole 14 that is a minute recess shown in FIG. 1 is formed in all of the circular pads 17.
＜電解ニッケルめっき液の調製＞
スルファミン酸ニッケルを６００ｇ／Ｌ、塩化ニッケルを１０ｇ／Ｌ、ホウ酸を３０ｇ／Ｌとなるように脱イオン水に溶解し、電解ニッケルめっき液を調製した。
上記電解ニッケルめっき液に対し、表１に示す添加剤を、表１に示す添加量となるように添加し、溶解した。
次いで１００ｇ／Ｌのスルファミン酸水溶液を適量加えてｐＨを３．６に調整し、本発明の電解ニッケルめっき液を調製した。 <Preparation of electrolytic nickel plating solution>
An electrolytic nickel plating solution was prepared by dissolving in deionized water so that nickel sulfamate was 600 g / L, nickel chloride was 10 g / L, and boric acid was 30 g / L.
The additives shown in Table 1 were added to the electrolytic nickel plating solution so as to have the addition amount shown in Table 1 and dissolved.
Next, an appropriate amount of 100 g / L sulfamic acid aqueous solution was added to adjust the pH to 3.6 to prepare the electrolytic nickel plating solution of the present invention.
スルファミン酸ニッケルを６００ｇ／Ｌ、塩化ニッケルを１０ｇ／Ｌ、ホウ酸を３０ｇ／Ｌとなるように脱イオン水に溶解し、電解ニッケルめっき液を調製した。
上記電解ニッケルめっき液に対し、表１に示す添加剤を、表１に示す添加量となるように添加し、溶解した。
次いで１００ｇ／Ｌのスルファミン酸水溶液を適量加えてｐＨを３．６に調整し、本発明の電解ニッケルめっき液を調製した。 <Preparation of electrolytic nickel plating solution>
An electrolytic nickel plating solution was prepared by dissolving in deionized water so that nickel sulfamate was 600 g / L, nickel chloride was 10 g / L, and boric acid was 30 g / L.
The additives shown in Table 1 were added to the electrolytic nickel plating solution so as to have the addition amount shown in Table 1 and dissolved.
Next, an appropriate amount of 100 g / L sulfamic acid aqueous solution was added to adjust the pH to 3.6 to prepare the electrolytic nickel plating solution of the present invention.
＜電解ニッケルめっきによるビアの充填＞
上記評価用プリント基板１に対して、表２に示す工程で、電解ニッケルめっきを行なった。電解ニッケルめっき工程では、外部電源を使用して電流密度１．０Ａ／ｄｍ２となるようにした。
なお、めっき面積は、ビア１４の側面を含んだ表面積ではなく、開口部（パッド）１７平面のみの面積として計算した。 <Via filling by electrolytic nickel plating>
Electrolytic nickel plating was performed on the evaluation printed circuit board 1 in the steps shown in Table 2. The electroless nickel plating step was made to be a current density of 1.0A / dm 2 using an external power source.
The plating area was calculated not as a surface area including the side surface of the via 14 but as an area of only the plane of the opening (pad) 17.
上記評価用プリント基板１に対して、表２に示す工程で、電解ニッケルめっきを行なった。電解ニッケルめっき工程では、外部電源を使用して電流密度１．０Ａ／ｄｍ２となるようにした。
なお、めっき面積は、ビア１４の側面を含んだ表面積ではなく、開口部（パッド）１７平面のみの面積として計算した。 <Via filling by electrolytic nickel plating>
Electrolytic nickel plating was performed on the evaluation printed circuit board 1 in the steps shown in Table 2. The electroless nickel plating step was made to be a current density of 1.0A / dm 2 using an external power source.
The plating area was calculated not as a surface area including the side surface of the via 14 but as an area of only the plane of the opening (pad) 17.
＜めっき充填性評価試験＞
めっき後の基板を研磨用の樹脂に埋没固定後に断面研磨し、金属顕微鏡にてビアの充填具合を観察した。
充填性について、ビアホール内部の析出量がビアホール外部の析出量よりも多い状態で、ビアホール内部にボイド（穴）やシーム（溝）が観測されない場合を「○」、それ以外の場合を「×」とした。
また、ビアホール外部におけるクラック（亀裂）の発生の有無を観測した。
充填性が「○」で、クラックの発生が無い場合を「良好」、それ以外の場合を「不良」と評価した。 <Plating fillability evaluation test>
The substrate after plating was buried and fixed in a polishing resin, and the cross-section was polished. The via filling state was observed with a metal microscope.
Regarding filling properties, “○” indicates that no voids (holes) or seams (grooves) are observed inside the via hole when the amount of precipitation inside the via hole is greater than the amount deposited outside the via hole, and “×” otherwise. It was.
In addition, the occurrence of cracks (cracks) outside the via hole was observed.
The case where the filling property was “◯” and no crack was generated was evaluated as “good”, and the other cases were evaluated as “bad”.
めっき後の基板を研磨用の樹脂に埋没固定後に断面研磨し、金属顕微鏡にてビアの充填具合を観察した。
充填性について、ビアホール内部の析出量がビアホール外部の析出量よりも多い状態で、ビアホール内部にボイド（穴）やシーム（溝）が観測されない場合を「○」、それ以外の場合を「×」とした。
また、ビアホール外部におけるクラック（亀裂）の発生の有無を観測した。
充填性が「○」で、クラックの発生が無い場合を「良好」、それ以外の場合を「不良」と評価した。 <Plating fillability evaluation test>
The substrate after plating was buried and fixed in a polishing resin, and the cross-section was polished. The via filling state was observed with a metal microscope.
Regarding filling properties, “○” indicates that no voids (holes) or seams (grooves) are observed inside the via hole when the amount of precipitation inside the via hole is greater than the amount deposited outside the via hole, and “×” otherwise. It was.
In addition, the occurrence of cracks (cracks) outside the via hole was observed.
The case where the filling property was “◯” and no crack was generated was evaluated as “good”, and the other cases were evaluated as “bad”.
めっき充填後の基板断面の顕微鏡写真を、図３～９に示す。また、評価結果を表３に示す。
3 to 9 show micrographs of the cross section of the substrate after plating filling. The evaluation results are shown in Table 3.
実施例１～４では、析出ニッケル１８の量は、ビアホール外部よりも微小凹部であるビアホールの方が多く、ボイドやシームがなく良好に充填されていた。また、ビアホールの外部にクラックは観察されなかった。
In Examples 1 to 4, the amount of precipitated nickel 18 was greater in via holes that are minute recesses than outside the via holes, and was well filled without voids or seams. Further, no cracks were observed outside the via hole.
比較例１では、ビアホールの内部と外部で、析出ニッケル１８の量が同程度なコンフォーマルめっき（追従めっき）であり、充填性は不良であった。
Comparative Example 1 was conformal plating (follow-up plating) in which the amount of deposited nickel 18 was the same inside and outside the via hole, and the filling property was poor.
比較例２では、ビアの内部にボイドＶが有り、充填性は不良であった。
In Comparative Example 2, there was a void V inside the via and the filling property was poor.
比較例３では、ビアの内部にボイドはなく、充填性は良好であるが、析出部が非常に脆く、クラックが発生しており、研磨後にビア上部で析出ニッケル１８の著しい剥離が見られた。従って、微小三次元構造体としては不良であった。
In Comparative Example 3, there was no void inside the via and the filling property was good, but the deposited part was very brittle and cracks occurred, and after the polishing, the deposited nickel 18 was remarkably peeled at the upper part of the via. . Therefore, it was a poor micro three-dimensional structure.
実施例１～４、比較例１～３の結果が示すように、一般式（Ａ）又は一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物を含有する電解ニッケルめっき液で電解めっきすることにより、電子部品内に形成された微小孔をニッケルで良好に充填することができ、微小三次元構造体を作成することが可能となった。
As the results of Examples 1 to 4 and Comparative Examples 1 to 3 show, 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) Thus, the micropores formed in the electronic component can be satisfactorily filled with nickel, and a micro three-dimensional structure can be created.
本発明の特定Ｎ置換カルボニルピリジニウム化合物を含有する電解ニッケル（合金）めっき液は、電子回路部品内の微小孔又は微小凹部を信頼性高く充填することができ、配線の更なる微細化に対応できるため、三次元配線形成や三次元ＭＥＭＳ部品等に広く応用することができる。
The electrolytic nickel (alloy) plating solution containing the specific N-substituted carbonylpyridinium compound of the present invention can reliably fill minute holes or minute recesses in electronic circuit components, and can cope with further miniaturization of wiring. Therefore, it can be widely applied to 3D wiring formation, 3D MEMS parts, and the like.
１ 評価用プリント基板
１０ 被めっき部周辺
１１ 基材
１２ ビルドアップ樹脂
１３ 銅箔
１４ ブラインドビアホール
１５ シード層
１６ ドライフィルムレジスト
１７ パッド
１８ 析出ニッケル
Ｖ ボイド DESCRIPTION OF SYMBOLS 1 Printed circuit board forevaluation 10 Peripheral part 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 V Void
１０ 被めっき部周辺
１１ 基材
１２ ビルドアップ樹脂
１３ 銅箔
１４ ブラインドビアホール
１５ シード層
１６ ドライフィルムレジスト
１７ パッド
１８ 析出ニッケル
Ｖ ボイド DESCRIPTION OF SYMBOLS 1 Printed circuit board for
Claims (10)
- ニッケル塩と、ｐＨ緩衝剤と、下記一般式（Ａ）で表されるＮ置換カルボニルピリジニウム化合物を含有することを特徴とする電解ニッケルめっき液又は電解ニッケル合金めっき液。
- Ｘ－がハロゲン化物イオンである請求項１に記載の電解ニッケルめっき液又は電解ニッケル合金めっき液。 2. The electrolytic nickel plating solution or electrolytic nickel alloy plating solution according to claim 1, wherein X − is a halide ion.
- ニッケル塩と、ｐＨ緩衝剤と、下記一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物を含有することを特徴とする電解ニッケルめっき液又は電解ニッケル合金めっき液。
- 上記ニッケル塩が、硫酸ニッケル、スルファミン酸ニッケル、塩化ニッケル、臭化ニッケル、炭酸ニッケル、硝酸ニッケル、ギ酸ニッケル、酢酸ニッケル、クエン酸ニッケル及びホウフッ化ニッケルからなる群より選ばれた１種以上である請求項１ないし請求項３の何れかの請求項に記載の電解ニッケルめっき液又は電解ニッケル合金めっき液。 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 3.
- 上記ｐＨ緩衝剤が、ホウ酸、メタホウ酸、酢酸、酒石酸及びクエン酸、並びにそれらの塩からなる群より選ばれた１種以上である請求項１ないし請求項４の何れかの請求項に記載の電解ニッケルめっき液又は電解ニッケル合金めっき液。 The said pH buffer is 1 or more types chosen from the group which consists of boric acid, metaboric acid, an acetic acid, tartaric acid, a citric acid, and those salts, The claim in any one of Claim 1 thru | or 4 Electrolytic nickel plating solution or electrolytic nickel alloy plating solution.
- 一般式（Ａ）で表されるＮ置換カルボニルピリジニウム化合物が、１－カルバモイルピリジニウムのハロゲン化物、１－（カルバモイルメチル）ピリジニウムのハロゲン化物、１－（ジメチルカルバモイル）ピリジニウムのハロゲン化物、１－（ジエチルカルバモイル）ピリジニウムのハロゲン化物、１－（ヒドラジノカルボニルメチル）ピリジニウムのハロゲン化物及び１－アセトニルピリジニウムのハロゲン化物からなる群より選ばれた１種以上の化合物である請求項２、請求項４又は請求項５に記載の電解ニッケルめっき液又は電解ニッケル合金めっき液。 The N-substituted carbonylpyridinium compound represented by the general formula (A) is a halide of 1-carbamoylpyridinium, a halide of 1- (carbamoylmethyl) pyridinium, a halide of 1- (dimethylcarbamoyl) pyridinium, 1- (diethyl The carbamoyl) pyridinium halide, 1- (hydrazinocarbonylmethyl) pyridinium halide, and 1-acetonylpyridinium halide are one or more compounds selected from the group consisting of 1 and 2 or 4 or The electrolytic nickel plating solution or electrolytic nickel alloy plating solution according to claim 5.
- 一般式（Ｂ）で表されるＮ置換カルボニルピリジニウム化合物が、１－（カルバモイルメチル）－４－（２－スルホエチル）ピリジニウムヒドロキシド分子内塩、１－（カルバモイルメチル）－４－（２－スルホプロピル）ピリジニウムヒドロキシド分子内塩、１－（カルバモイル）－４－（２－スルホエチル）ピリジニウムヒドロキシド分子内塩、１－（カルバモイル）－４－（２－スルホプロピル）ピリジニウムヒドロキシド分子内塩、１－（ジメチルカルバモイル）－４－（２－スルホエチル）ピリジニウムヒドロキシド分子内塩及び１－（ジメチルカルバモイル）－４－（２－スルホプロピル）ピリジニウムヒドロキシド分子内塩からなる群より選ばれた１種以上の化合物である請求項３ないし請求項５の何れかの請求項に記載の電解ニッケルめっき液又は電解ニッケル合金めっき液。 An N-substituted carbonylpyridinium compound represented by the general formula (B) is a 1- (carbamoylmethyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (carbamoylmethyl) -4- (2-sulfo). Propyl) pyridinium hydroxide inner salt, 1- (carbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt, 1- (carbamoyl) -4- (2-sulfopropyl) pyridinium hydroxide inner salt, 1 selected from the group consisting of 1- (dimethylcarbamoyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt and 1- (dimethylcarbamoyl) -4- (2-sulfopropyl) pyridinium hydroxide inner salt The compound according to any one of claims 3 to 5, wherein the compound is a compound of more than one species. Solution nickel plating solution or an electroless nickel alloy plating solution.
- 電子回路部品内に形成された微小孔又は微小凹部の充填用である請求項１ないし請求項７の何れかの請求項に記載の電解ニッケルめっき液又は電解ニッケル合金めっき液。 The electrolytic nickel plating solution or the electrolytic nickel alloy plating solution according to any one of claims 1 to 7, wherein the electrolytic nickel plating solution or the electrolytic nickel alloy plating solution is used for filling minute holes or minute recesses formed in an electronic circuit component.
- 電子回路部品内に形成された微小孔又は微小凹部の表面に予め電解めっき用シード層を施した後、該電子回路部品を請求項１ないし請求項８の何れかの請求項に記載の電解ニッケルめっき液又は電解ニッケル合金めっき液に浸漬し、外部電源を使用して電解めっきをすることを特徴とするニッケル又はニッケル合金めっき充填方法。 The electrolytic nickel according to any one of claims 1 to 8, wherein a seed layer for electrolytic plating is preliminarily applied to the surface of a minute hole or minute recess formed in the electronic circuit component. A nickel or nickel alloy plating filling method characterized by immersing in a plating solution or an electrolytic nickel alloy plating solution and performing electrolytic plating using an external power source.
- 請求項９に記載のニッケル又はニッケル合金めっき充填方法により微小孔又は微小凹部にめっき充填する工程を含むことを特徴とする微小三次元構造体の製造方法。 A method for producing a micro three-dimensional structure comprising a step of plating and filling micropores or microrecesses by the nickel or nickel alloy plating filling method according to claim 9.
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| JP2018518251A JP6860933B2 (en) | 2016-05-18 | 2017-05-11 | Electrolytic nickel (alloy) plating solution |
| CN201780030115.7A CN109154093B (en) | 2016-05-18 | 2017-05-11 | Electrolytic nickel (alloy) plating solution |
| KR1020187032988A KR102354192B1 (en) | 2016-05-18 | 2017-05-11 | Electrolytic nickel (alloy) plating solution |
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| JP2015101751A (en) * | 2013-11-25 | 2015-06-04 | 日本高純度化学株式会社 | Electrolytic gold plating solution and gold film produced using the same |
| JP2016027211A (en) * | 2013-05-08 | 2016-02-18 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ | Galvanic nickel or nickel alloy dc electroplating bath for depositing semi-bright nickel or nickel alloy, method for electroplating and use of bath and compounds for the same |
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| US5547832A (en) * | 1992-07-07 | 1996-08-20 | Eastman Kodak Company | Method for hardening photographic materials |
| ES2340973T3 (en) * | 2008-02-29 | 2010-06-11 | Atotech Deutschland Gmbh | PIROPHOSPHATE BASED BATHROOM FOR THE DEPOSITION OF TIN ALLOY LAYERS. |
| JP6367322B2 (en) * | 2013-06-17 | 2018-08-01 | アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ | Method for copper plating through silicon via using wet wafer back contact |
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| JP2015101751A (en) * | 2013-11-25 | 2015-06-04 | 日本高純度化学株式会社 | Electrolytic gold plating solution and gold film produced using the same |
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| KR20190008232A (en) | 2019-01-23 |
| TW201807261A (en) | 2018-03-01 |
| CN109154093B (en) | 2020-11-27 |
| CN109154093A (en) | 2019-01-04 |
| JPWO2017199835A1 (en) | 2019-03-14 |
| TWI726101B (en) | 2021-05-01 |
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| JP6860933B2 (en) | 2021-04-21 |
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