JPH11335888A - Plating liquid and plating - Google Patents

Plating liquid and plating

Info

Publication number
JPH11335888A
JPH11335888A JP10142560A JP14256098A JPH11335888A JP H11335888 A JPH11335888 A JP H11335888A JP 10142560 A JP10142560 A JP 10142560A JP 14256098 A JP14256098 A JP 14256098A JP H11335888 A JPH11335888 A JP H11335888A
Authority
JP
Japan
Prior art keywords
plating
copper
hole
plating solution
thickness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP10142560A
Other languages
Japanese (ja)
Inventor
Takeshi Itabashi
武之 板橋
Toshio Hashiba
登志雄 端場
Haruo Akaboshi
晴夫 赤星
Shinichi Fukada
晋一 深田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Priority to JP10142560A priority Critical patent/JPH11335888A/en
Publication of JPH11335888A publication Critical patent/JPH11335888A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To form wiring, or the like, which obviate the generation of voids and seams, and have reliability by stirring a plating liquid contg. a material reduced by the potential nobler than a reduction potential on a body to be plated with plating metal ions by using the liquid described above. SOLUTION: The plating liquid is formed by incorporating the material reduced by the potential nobler than the reduction potential on the body to be plated with the plating metal ions, such as copper, at a concn. of about 0.0001 to 1 mol/l into the liquid. The amt. of the material reduced by the potential nobler than the potential of the plating metal included in the plating liquid or the reductant thereof, which is included in the plating metal deposited on the surface of the body to be plated, is preferably <=10 ppm. The plating liquid is stirred by blowing gas during the course of executing plating by using this plating liquid or by using a stirrer. The additive material effective when the plating liquid is copper includes materials, such as hydrogen peroxide, ammonium persulfate and benzoquinone, which are nobler in the reduction potential than the potential of the electrodeposition of copper.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【発明の属する技術分野】本発明は新規なめっき液およ
びめっき方法に関し、特に片側閉塞型の層間接続孔や微
細溝の側壁，底面への析出性に優れためっき液およびめ
っき方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel plating solution and a novel plating method, and more particularly to a plating solution and a plating method excellent in the deposition property on the side walls and bottom surfaces of one-side closed interlayer connection holes and fine grooves.

【従来の技術】絶縁体に形成した穴や溝の内壁に金属を
析出させる技術は、ＬＳＩ，薄膜多層基板，ビルドアッ
プ基板等の高密度配線基板の層間接続技術に応用されて
いる場合が多い。ＬＳＩの層間接続ではめっき等のウエ
ットメタライズではなく、スパッタあるいはＣＶＤ（化
学気相成長法）といったドライメタライズ法を用いてい
た。例えば、特開平6−168907 号ではスパッタリング法
によりアルミニウムをビア内部に充填する方法が開示さ
れている。また、特開平8−31932号では、六フッ化タン
グステンガスのモノシラン還元ＣＶＤ法、あるいは水素
還元ＣＶＤ法でコンタクトホール内にタングステンを充
填する方法が開示されている。更に、特開平6−236879
号では有機銅化合物を原料とし、ＣＶＤ法により銅の接
続プラグを形成する方法について開示している。しか
し、これらはいずれもドライメタライズ法であり、真空
系を備えた装置で行う方法であるため、装置コストが高
く、またスループットが低いという問題がある。また、
スパッタ法等のいわゆるＰＶＤ法（物理気相成長法）で
は穴，溝の側壁に対するカバレッジ性が悪く、穴，溝内
に金属が充填されない、いわゆるボイドが発生し、信頼
性の低下をもたらし問題となっている。また、スパッタ
法等ＰＶＤ法にくらべ穴，溝の側壁に対するカバレッジ
性が若干良好であるとされているＣＶＤ法では、形成し
た膜が不純物を多く含み、純度が低いという問題があ
る。純度の低下は電気抵抗の増大や、信頼性の低下をも
たらし問題となっている。穴や溝側面のカバレッジ性が
比較的良好であり、膜の純度が高く信頼性が確保できる
層間接続法として、めっき法を用いた方法が提案されて
いる。特開平7−283219号公報では電気めっきにより微
***，溝を埋める方法が開示されている。また、特開平
7−321111号公報では、スプレーパイロリシスにより酸
化亜鉛薄膜を溝，穴内に形成した後、貴金属層をその酸
化亜鉛と貴金属イオンの置換反応により析出させ、更に
その貴金属層を起点として電気めっきあるいは無電解め
っきにより溝，穴を充填する方法について開示してい
る。また、USP5,695,810ではＣｏＷＰ合金を下地膜とし
て無電解めっきにより微***，溝を充填した構造が開示
されている。特開平5−315336 号公報では微***，溝内
にボイドが残らないようにするため、めっきの後、低照
射エネルギーのレーザを照射し、めっき金属を流動さ
せ、ボイドを充填する方法について開示している。しか
し、今日まで行われてきたこれらの方法では、元来、微
***，溝の側壁部には電界がかかりにくいため絶縁層表
面や穴，溝の上面エッジ部に比べ、穴，溝の側壁部のめ
っき膜厚が小さくなる。この場合、穴，溝が充填される
前に穴，溝の入口が塞がり、穴，溝内部に空洞が残る、
いわゆるボイドの発生が問題となる。また、無電解めっ
きを用いたUSP5,695,810でも、電気めっきと同様穴，溝
の上面エッジ部の膜厚が厚くなり、ボイドが発生してし
まう現象が問題となっていた。一方、薄膜多層基板やビ
ルドアップ基板でも無電解めっきや電気めっき技術を用
いて微小ビアホールを充填する方法も開示されている
が、何れもビアホール底面からメッキを析出させる方法
である。例えば特開平6−302965 号，特開平5−335713
号がある。特開平6−302965 号ではめっき厚みのコント
ロールは非常に困難であるため、最終的に研磨を施して
いる。また、特開平5−335713 号でも電解あるいは無電
解めっきによりビアホール内を充填する方法について開
示されている。しかし、この方法では先ず無電解めっき
によるビアホール充填は不可能である。無電解めっき反
応はビアホール上層部の表側導体端面でも進行するた
め、時間と共にビアホール開口部が小さくなり塞がって
しまうからである。この場合ビアホール内部にはボイド
状の空間が残り、基板の信頼性は著しく低下するため問
題である。また、電気めっきによる場合でも、ビアホー
ル底部よりめっきされてきた金属がビアホール上層部の
表側導体端面に接触した瞬間、ビアホール上層部の表側
導体端面からもめっき反応が進行し、ビアホール径が表
側導体厚みの２倍以下の場合にはビアホール開口部は塞
がってしまう。この場合もまた、ビアホール内部にはボ
イド状の空間が残り、基板の信頼性は著しく低下するた
め問題である。更に、ビアホール径が表側導体厚みの２
倍以上の場合、ビアホール開口部は閉塞されることは無
いが、表側導体表面に達した時のめっき形状はビアホー
ル内部をめっきしていたときの「円柱状」ではなく、
「きのこ状」となってしまう。これはめっき反応が異方
性を示さず、等方的に成長するためである。また、充填
をせず、ビアホール内壁面に析出させ、上下の導通をと
る方法もあり、これは薄膜多層基板やビルドアップ基板
では最も一般的な層間接続方法である。断面の模式図を
図２に示した。めっき法によりこの様な形状のビアホー
ル接続を行う場合には電界の集中しやすいビアホール上
面エッジ部の膜厚が厚くなってしまい、ビアホール底部
のめっき膜厚を確保できず、信頼性の低い配線基板とな
ってしまう。2. Description of the Related Art A technique for depositing a metal on the inner wall of a hole or a groove formed in an insulator is often applied to an interlayer connection technique of a high-density wiring board such as an LSI, a thin-film multilayer board, a build-up board, and the like. . For the interlayer connection of LSI, a dry metallization method such as sputtering or CVD (chemical vapor deposition) is used instead of wet metallization such as plating. For example, Japanese Patent Application Laid-Open No. 6-168907 discloses a method in which aluminum is filled inside a via by a sputtering method. Japanese Patent Application Laid-Open No. 8-31932 discloses a method in which tungsten is filled in a contact hole by a monosilane reduction CVD method using tungsten hexafluoride gas or a hydrogen reduction CVD method. Further, JP-A-6-236879
Discloses a method of forming a copper connection plug by a CVD method using an organic copper compound as a raw material. However, these methods are all dry metallization methods and methods using a vacuum system, so that there is a problem that the apparatus cost is high and the throughput is low. Also,
In a so-called PVD method (physical vapor deposition method) such as a sputtering method, the coverage of the side wall of a hole or a groove is poor, so that a metal is not filled in the hole or the groove, so-called voids are generated, and the reliability is deteriorated. Has become. Further, the CVD method, which is said to have slightly better coverage of the side walls of the holes and grooves than the PVD method such as the sputtering method, has a problem that the formed film contains many impurities and has low purity. A decrease in purity is a problem because it causes an increase in electric resistance and a decrease in reliability. A method using a plating method has been proposed as an interlayer connection method in which the coverage of holes and grooves is relatively good and the film has high purity and high reliability. Japanese Patent Application Laid-Open No. 7-283219 discloses a method for filling minute holes and grooves by electroplating. In addition,
In JP-A-7-321111, after a zinc oxide thin film is formed in a groove or a hole by spray pyrolysis, a noble metal layer is deposited by a substitution reaction between the zinc oxide and a noble metal ion, and further, electroplating or non-plating is started from the noble metal layer. A method for filling grooves and holes by electrolytic plating is disclosed. Further, US Pat. No. 5,695,810 discloses a structure in which minute holes and grooves are filled by electroless plating using a CoWP alloy as a base film. Japanese Patent Application Laid-Open No. 5-315336 discloses a method of irradiating a low-irradiation energy laser after plating to flow a plating metal and filling voids in order to prevent voids from remaining in micro holes and grooves. ing. However, in these methods which have been performed to date, originally, an electric field is hardly applied to the side walls of the minute holes and the grooves, so that the side walls of the holes and the grooves are compared with the surface of the insulating layer and the upper edges of the holes and the grooves. Plating film thickness becomes small. In this case, before the hole or groove is filled, the entrance of the hole or groove is closed and a cavity remains inside the hole or groove.
The generation of so-called voids becomes a problem. Also in USP 5,695,810 using electroless plating, the phenomenon that the film thickness of the upper edge portion of the hole or groove becomes large and voids are generated similarly to the electroplating has been a problem. On the other hand, a method of filling minute via holes with a thin film multilayer substrate or a build-up substrate using electroless plating or electroplating technology has also been disclosed, but all of them are methods of depositing plating from the bottom surface of the via hole. For example, JP-A-6-302965, JP-A-5-335713
There is a number. In JP-A-6-302965, since it is very difficult to control the plating thickness, polishing is finally performed. Japanese Patent Application Laid-Open No. 5-335713 also discloses a method of filling the inside of a via hole by electrolytic or electroless plating. However, in this method, first, via hole filling by electroless plating is impossible. This is because the electroless plating reaction also proceeds on the front-side conductor end surface in the upper portion of the via hole, and the opening of the via hole becomes smaller and closes over time. In this case, a void-shaped space remains inside the via hole, and the reliability of the substrate is significantly reduced, which is a problem. Also, even in the case of electroplating, at the moment when the metal plated from the bottom of the via hole comes into contact with the front conductor end surface of the upper layer of the via hole, the plating reaction also proceeds from the front conductor end surface of the upper layer of the via hole, and the via hole diameter is reduced by the thickness of the front conductor. If it is less than twice, the via hole opening will be closed. Also in this case, a void-shaped space remains inside the via hole, and the reliability of the substrate is significantly reduced, which is a problem. Furthermore, the via hole diameter is 2 mm of the front side conductor thickness.
If it is more than twice, the via hole opening will not be closed, but the plating shape when reaching the front side conductor surface is not `` columnar '' when plating the inside of the via hole,
It becomes "mushroom-like". This is because the plating reaction does not show anisotropy and grows isotropically. Further, there is also a method of depositing on the inner wall surface of the via hole without filling and establishing vertical conduction, and this is the most common interlayer connection method for a thin film multilayer substrate or a build-up substrate. FIG. 2 shows a schematic diagram of the cross section. When a via hole connection of such a shape is made by plating, the thickness of the upper edge portion of the via hole where the electric field tends to concentrate tends to be large, so that the plating film thickness at the bottom of the via hole cannot be secured, and the wiring board having low reliability is not provided. Will be.

【発明が解決しようとする課題】上述したようにドライ
メタライズ法で微***内に金属を充填する場合には、真
空系を備えた装置を使用するため、装置コストが高く、
またスループットが低いという問題がある。また、スパ
ッタ法等のいわゆるＰＶＤ法（物理気相成長法）では
穴，溝の側壁に対するカバレッジ性が悪く、穴，溝内に
金属が充填されない、いわゆるボイドが発生し、信頼性
の低下をもたらし問題となっている。また、スパッタ法
等ＰＶＤ法にくらべ穴，溝の側壁に対するカバレッジ性
が若干良好であるとされているＣＶＤ法では、形成した
膜が不純物を多く含み、純度が低いという問題がある。
純度の低下は電気抵抗の増大や、信頼性の低下をもたら
し問題となっている。更に、ＣＶＤ法では使用する原料
が高価な化合物であるため、コスト面でデメリットが非
常に大きい。一方、ウエットメタライズ法で微***内を
金属充填する場合には、上述のように電気めっき法と無
電解めっき法がある。電気めっきで微***，溝を充填す
る場合には、微***，溝の上面エッジ部に電界が集中す
るため、図３に示したように、入口が塞がり、内部にボ
イドが発生し易いという問題がある。配線密度の高密度
化を達成するためには、微***では径が小さく深い穴
（＝アスペクト比の大きい穴）、配線形成用の微小溝で
は線幅が小さく深い溝（＝アスペクト比の大きい溝）を
充填する必要があるが、通常の電気めっき法を用いる限
り、アスペクト比が大きいほどボイドは発生しやすいた
め、高密度配線形成のネックとなっている。従って、電
気めっき法を用いる場合には微***，溝の上面エッジ部
へのめっき金属の析出を抑制する必要がある。無電解め
っき法を用いる場合には均一な析出が期待できるが、図
４に示したように、最終的には中心部に筋状の「シー
ム」と呼ばれる空間ができる。このシーム内はめっき液
やその後の洗浄水等で汚染されている可能性があるた
め、その発生を抑制する必要があるが、通常の無電解め
っき法では原理的に不可能である。また、充填をせず、
ビアホール内壁面に析出させ、上下の導通をとる方法も
あり、これは薄膜多層基板やビルドアップ基板では最も
一般的な層間接続方法である。めっき法によりこの様な
形状のビアホール接続を行う場合には電界の集中しやす
いビアホール上面エッジ部の膜厚が厚くなってしまい、
ビアホール底部のめっき膜厚を確保できず、信頼性の低
い配線基板となってしまい問題となっている。本発明の
目的は、ボイド，シームの生じにくいめっき液及びめっ
き方法を提供するにある。As described above, when a metal is filled in a fine hole by a dry metallization method, an apparatus having a vacuum system is used, so that the apparatus cost is high.
There is also a problem that the throughput is low. Also, in a so-called PVD method (physical vapor deposition method) such as a sputtering method, the coverage of the side wall of the hole or groove is poor, and a metal is not filled in the hole or groove, so-called voids are generated, and the reliability is reduced. It is a problem. Further, the CVD method, which is said to have slightly better coverage of the side walls of the holes and grooves than the PVD method such as the sputtering method, has a problem that the formed film contains many impurities and has low purity.
A decrease in purity is a problem because it causes an increase in electric resistance and a decrease in reliability. Furthermore, since the starting material used in the CVD method is an expensive compound, the cost is very disadvantageous. On the other hand, when metal is filled in the minute holes by the wet metallizing method, there are an electroplating method and an electroless plating method as described above. When filling the micro holes and grooves by electroplating, the electric field concentrates on the upper edge of the micro holes and grooves, so that as shown in FIG. 3, the entrance is closed and a void is easily generated inside. There is. In order to achieve higher wiring density, a fine hole has a small diameter and a deep hole (= a hole having a large aspect ratio), and a fine groove for forming a wiring has a small line width and a deep groove (= a groove having a large aspect ratio). However, as long as a normal electroplating method is used, voids are more likely to be generated as the aspect ratio is larger, which is a bottleneck in forming a high-density wiring. Therefore, when the electroplating method is used, it is necessary to suppress the deposition of the plating metal on the upper surface edge of the minute holes and grooves. When the electroless plating method is used, uniform deposition can be expected, but finally, as shown in FIG. 4, a space called a streak “seam” is formed at the center. Since the inside of the seam may be contaminated with a plating solution or subsequent washing water, it is necessary to suppress the occurrence of the contamination, but it is impossible in principle with a normal electroless plating method. Also, without filling
There is also a method in which deposition is performed on the inner wall surface of the via hole to establish vertical conduction, and this is the most common interlayer connection method for a thin-film multilayer substrate or a build-up substrate. When a via hole connection of such a shape is performed by plating, the thickness of the upper edge portion of the via hole where the electric field tends to concentrate tends to be large,
The plating film thickness at the bottom of the via hole cannot be ensured, resulting in a wiring board with low reliability, which is a problem. An object of the present invention is to provide a plating solution and a plating method that are less likely to cause voids and seams.

【課題を解決するための手段】本発明は、めっき金属イ
オンの被めっき体上での還元電位よりも、貴な電位で還
元される物質を含むめっき液である。第２は、そのめっ
き金属イオンの被めっき体上での還元電位よりも、貴な
電位で還元される物質の濃度が０.０００１mol／ｌ〜１
mol／ｌ であることを特徴とするめっき液である。第３
は、めっき金属の純度を保つために、めっき液中に含ま
れるめっき金属よりも貴な電位で還元される物質または
該物質の還元体の、被めっき体表面に析出しためっき金
属中に含まれる量が１０ppm 以下であることを特徴とす
るめっき液である。第４は、それらめっき液を用いため
っき方法で、めっきを行っている最中に、ガスを吹き込
んだり、あるいは撹拌器等の機器を用いて機械的にめっ
き液を撹拌することを特徴とするめっき方法である。本
発明のめっき液，めっき方法の応用は多岐に渡るが、こ
こではＬＳＩのダマシンプロセスと高密度プリント基板
の１種であるビルドアップ基板への実施形態を説明す
る。ＬＳＩダマシンプロセスの概略フローを断面模式図
で図１に示した。シリコン基板上に絶縁層（酸化膜）を
形成し、定法により穴または溝を形成する(図１ａ)。次
いで、めっき金属と絶縁層との反応やめっき金属が絶縁
層内へ拡散することを防止するため、絶縁層表面にバリ
ヤー層を形成する（図１ｂ）。バリヤー層としては、Ｔ
ｉＮやＴａ，Ｗ等の高融点金属が用いられる場合が多
い。バリヤー層形成後、電気めっきを施すために基板全
面にシード層を形成する。シード層の形成には、一般的
にスパッタ法が用いられる（図１ｃ）。その後、このシ
ード層を種に、電気めっきにより穴，溝を埋め込むに十
分な厚みだけメッキを行う。この時、通常の電気めっき
法では穴，溝のエッジ部に電界が集中し、穴，溝が充填
される以前に穴，溝の入口が塞がり、十分に充填されず
ボイドが残ることになる。しかし、本発明のめっき液を
用いることによりボイドの発生は完全に回避することが
できる。本発明のめっき液には、めっき金属イオンより
貴な電位で還元される添加剤が含有されているため、め
っき反応の電位で添加剤は還元される。めっき液中で被
めっき体表面（カソード）とアノードの間に流れた電気
量（クーロン量）に対する、析出しためっき金属の化学
当量を電流効率と称するが、この様な添加剤を含む場合
には電流効率は１以下となる。ちなみに、流れた電流の
全てがめっき反応に使われた場合の電流効率は１であ
り、副反応によりめっき反応以外に電流が消費された場
合の電流効率は１以下となる。この様に、自らが被めっ
き体表面で還元され、電流効率を低下させる添加剤を含
む本発明のめっき液を用いた場合には穴，溝の充填に大
きな効果を発揮させることが可能である。めっき開始直
後では穴，溝の内壁面およびそれ以外の基板表面といっ
た、全てのシード層表面で添加剤の還元反応とめっき金
属の還元反応が同時に進行し、電流効率は１よりもかな
り小さな値となる。しかし、しばらくの時間、一般的に
は数秒間が経過すると穴，溝内壁面の電流効率は１に近
い値となり、穴，溝内壁面以外の基板表面に比べ電流効
率は大きな値となる。すなわち、数秒後、穴，溝内壁面
でのめっき反応の電流効率が１に近い値となるのに対
し、穴，溝内壁面以外の表面でのめっき反応の電流効率
はあまり上昇せず、依然として１以下の小さな値とな
る。一定時間経過後のめっき反応の電流効率は 穴，溝内壁面＞それ以外の表面 となるのである。これは添加剤の還元反応が、物質供給
律速になることによる。すなわち、めっき開始時では
穴，溝内にあるめっき液中にもバルクのめっき液と同量
の添加剤が含まれているが、めっき開始後、穴，溝内の
めっき液中の添加剤はすぐに還元消費される。穴，溝内
のめっき液は滞留しているため、バルクのめっき液から
穴，溝内のめっき液への添加剤の供給はほとんど拡散に
よることになるが、電解還元による消費に追いつかない
ため、穴，溝内のめっき液中の添加剤濃度はほとんど０
となり、めっき反応の電流効率は１に近い値となる。こ
れに対し、穴，溝内壁面以外の表面では、添加剤はスム
ーズに供給されるため、めっき反応の電流効率は１以下
の値となり、穴，溝内壁面でのめっき反応の電流効率よ
りも小さな値となる。更に、めっき液を撹拌することに
より、穴，溝内壁面以外の表面への添加剤の供給はより
スムーズになるが、一方、穴，溝内のめっき液は滞留し
ているため、撹拌の影響をあまり受けない。従って、め
っき液を撹拌することにより、穴，溝内壁面でのめっき
反応の電流効率と、穴，溝内壁面以外の表面でのめっき
反応の電流効率の差を大きくすることができる。めっき
反応の電流効率を、「穴，溝内壁面＞それ以外の表面」
とすることにより、めっき膜厚は「穴，溝内壁面へ析出
しためっき膜厚＞それ以外の表面に析出しためっき膜
厚」とすることができる。以上の作用機構により、めっ
き過程では図１ｄに示したように、穴，溝内に優先的に
めっき析出が生じ、穴，溝内のめっき膜厚がその他の表
面のめっき膜厚に比べ大きくなる。その結果、シームや
ボイドが残らず、図１ｅのように穴，溝内は完全に充填
される。本発明を用いることにより、従来充填不可能で
あったアスペクト比の大きな穴，溝を充填可能になるの
である。更に、本発明のビルドアップ基板への実施の形
態を説明する。ビルドアップ基板の場合でも、めっきに
より、層間接続用のビアホールを完全に充填する場合に
は、上述のＬＳＩダマシンプロセスの場合と同様であ
る。従って、ここではめっきによりビアホールを完全に
充填しない場合のめっき方法について言及する。先ず図
５ａに断面の概略図で示したように、ガラスエポキシ等
で形成した内層回路基板表面にビルドアップの絶縁層を
形成し、ビアホールを形成する。その後、基板全面に薄
く無電解めっきを施すか、一般に「ダイレクトプレーテ
ィング」と称される、絶縁基板表面に直接電気めっきを
可能にする特殊な前処理を施し（図５ｂ）、基板表面全
体を導通化させ、電気めっきを行う。通常のめっき液を
用いた場合には、めっき後のビアホール部の断面形態は
図２のように、ビアホール入口のエッジ部のめっき膜厚
が大きく、ビアホール底部のめっき膜厚が小さな形態と
なる。ビアホール底部のめっき膜厚を大きくし、信頼性
を確保するためにめっき膜厚全体を厚くすることが考え
られるが、ビルドアップ基板ではめっきで形成した導体
を、エッチングして回路を形成するため、基板表面のめ
っき膜厚の増加はエッチング精度の低下をもたらし、問
題である。本発明を用いた場合には表面のめっき膜厚を
増加させることなく、ビアホール底部のめっき膜厚を大
きくすることができる。すなわち、めっき反応の電流効
率が、ビアホール内の方が表面にくらべ大きくなるため
である。これは、上述のＬＳＩダマシンプロセスの場合
と同様、添加剤の還元反応が物質供給律速になることに
よる。ビアホール内のめっき液中の添加剤はめっき開始
後、すぐに還元消費されてしまい、めっき反応の電流効
率は１に近い値に上昇するが、表面の添加剤はバルクよ
り十分に供給され、電流効率は低いままである。従っ
て、めっき液を撹拌する効果も、ＬＳＩダマシンプロセ
スの場合と同様に期待できる。以上の効果により、めっ
き後の基板断面は図５ｃの様にビアホール内部の特に底
部に近い部分のめっき膜厚が、基板表面のめっき膜厚に
比べ大きいという、接続信頼性においては非常に有利な
構造となる。以上の効果は、めっき金属イオンの還元電
位よりも貴な電位で還元される物質を含むめっき液であ
ればどのようなめっき液でも良く、金属の種類やめっき
液の種類によらない。添加剤の濃度としては、添加剤の
還元反応が物質供給律速になる範囲であり、通常、０.
０００１mol／ｌ〜１.０mol／ｌ 程度の範囲である。添
加剤の種類としては、めっき液により異なるため限定は
できないが、電気抵抗やめっき膜の延性などの物性が問
題となる場合が多く、その場合には添加剤の還元体また
は添加剤自身が多量にめっき膜中に混入する系は避ける
べきである。膜中に多量に混入する添加剤としては金属
イオンが考えられるが、添加剤として金属イオンを用い
るのは、上記のような物性が問題となる場合には避けた
ほうが望ましい。特に、めっき金属が銅の場合に有効な
添加剤としては過酸化水素，過硫酸アンモニウム，ベン
ゾキノン類でめっき液中で、銅上での還元電位が銅の電
析の電位より貴な物質等がある。そのようなベンゾキノ
ン類としては、１，４−ベンゾキノン、メチル−１，４
−ベンゾキノン、２，５−ジメチル−１，４−ベンゾキ
ノン、２，３−ジメチル−１，４−ベンゾキノン、トリ
メチル−１，４−ベンゾキノン、２−メチル−５−イソ
プロピル−１，４−ベンゾキノン、ヒドロキシ−１，４
−ベンゾキノン、２，５−ジヒドロキシ−１，４−ベン
ゾキノン、２，５−ジヒドロキシ−３，６−ジクロロ−
１，４−ベンゾキノン、２，５−ジメトキシ−１，４−
ベンゾキノン、２，６−ジメトキシ−１，４−ベンゾキ
ノン、２，５−ジエトキシ−１，４−ベンゾキノン、ク
ロロ−１，４−ベンゾキノン、２，３−ジクロロ−１，
４−ベンゾキノン、２，５−ジクロロ−１，４−ベンゾ
キノン、２，６−ジクロロ−１，４−ベンゾキノン、ブ
ロモ−１，４−ベンゾキノン、２，５−ジブロモ−１，
４−ベンゾキノン、２−クロロ−５−メチル−１，４−
ベンゾキノン、１，２−ベンゾキノン、メチル−１，２
−ベンゾキノン、４−カルボキシ−１，２−ベンゾキノ
ン、４−カルボエトキシ−１，２−ベンゾキノン、３−
ヒドロキシ−１，２−ベンゾキノン、３−ヒドロキシ−
５−カルボキシ−１，２−ベンゾキノン、テトラクロロ
−１，２−ベンゾキノン、テトラブロモ−１，２−ベン
ゾキノン、１，４−ナフトキノン、１，４−ナフトキノ
ン−２−スルフォネイト、９，１０−アントラキノン、
９，１０−アントラキノン−２−スルフォネイト、９，
１０−アントラキノン−１−スルフォネイト、９，１０
−アントラキノン−１，８−ジスルフォネイト、９，１
０−アントラキノン−１，５−ジスルフォネイト、５，
８−キノリンキノンがある。また、めっき方法として
は、前述したようにめっき液を撹拌するこでめっき反応
の電流効率に差を生じさせる効果をより高めることが可
能であるため、めっき中にめっき液を撹拌することは非
常に有効である。以下、本発明を実施する具体例につい
て述べる。尚、これらの絶縁材料の形状，材質や導体金
属の種類は本発明を限定するものではない。SUMMARY OF THE INVENTION The present invention is a plating solution containing a substance that is reduced at a noble potential rather than a reduction potential of plating metal ions on a body to be plated. Second, the concentration of the substance reduced at a noble potential than the reduction potential of the plating metal ions on the plate is 0.0001 mol / l to 1 mol / l.
mol / l. Third
Is contained in the plating metal deposited on the surface of the body to be plated, of a substance reduced at a nobleer potential than the plating metal contained in the plating solution or a reduced form of the substance, in order to maintain the purity of the plating metal. A plating solution characterized in that the amount is 10 ppm or less. Fourth, a plating method using these plating solutions is characterized by blowing gas or mechanically stirring the plating solution using a device such as a stirrer during plating. This is a plating method. The plating solution and plating method of the present invention can be applied to a wide variety of applications. Here, an embodiment will be described for a damascene process of an LSI and a build-up substrate which is a kind of high-density printed circuit board. FIG. 1 is a schematic cross-sectional view showing a schematic flow of the LSI damascene process. An insulating layer (oxide film) is formed on a silicon substrate, and holes or grooves are formed by a conventional method (FIG. 1A). Next, a barrier layer is formed on the surface of the insulating layer in order to prevent the reaction between the plating metal and the insulating layer and the diffusion of the plating metal into the insulating layer (FIG. 1B). As the barrier layer, T
In many cases, a high melting point metal such as iN, Ta, or W is used. After the formation of the barrier layer, a seed layer is formed on the entire surface of the substrate for electroplating. For forming the seed layer, a sputtering method is generally used (FIG. 1C). Then, using this seed layer as a seed, plating is performed by electroplating to a thickness sufficient to fill the holes and grooves. At this time, in an ordinary electroplating method, an electric field concentrates on the edges of the holes and the grooves, and before the holes and the grooves are filled, the entrances of the holes and the grooves are closed, and the holes and grooves are not sufficiently filled to leave voids. However, generation of voids can be completely avoided by using the plating solution of the present invention. Since the plating solution of the present invention contains an additive that is reduced at a potential nobler than the plating metal ions, the additive is reduced at the potential of the plating reaction. The chemical equivalent of the deposited plating metal with respect to the amount of electricity (coulomb) flowing between the surface of the object to be plated (cathode) and the anode in the plating solution is referred to as current efficiency. The current efficiency becomes 1 or less. Incidentally, the current efficiency when all the flowing current is used for the plating reaction is 1, and the current efficiency when current is consumed other than the plating reaction by the side reaction is 1 or less. As described above, when the plating solution of the present invention containing an additive which is reduced on the surface of the body to be plated and contains an additive that reduces the current efficiency is used, it is possible to exert a great effect on filling holes and grooves. . Immediately after plating starts, the reduction reaction of the additive and the reduction reaction of the plating metal proceed simultaneously on all the seed layer surfaces such as the inner wall surfaces of the holes and grooves and the other substrate surfaces, and the current efficiency is considerably smaller than 1. Become. However, after a while, generally several seconds, the current efficiency of the inner wall surface of the hole or groove becomes a value close to 1, and the current efficiency becomes larger than that of the substrate surface other than the inner wall surface of the hole or groove. That is, after several seconds, the current efficiency of the plating reaction on the inner wall surface of the hole and the groove becomes a value close to 1, whereas the current efficiency of the plating reaction on the surface other than the inner wall surface of the hole and the groove does not increase so much. It becomes a small value of 1 or less. After a certain period of time, the current efficiency of the plating reaction is as follows: hole, groove inner wall surface> other surface. This is because the reduction reaction of the additive becomes a substance supply rate-determining substance. That is, at the start of plating, the plating solution in the holes and grooves contains the same amount of additive as the bulk plating solution. Immediately reduced consumption. Since the plating solution in the holes and grooves is stagnant, the supply of the additive from the bulk plating solution to the plating solution in the holes and grooves is almost entirely due to diffusion, but it cannot catch up with the consumption by electrolytic reduction. Almost no additive concentration in plating solution in holes and grooves
And the current efficiency of the plating reaction is close to 1. On the other hand, on surfaces other than the hole and groove inner wall surfaces, the additive is supplied smoothly, so that the current efficiency of the plating reaction is 1 or less, which is smaller than the current efficiency of the plating reaction on the hole and groove inner wall surfaces. It will be a small value. Further, by stirring the plating solution, the supply of the additive to the surface other than the inner wall surface of the hole and the groove becomes smoother, but the plating solution in the hole and the groove stays. Do not receive much. Therefore, by stirring the plating solution, the difference between the current efficiency of the plating reaction on the inner wall surface of the hole and the groove and the current efficiency of the plating reaction on the surface other than the inner wall surface of the hole and the groove can be increased. The current efficiency of the plating reaction is determined by the following formula:
By doing so, the plating film thickness can be set to “the plating film thickness deposited on the inner wall surface of the hole or the groove> the plating film thickness deposited on other surfaces”. By the above action mechanism, in the plating process, as shown in FIG. 1d, plating deposition occurs preferentially in the holes and grooves, and the plating film thickness in the holes and grooves becomes larger than the plating film thickness on other surfaces. . As a result, no seams or voids remain, and the holes and grooves are completely filled as shown in FIG. 1e. By using the present invention, it becomes possible to fill holes and grooves having a large aspect ratio, which cannot be filled conventionally. Further, an embodiment of a build-up board of the present invention will be described. Even in the case of a build-up substrate, when the via holes for interlayer connection are completely filled by plating, the same as in the case of the above-described LSI damascene process. Therefore, here, a plating method when the via hole is not completely filled by plating will be described. First, as shown in a schematic sectional view of FIG. 5A, a build-up insulating layer is formed on the surface of an inner circuit board formed of glass epoxy or the like, and a via hole is formed. After that, the entire surface of the substrate is thinly electrolessly plated or subjected to a special pretreatment for directly electroplating the surface of the insulating substrate, which is generally called "direct plating" (FIG. 5b). Conduction is performed and electroplating is performed. When a normal plating solution is used, the cross-sectional shape of the via hole after plating is such that the plating thickness at the edge of the via hole entrance is large and the plating thickness at the bottom of the via hole is small, as shown in FIG. It is conceivable to increase the plating film thickness at the bottom of the via hole and to increase the entire plating film thickness in order to ensure reliability.However, in the case of a build-up board, the conductor formed by plating is etched to form a circuit. Increasing the plating film thickness on the substrate surface causes a decrease in etching accuracy, which is a problem. When the present invention is used, the plating thickness at the bottom of the via hole can be increased without increasing the plating thickness on the surface. That is, the current efficiency of the plating reaction is larger in the via hole than in the surface. This is because, as in the case of the above-described LSI damascene process, the reduction reaction of the additive is rate-controlled by the substance supply. The additives in the plating solution in the via holes are reduced and consumed immediately after the start of plating, and the current efficiency of the plating reaction rises to a value close to 1, but the additives on the surface are sufficiently supplied from the bulk, Efficiency remains low. Therefore, the effect of stirring the plating solution can be expected as in the case of the LSI damascene process. Due to the above effects, the cross-section of the substrate after plating is very advantageous in connection reliability, as shown in FIG. 5c, where the plating film thickness in the via hole especially near the bottom is larger than the plating film thickness on the substrate surface. Structure. The above effects can be obtained by any plating solution containing a substance that is reduced at a potential nobler than the reduction potential of the plating metal ion, and does not depend on the type of metal or plating solution. The concentration of the additive is within a range in which the reduction reaction of the additive is controlled by the substance supply, and is usually 0.1%.
It is in the range of about 0001 mol / l to 1.0 mol / l. The type of additive depends on the plating solution and cannot be limited.However, physical properties such as electrical resistance and ductility of the plating film often pose a problem. In this case, a large amount of the reduced form of the additive or the additive itself is used. The system mixed into the plating film should be avoided. A metal ion can be considered as an additive mixed in a large amount into the film. However, it is desirable to avoid using a metal ion as an additive when the above-mentioned physical properties are problematic. In particular, when the plating metal is copper, effective additives include hydrogen peroxide, ammonium persulfate, and benzoquinones. In the plating solution, there are substances whose reduction potential on copper is more noble than the potential of copper deposition. . Such benzoquinones include 1,4-benzoquinone, methyl-1,4
-Benzoquinone, 2,5-dimethyl-1,4-benzoquinone, 2,3-dimethyl-1,4-benzoquinone, trimethyl-1,4-benzoquinone, 2-methyl-5-isopropyl-1,4-benzoquinone, hydroxy -1, 4
-Benzoquinone, 2,5-dihydroxy-1,4-benzoquinone, 2,5-dihydroxy-3,6-dichloro-
1,4-benzoquinone, 2,5-dimethoxy-1,4-
Benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,5-diethoxy-1,4-benzoquinone, chloro-1,4-benzoquinone, 2,3-dichloro-1,
4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, bromo-1,4-benzoquinone, 2,5-dibromo-1,
4-benzoquinone, 2-chloro-5-methyl-1,4-
Benzoquinone, 1,2-benzoquinone, methyl-1,2
-Benzoquinone, 4-carboxy-1,2-benzoquinone, 4-carbethoxy-1,2-benzoquinone, 3-
Hydroxy-1,2-benzoquinone, 3-hydroxy-
5-carboxy-1,2-benzoquinone, tetrachloro-1,2-benzoquinone, tetrabromo-1,2-benzoquinone, 1,4-naphthoquinone, 1,4-naphthoquinone-2-sulfonate, 9,10-anthraquinone,
9,10-anthraquinone-2-sulfonate,
10-anthraquinone-1-sulfonate, 9,10
Anthraquinone-1,8-disulfonate, 9.1
0-anthraquinone-1,5-disulfonate, 5,
There is 8-quinoline quinone. In addition, as described above, it is very difficult to stir the plating solution during plating, because the effect of causing a difference in the current efficiency of the plating reaction can be enhanced by stirring the plating solution as described above. It is effective for Hereinafter, specific examples for implementing the present invention will be described. The shape and material of these insulating materials and the types of conductive metals do not limit the present invention.

【発明の実施の形態】本発明を実施するに当たり以下の
基板および処理液を用いた。 ・［基板１］シリコン基板上にＳｉＯ2 絶縁層を１μｍ
形成し、このＳｉＯ2 絶縁層に定法のドライエッチング
によりφ０.２μｍ ，深さ１μｍの穴を加工した。次い
で、スパッタ法によりＴａのバリヤー層を、穴の側壁部
で３０ｎｍになるように形成し、さらにスパッタ法で銅
シード層を、穴側壁で３０ｎｍになるように形成した基
板。 ・［基板２］シリコン基板上にＳｉＯ2 絶縁層を１μｍ
形成し、このＳｉＯ2 絶縁層に定法のドライエッチング
により幅０.２μｍ ，深さ１μｍの溝を加工した。次い
で、スパッタ法によりＴａのバリヤー層を、溝の側壁部
で３０ｎｍになるように形成し、さらにスパッタ法で銅
シード層を、溝側壁で３０ｎｍになるように形成した基
板。 ・［基板３］シリコン基板上にＳｉＯ2 絶縁層を１μｍ
形成し、このＳｉＯ2 絶縁層に定法のドライエッチング
によりφ０.２μｍ ，深さ１μｍの穴を加工した。次い
で、さらにＳｉＯ2 絶縁層を１μｍ形成しこのＳｉＯ2
絶縁層に定法のドライエッチングにより幅０.２μｍ ，
深さ１μｍの溝を加工した。この基板では、一部分で上
層の溝と、下層の穴がつながった形になっており、いわ
ゆるデュアルダマシンの形態になっている。その後、ス
パッタ法によりＴａのバリヤー層を、穴と溝の側壁部で
３０ｎｍになるように形成し、さらにスパッタ法で銅シ
ード層を、穴と溝側壁で３０ｎｍになるように形成した
基板。 ・［基板４］ガラスエポキシ基材上に厚さ１８μｍの銅
箔を有する銅張り積層板表面に、エッチングレジストを
形成し、エッチングにより銅パターンを形成した。その
後、エッチングレジストを剥離後、銅パターン表面を化
学的に酸化し、粗化する、いわゆるブラウンオキサイド
処理を施した基板。 ・［基板５］セラミックグリーンシート表面に、銅ペー
ストを所定のパターンにスクリーン印刷して１５層積層
し、同時焼成したセラミック配線基板。 ・［基板６］ポリイミド表面に、スパッタリングにより
クロムを厚さ０.０５μｍ 、次いで銅を厚さ５.０μ
ｍ、更にクロムを厚さ０.０５μｍ形成後、表面にエッ
チングレジストを形成し、エッチングによりクロム／銅
／クロムの３層導体パターンを形成した基板。 ・［電気銅めっき液］ 硫酸銅・・・７５ｇ／ｌ 濃硫酸・・・１００ｍｌ／ｌ 添加剤・・・・各実施例中に記載 ・［電気ニッケルめっき液］ 硫酸ニッケル・・・２８０ｇ／ｌ 塩化ニッケル・・・４５ｇ／ｌ ほう酸・・・４０ｇ／ｌ 添加剤・・・・各実施例中に記載 〔実施例１〕φ８インチの基板１を用いた。めっき液
は、上記電気銅めっき液に添加剤として過酸化水素を
０.０１mol／ｌの濃度になるように加えたものを用い
た。基板を超純水にて洗浄後、過酸化水素を添加した総
量４０リットルの電気銅めっき液中に浸清し、電流密度
０.８Ａ／ｄｍ2で、５分間めっきを行った。この時、め
っき液はめっき槽外部のろ過フィルターとの間を、毎分
５０リットルの循環量で循環しており、この循環流によ
りめっき液は十分に撹拌されている。５分のめっき後、
基板をめっき液より取り出し、φ０.２μｍ の穴へのめ
っき銅埋め込み性を評価した。１００穴以上の穴を断面
観察した結果、すべての穴で銅が完全に埋め込まれてお
り、ボイド等の欠陥は無いことがわかった。以上の結果
より、本発明は微***への銅の埋め込みに対し、非常に
有効であることが分かった。更に、銅めっきにより埋め
込まれる過程を観察した。上記と同様な条件でめっきを
行い、めっき開始３０秒後、基板をめっき液中より取り
出し、穴断面を電子顕微鏡により観察した。その結果、
基板表面のめっき膜厚はほとんど増加していないのに対
し、穴内のめっき膜厚は表面のめっき膜厚の２倍程度に
なっていることがわかった。上記添加剤を含むめっき液
を用いることにより、本発明の作用機構である、穴内の
めっき反応の電流効率が、表面のめっき反応の電流効率
よりも高くなるという状況を発現できることが明らかと
なった。 〔実施例２〕φ８インチの基板１を用いた。めっき液
は、上記電気銅めっき液に添加剤として１，４−ベンゾ
キノンを０.０１mol／ｌの濃度になるように加えたもの
を用いた。基板を超純水にて洗浄後、ベンゾキノンを添
加した総量４０リットルの電気銅めっき液中に浸清し、
電流密度０.８Ａ／ｄｍ2で、５分間めっきを行った。こ
の時、めっき液はめっき槽外部のろ過フィルターとの間
を、毎分５０リットルの循環量で循環しており、この循
環流によりめっき液は十分に撹拌されている。５分のめ
っき後、基板をめっき液より取り出し、φ０.２μｍ の
穴へのめっき銅埋め込み性を評価した。１００穴以上の
穴を断面観察した結果、すべての穴で銅が完全に埋め込
まれており、ボイド等の欠陥は無いことがわかった。以
上の結果より、本発明は微***への銅の埋め込みに対
し、非常に有効であることが分かった。更に、銅めっき
により埋め込まれる過程を観察した。上記と同様な条件
でめっきを行い、めっき開始３０秒後、基板をめっき液
中より取り出し、穴断面を電子顕微鏡により観察した。
その結果、基板表面のめっき膜厚はほとんど増加してい
ないのに対し、穴内のめっき膜厚は表面のめっき膜厚の
２倍程度になっていることがわかった。上記添加剤を含
むめっき液を用いることにより、本発明の作用機構であ
る、穴内のめっき反応の電流効率が、表面のめっき反応
の電流効率よりも高くなるという状況を発現できること
が明らかとなった。 〔実施例３〕めっき液に加える添加剤をメチル−１，４
−ベンゾキノンとした以外は、すべて実施例２と同様な
検討を行った。その結果、すべての穴で銅が完全に埋め
込まれており、ボイド等の欠陥は無いことがわかった。
以上より、本発明は微***への銅の埋め込みに対し、非
常に有効であることが分かった。更に、銅めっきにより
埋め込まれる過程を観察した。上記と同様な条件でめっ
きを行い、めっき開始３０秒後、基板をめっき液中より
取り出し、穴断面を電子顕微鏡により観察した。その結
果、基板表面のめっき膜厚はほとんど増加していないの
に対し、穴内のめっき膜厚は表面のめっき膜厚の２倍程
度になっていることがわかった。上記添加剤を含むめっ
き液を用いることにより、本発明の作用機構である、穴
内のめっき反応の電流効率が、表面のめっき反応の電流
効率よりも高くなるという状況を発現できることが明ら
かとなった。 〔実施例４〕めっき液に加える添加剤を２，５−ジメチ
ル−１，４−ベンゾキノンとした以外は、すべて実施例
２と同様な検討を行った。その結果、すべての穴で銅が
完全に埋め込まれており、ボイド等の欠陥は無いことが
わかった。以上より、本発明は微***への銅の埋め込み
に対し、非常に有効であることが分かった。更に、銅め
っきにより埋め込まれる過程を観察した。上記と同様な
条件でめっきを行い、めっき開始３０秒後、基板をめっ
き液中より取り出し、穴断面を電子顕微鏡により観察し
た。その結果、基板表面のめっき膜厚はほとんど増加し
ていないのに対し、穴内のめっき膜厚は表面のめっき膜
厚の２倍程度になっていることがわかった。上記添加剤
を含むめっき液を用いることにより、本発明の作用機構
である、穴内のめっき反応の電流効率が、表面のめっき
反応の電流効率よりも高くなるという状況を発現できる
ことが明らかとなった。 〔実施例５〕めっき液に加える添加剤を２，３−ジメチ
ル−１，４−ベンゾキノンとした以外は、すべて実施例
２と同様な検討を行った。その結果、すべての穴で銅が
完全に埋め込まれており、ボイド等の欠陥は無いことが
わかった。以上より、本発明は微***への銅の埋め込み
に対し、非常に有効であることが分かった。更に、銅め
っきにより埋め込まれる過程を観察した。上記と同様な
条件でめっきを行い、めっき開始３０秒後、基板をめっ
き液中より取り出し、穴断面を電子顕微鏡により観察し
た。その結果、基板表面のめっき膜厚はほとんど増加し
ていないのに対し、穴内のめっき膜厚は表面のめっき膜
厚の２倍程度になっていることがわかった。上記添加剤
を含むめっき液を用いることにより、本発明の作用機構
である、穴内のめっき反応の電流効率が、表面のめっき
反応の電流効率よりも高くなるという状況を発現できる
ことが明らかとなった。 〔実施例６〕めっき液に加える添加剤をトリメチル−
１，４−ベンゾキノンとした以外は、すべて実施例２と
同様な検討を行った。その結果、すべての穴で銅が完全
に埋め込まれており、ボイド等の欠陥は無いことがわか
った。以上より、本発明は微***への銅の埋め込みに対
し、非常に有効であることが分かった。更に、銅めっき
により埋め込まれる過程を観察した。上記と同様な条件
でめっきを行い、めっき開始３０秒後、基板をめっき液
中より取り出し、穴断面を電子顕微鏡により観察した。
その結果、基板表面のめっき膜厚はほとんど増加してい
ないのに対し、穴内のめっき膜厚は表面のめっき膜厚の
２倍程度になっていることがわかった。上記添加剤を含
むめっき液を用いることにより、本発明の作用機構であ
る、穴内のめっき反応の電流効率が、表面のめっき反応
の電流効率よりも高くなるという状況を発現できること
が明らかとなった。 〔実施例７〕めっき液に加える添加剤を２−メチル−５
−イソプロピル−１，４−ベンゾキノンとした以外は、
すべて実施例２と同様な検討を行った。その結果、すべ
ての穴で銅が完全に埋め込まれており、ボイド等の欠陥
は無いことがわかった。以上より、本発明は微***への
銅の埋め込みに対し、非常に有効であることが分かっ
た。更に、銅めっきにより埋め込まれる過程を観察し
た。上記と同様な条件でめっきを行い、めっき開始３０
秒後、基板をめっき液中より取り出し、穴断面を電子顕
微鏡により観察した。その結果、基板表面のめっき膜厚
はほとんど増加していないのに対し、穴内のめっき膜厚
は表面のめっき膜厚の２倍程度になっていることがわか
った。上記添加剤を含むめっき液を用いることにより、
本発明の作用機構である、穴内のめっき反応の電流効率
が、表面のめっき反応の電流効率よりも高くなるという
状況を発現できることが明らかとなった。 〔実施例８〕めっき液に加える添加剤をヒドロキシ−
１，４−ベンゾキノンとした以外は、すべて実施例２と
同様な検討を行った。その結果、すべての穴で銅が完全
に埋め込まれており、ボイド等の欠陥は無いことがわか
った。以上より、本発明は微***への銅の埋め込みに対
し、非常に有効であることが分かった。更に、銅めっき
により埋め込まれる過程を観察した。上記と同様な条件
でめっきを行い、めっき開始３０秒後、基板をめっき液
中より取り出し、穴断面を電子顕微鏡により観察した。
その結果、基板表面のめっき膜厚はほとんど増加してい
ないのに対し、穴内のめっき膜厚は表面のめっき膜厚の
２倍程度になっていることがわかった。上記添加剤を含
むめっき液を用いることにより、本発明の作用機構であ
る、穴内のめっき反応の電流効率が、表面のめっき反応
の電流効率よりも高くなるという状況を発現できること
が明らかとなった。 〔実施例９〕めっき液に加える添加剤を２，５−ジヒド
ロキシ−１，４−ベンゾキノンとした以外は、すべて実
施例２と同様な検討を行った。その結果、すべての穴で
銅が完全に埋め込まれており、ボイド等の欠陥は無いこ
とがわかった。以上より、本発明は微***への銅の埋め
込みに対し、非常に有効であることが分かった。更に、
銅めっきにより埋め込まれる過程を観察した。上記と同
様な条件でめっきを行い、めっき開始３０秒後、基板を
めっき液中より取り出し、穴断面を電子顕微鏡により観
察した。その結果、基板表面のめっき膜厚はほとんど増
加していないのに対し、穴内のめっき膜厚は表面のめっ
き膜厚の２倍程度になっていることがわかった。上記添
加剤を含むめっき液を用いることにより、本発明の作用
機構である、穴内のめっき反応の電流効率が、表面のめ
っき反応の電流効率よりも高くなるという状況を発現で
きることが明らかとなった。 〔実施例１０〕めっき液に加える添加剤を２，５−ジヒ
ドロキシ−３，６−ジクロロ−１，４−ベンゾキノンと
した以外は、すべて実施例２と同様な検討を行った。そ
の結果、すべての穴で銅が完全に埋め込まれており、ボ
イド等の欠陥は無いことがわかった。以上より、本発明
は微***への銅の埋め込みに対し、非常に有効であるこ
とが分かった。更に、銅めっきにより埋め込まれる過程
を観察した。上記と同様な条件でめっきを行い、めっき
開始３０秒後、基板をめっき液中より取り出し、穴断面
を電子顕微鏡により観察した。その結果、基板表面のめ
っき膜厚はほとんど増加していないのに対し、穴内のめ
っき膜厚は表面のめっき膜厚の２倍程度になっているこ
とがわかった。上記添加剤を含むめっき液を用いること
により、本発明の作用機構である、穴内のめっき反応の
電流効率が、表面のめっき反応の電流効率よりも高くな
るという状況を発現できることが明らかとなった。 〔実施例１１〕めっき液に加える添加剤を２，５−ジメ
トキシ−１，４−ベンゾキノンとした以外は、すべて実
施例２と同様な検討を行った。その結果、すべての穴で
銅が完全に埋め込まれており、ボイド等の欠陥は無いこ
とがわかった。以上より、本発明は微***への銅の埋め
込みに対し、非常に有効であることが分かった。更に、
銅めっきにより埋め込まれる過程を観察した。上記と同
様な条件でめっきを行い、めっき開始３０秒後、基板を
めっき液中より取り出し、穴断面を電子顕微鏡により観
察した。その結果、基板表面のめっき膜厚はほとんど増
加していないのに対し、穴内のめっき膜厚は表面のめっ
き膜厚の２倍程度になっていることがわかった。上記添
加剤を含むめっき液を用いることにより、本発明の作用
機構である、穴内のめっき反応の電流効率が、表面のめ
っき反応の電流効率よりも高くなるという状況を発現で
きることが明らかとなった。 〔実施例１２〕めっき液に加える添加剤を２，６−ジメ
トキシ−１，４−ベンゾキノンとした以外は、すべて実
施例２と同様な検討を行った。その結果、すべての穴で
銅が完全に埋め込まれており、ボイド等の欠陥は無いこ
とがわかった。以上より、本発明は微***への銅の埋め
込みに対し、非常に有効であることが分かった。更に、
銅めっきにより埋め込まれる過程を観察した。上記と同
様な条件でめっきを行い、めっき開始３０秒後、基板を
めっき液中より取り出し、穴断面を電子顕微鏡により観
察した。その結果、基板表面のめっき膜厚はほとんど増
加していないのに対し、穴内のめっき膜厚は表面のめっ
き膜厚の２倍程度になっていることがわかった。上記添
加剤を含むめっき液を用いることにより、本発明の作用
機構である、穴内のめっき反応の電流効率が、表面のめ
っき反応の電流効率よりも高くなるという状況を発現で
きることが明らかとなった。 〔実施例１３〕めっき液に加える添加剤を２，５−ジエ
トキシ−１，４−ベンゾキノンとした以外は、すべて実
施例２と同様な検討を行った。その結果、すべての穴で
銅が完全に埋め込まれており、ボイド等の欠陥は無いこ
とがわかった。以上より、本発明は微***への銅の埋め
込みに対し、非常に有効であることが分かった。更に、
銅めっきにより埋め込まれる過程を観察した。上記と同
様な条件でめっきを行い、めっき開始３０秒後、基板を
めっき液中より取り出し、穴断面を電子顕微鏡により観
察した。その結果、基板表面のめっき膜厚はほとんど増
加していないのに対し、穴内のめっき膜厚は表面のめっ
き膜厚の２倍程度になっていることがわかった。上記添
加剤を含むめっき液を用いることにより、本発明の作用
機構である、穴内のめっき反応の電流効率が、表面のめ
っき反応の電流効率よりも高くなるという状況を発現で
きることが明らかとなった。 〔実施例１４〕めっき液に加える添加剤をクロロ−１，
４−ベンゾキノンとした以外は、すべて実施例２と同様
な検討を行った。その結果、すべての穴で銅が完全に埋
め込まれており、ボイド等の欠陥は無いことがわかっ
た。以上より、本発明は微***への銅の埋め込みに対
し、非常に有効であることが分かった。更に、銅めっき
により埋め込まれる過程を観察した。上記と同様な条件
でめっきを行い、めっき開始３０秒後、基板をめっき液
中より取り出し、穴断面を電子顕微鏡により観察した。
その結果、基板表面のめっき膜厚はほとんど増加してい
ないのに対し、穴内のめっき膜厚は表面のめっき膜厚の
２倍程度になっていることがわかった。上記添加剤を含
むめっき液を用いることにより、本発明の作用機構であ
る、穴内のめっき反応の電流効率が、表面のめっき反応
の電流効率よりも高くなるという状況を発現できること
が明らかとなった。 〔実施例１５〕めっき液に加える添加剤を２，３−ジク
ロロ−１，４−ベンゾキノンとした以外は、すべて実施
例２と同様な検討を行った。その結果、すべての穴で銅
が完全に埋め込まれており、ボイド等の欠陥は無いこと
がわかった。以上より、本発明は微***への銅の埋め込
みに対し、非常に有効であることが分かった。更に、銅
めっきにより埋め込まれる過程を観察した。上記と同様
な条件でめっきを行い、めっき開始３０秒後、基板をめ
っき液中より取り出し、穴断面を電子顕微鏡により観察
した。その結果、基板表面のめっき膜厚はほとんど増加
していないのに対し、穴内のめっき膜厚は表面のめっき
膜厚の２倍程度になっていることがわかった。上記添加
剤を含むめっき液を用いることにより、本発明の作用機
構である、穴内のめっき反応の電流効率が、表面のめっ
き反応の電流効率よりも高くなるという状況を発現でき
ることが明らかとなった。 〔実施例１６〕めっき液に加える添加剤を２，５−ジク
ロロ−１，４−ベンゾキノンとした以外は、すべて実施
例２と同様な検討を行った。その結果、すべての穴で銅
が完全に埋め込まれており、ボイド等の欠陥は無いこと
がわかった。以上より、本発明は微***への銅の埋め込
みに対し、非常に有効であることが分かった。更に、銅
めっきにより埋め込まれる過程を観察した。上記と同様
な条件でめっきを行い、めっき開始３０秒後、基板をめ
っき液中より取り出し、穴断面を電子顕微鏡により観察
した。その結果、基板表面のめっき膜厚はほとんど増加
していないのに対し、穴内のめっき膜厚は表面のめっき
膜厚の２倍程度になっていることがわかった。上記添加
剤を含むめっき液を用いることにより、本発明の作用機
構である、穴内のめっき反応の電流効率が、表面のめっ
き反応の電流効率よりも高くなるという状況を発現でき
ることが明らかとなった。 〔実施例１７〕めっき液に加える添加剤を２，６−ジク
ロロ−１，４−ベンゾキノンとした以外は、すべて実施
例２と同様な検討を行った。その結果、すべての穴で銅
が完全に埋め込まれており、ボイド等の欠陥は無いこと
がわかった。以上より、本発明は微***への銅の埋め込
みに対し、非常に有効であることが分かった。更に、銅
めっきにより埋め込まれる過程を観察した。上記と同様
な条件でめっきを行い、めっき開始３０秒後、基板をめ
っき液中より取り出し、穴断面を電子顕微鏡により観察
した。その結果、基板表面のめっき膜厚はほとんど増加
していないのに対し、穴内のめっき膜厚は表面のめっき
膜厚の２倍程度になっていることがわかった。上記添加
剤を含むめっき液を用いることにより、本発明の作用機
構である、穴内のめっき反応の電流効率が、表面のめっ
き反応の電流効率よりも高くなるという状況を発現でき
ることが明らかとなった。 〔実施例１８〕めっき液に加える添加剤をブロモ−１，
４−ベンゾキノンとした以外は、すべて実施例２と同様
な検討を行った。その結果、すべての穴で銅が完全に埋
め込まれており、ボイド等の欠陥は無いことがわかっ
た。以上より、本発明は微***への銅の埋め込みに対
し、非常に有効であることが分かった。更に、銅めっき
により埋め込まれる過程を観察した。上記と同様な条件
でめっきを行い、めっき開始３０秒後、基板をめっき液
中より取り出し、穴断面を電子顕微鏡により観察した。
その結果、基板表面のめっき膜厚はほとんど増加してい
ないのに対し、穴内のめっき膜厚は表面のめっき膜厚の
２倍程度になっていることがわかった。上記添加剤を含
むめっき液を用いることにより、本発明の作用機構であ
る、穴内のめっき反応の電流効率が、表面のめっき反応
の電流効率よりも高くなるという状況を発現できること
が明らかとなった。 〔実施例１９〕めっき液に加える添加剤を２，５−ジブ
ロモ−１，４−ベンゾキノンとした以外は、すべて実施
例２と同様な検討を行った。その結果、すべての穴で銅
が完全に埋め込まれており、ボイド等の欠陥は無いこと
がわかった。以上より、本発明は微***への銅の埋め込
みに対し、非常に有効であることが分かった。更に、銅
めっきにより埋め込まれる過程を観察した。上記と同様
な条件でめっきを行い、めっき開始３０秒後、基板をめ
っき液中より取り出し、穴断面を電子顕微鏡により観察
した。その結果、基板表面のめっき膜厚はほとんど増加
していないのに対し、穴内のめっき膜厚は表面のめっき
膜厚の２倍程度になっていることがわかった。上記添加
剤を含むめっき液を用いることにより、本発明の作用機
構である、穴内のめっき反応の電流効率が、表面のめっ
き反応の電流効率よりも高くなるという状況を発現でき
ることが明らかとなった。 〔実施例２０〕めっき液に加える添加剤を２−クロロ−
５−メチル−１，４−ベンゾキノンとした以外は、すべ
て実施例２と同様な検討を行った。その結果、すべての
穴で銅が完全に埋め込まれており、ボイド等の欠陥は無
いことがわかった。以上より、本発明は微***への銅の
埋め込みに対し、非常に有効であることが分かった。更
に、銅めっきにより埋め込まれる過程を観察した。上記
と同様な条件でめっきを行い、めっき開始３０秒後、基
板をめっき液中より取り出し、穴断面を電子顕微鏡によ
り観察した。その結果、基板表面のめっき膜厚はほとん
ど増加していないのに対し、穴内のめっき膜厚は表面の
めっき膜厚の２倍程度になっていることがわかった。上
記添加剤を含むめっき液を用いることにより、本発明の
作用機構である、穴内のめっき反応の電流効率が、表面
のめっき反応の電流効率よりも高くなるという状況を発
現できることが明らかとなった。 〔実施例２１〕めっき液に加える添加剤を１，２−ベン
ゾキノンとした以外は、すべて実施例２と同様な検討を
行った。その結果、すべての穴で銅が完全に埋め込まれ
ており、ボイド等の欠陥は無いことがわかった。以上よ
り、本発明は微***への銅の埋め込みに対し、非常に有
効であることが分かった。更に、銅めっきにより埋め込
まれる過程を観察した。上記と同様な条件でめっきを行
い、めっき開始３０秒後、基板をめっき液中より取り出
し、穴断面を電子顕微鏡により観察した。その結果、基
板表面のめっき膜厚はほとんど増加していないのに対
し、穴内のめっき膜厚は表面のめっき膜厚の２倍程度に
なっていることがわかった。上記添加剤を含むめっき液
を用いることにより、本発明の作用機構である、穴内の
めっき反応の電流効率が、表面のめっき反応の電流効率
よりも高くなるという状況を発現できることが明らかと
なった。 〔実施例２２〕めっき液に加える添加剤をメチル−１，
２−ベンゾキノンとした以外は、すべて実施例２と同様
な検討を行った。その結果、すべての穴で銅が完全に埋
め込まれており、ボイド等の欠陥は無いことがわかっ
た。以上より、本発明は微***への銅の埋め込みに対
し、非常に有効であることが分かった。更に、銅めっき
により埋め込まれる過程を観察した。上記と同様な条件
でめっきを行い、めっき開始３０秒後、基板をめっき液
中より取り出し、穴断面を電子顕微鏡により観察した。
その結果、基板表面のめっき膜厚はほとんど増加してい
ないのに対し、穴内のめっき膜厚は表面のめっき膜厚の
２倍程度になっていることがわかった。上記添加剤を含
むめっき液を用いることにより、本発明の作用機構であ
る、穴内のめっき反応の電流効率が、表面のめっき反応
の電流効率よりも高くなるという状況を発現できること
が明らかとなった。 〔実施例２３〕めっき液に加える添加剤を４−カルボキ
シ−１，２−ベンゾキノンとした以外は、すべて実施例
２と同様な検討を行った。その結果、すべての穴で銅が
完全に埋め込まれており、ボイド等の欠陥は無いことが
わかった。以上より、本発明は微***への銅の埋め込み
に対し、非常に有効であることが分かった。更に、銅め
っきにより埋め込まれる過程を観察した。上記と同様な
条件でめっきを行い、めっき開始３０秒後、基板をめっ
き液中より取り出し、穴断面を電子顕微鏡により観察し
た。その結果、基板表面のめっき膜厚はほとんど増加し
ていないのに対し、穴内のめっき膜厚は表面のめっき膜
厚の２倍程度になっていることがわかった。上記添加剤
を含むめっき液を用いることにより、本発明の作用機構
である、穴内のめっき反応の電流効率が、表面のめっき
反応の電流効率よりも高くなるという状況を発現できる
ことが明らかとなった。 〔実施例２４〕めっき液に加える添加剤を４−カルボエ
トキシ−１，２−ベンゾキノンとした以外は、すべて実
施例２と同様な検討を行った。その結果、すべての穴で
銅が完全に埋め込まれており、ボイド等の欠陥は無いこ
とがわかった。以上より、本発明は微***への銅の埋め
込みに対し、非常に有効であることが分かった。更に、
銅めっきにより埋め込まれる過程を観察した。上記と同
様な条件でめっきを行い、めっき開始３０秒後、基板を
めっき液中より取り出し、穴断面を電子顕微鏡により観
察した。その結果、基板表面のめっき膜厚はほとんど増
加していないのに対し、穴内のめっき膜厚は表面のめっ
き膜厚の２倍程度になっていることがわかった。上記添
加剤を含むめっき液を用いることにより、本発明の作用
機構である、穴内のめっき反応の電流効率が、表面のめ
っき反応の電流効率よりも高くなるという状況を発現で
きることが明らかとなった。 〔実施例２５〕めっき液に加える添加剤を３−ヒドロキ
シ−１，２−ベンゾキノンとした以外は、すべて実施例
２と同様な検討を行った。その結果、すべての穴で銅が
完全に埋め込まれており、ボイド等の欠陥は無いことが
わかった。以上より、本発明は微***への銅の埋め込み
に対し、非常に有効であることが分かった。更に、銅め
っきにより埋め込まれる過程を観察した。上記と同様な
条件でめっきを行い、めっき開始３０秒後、基板をめっ
き液中より取り出し、穴断面を電子顕微鏡により観察し
た。その結果、基板表面のめっき膜厚はほとんど増加し
ていないのに対し、穴内のめっき膜厚は表面のめっき膜
厚の２倍程度になっていることがわかった。上記添加剤
を含むめっき液を用いることにより、本発明の作用機構
である、穴内のめっき反応の電流効率が、表面のめっき
反応の電流効率よりも高くなるという状況を発現できる
ことが明らかとなった。 〔実施例２６〕めっき液に加える添加剤を３−ヒドロキ
シ−５−カルボキシ−１，２−ベンゾキノンとした以外
は、すべて実施例２と同様な検討を行った。その結果、
すべての穴で銅が完全に埋め込まれており、ボイド等の
欠陥は無いことがわかった。以上より、本発明は微***
への銅の埋め込みに対し、非常に有効であることが分か
った。更に、銅めっきにより埋め込まれる過程を観察し
た。上記と同様な条件でめっきを行い、めっき開始３０
秒後、基板をめっき液中より取り出し、穴断面を電子顕
微鏡により観察した。その結果、基板表面のめっき膜厚
はほとんど増加していないのに対し、穴内のめっき膜厚
は表面のめっき膜厚の２倍程度になっていることがわか
った。上記添加剤を含むめっき液を用いることにより、
本発明の作用機構である、穴内のめっき反応の電流効率
が、表面のめっき反応の電流効率よりも高くなるという
状況を発現できることが明らかとなった。 〔実施例２７〕めっき液に加える添加剤をテトラクロロ
−１，２−ベンゾキノンとした以外は、すべて実施例２
と同様な検討を行った。その結果、すべての穴で銅が完
全に埋め込まれており、ボイド等の欠陥は無いことがわ
かった。以上より、本発明は微***への銅の埋め込みに
対し、非常に有効であることが分かった。更に、銅めっ
きにより埋め込まれる過程を観察した。上記と同様な条
件でめっきを行い、めっき開始３０秒後、基板をめっき
液中より取り出し、穴断面を電子顕微鏡により観察し
た。その結果、基板表面のめっき膜厚はほとんど増加し
ていないのに対し、穴内のめっき膜厚は表面のめっき膜
厚の２倍程度になっていることがわかった。上記添加剤
を含むめっき液を用いることにより、本発明の作用機構
である、穴内のめっき反応の電流効率が、表面のめっき
反応の電流効率よりも高くなるという状況を発現できる
ことが明らかとなった。 〔実施例２８〕めっき液に加える添加剤をテトラブロモ
−１，２−ベンゾキノンとした以外は、すべて実施例２
と同様な検討を行った。その結果、すべての穴で銅が完
全に埋め込まれており、ボイド等の欠陥は無いことがわ
かった。以上より、本発明は微***への銅の埋め込みに
対し、非常に有効であることが分かった。更に、銅めっ
きにより埋め込まれる過程を観察した。上記と同様な条
件でめっきを行い、めっき開始３０秒後、基板をめっき
液中より取り出し、穴断面を電子顕微鏡により観察し
た。その結果、基板表面のめっき膜厚はほとんど増加し
ていないのに対し、穴内のめっき膜厚は表面のめっき膜
厚の２倍程度になっていることがわかった。上記添加剤
を含むめっき液を用いることにより、本発明の作用機構
である、穴内のめっき反応の電流効率が、表面のめっき
反応の電流効率よりも高くなるという状況を発現できる
ことが明らかとなった。 〔実施例２９〕めっき液に加える添加剤を１，４−ナフ
トキノンとした以外は、すべて実施例２と同様な検討を
行った。その結果、すべての穴で銅が完全に埋め込まれ
ており、ボイド等の欠陥は無いことがわかった。以上よ
り、本発明は微***への銅の埋め込みに対し、非常に有
効であることが分かった。更に、銅めっきにより埋め込
まれる過程を観察した。上記と同様な条件でめっきを行
い、めっき開始３０秒後、基板をめっき液中より取り出
し、穴断面を電子顕微鏡により観察した。その結果、基
板表面のめっき膜厚はほとんど増加していないのに対
し、穴内のめっき膜厚は表面のめっき膜厚の２倍程度に
なっていることがわかった。上記添加剤を含むめっき液
を用いることにより、本発明の作用機構である、穴内の
めっき反応の電流効率が、表面のめっき反応の電流効率
よりも高くなるという状況を発現できることが明らかと
なった。 〔実施例３０〕めっき液に加える添加剤を１，４−ナフ
トキノン−２−スルフォネイトとした以外は、すべて実
施例２と同様な検討を行った。その結果、すべての穴で
銅が完全に埋め込まれており、ボイド等の欠陥は無いこ
とがわかった。以上より、本発明は微***への銅の埋め
込みに対し、非常に有効であることが分かった。更に、
銅めっきにより埋め込まれる過程を観察した。上記と同
様な条件でめっきを行い、めっき開始３０秒後、基板を
めっき液中より取り出し、穴断面を電子顕微鏡により観
察した。その結果、基板表面のめっき膜厚はほとんど増
加していないのに対し、穴内のめっき膜厚は表面のめっ
き膜厚の２倍程度になっていることがわかった。上記添
加剤を含むめっき液を用いることにより、本発明の作用
機構である、穴内のめっき反応の電流効率が、表面のめ
っき反応の電流効率よりも高くなるという状況を発現で
きることが明らかとなった。 〔実施例３１〕めっき液に加える添加剤を９，１０−ア
ントラキノンとした以外は、すべて実施例２と同様な検
討を行った。その結果、すべての穴で銅が完全に埋め込
まれており、ボイド等の欠陥は無いことがわかった。以
上より、本発明は微***への銅の埋め込みに対し、非常
に有効であることが分かった。更に、銅めっきにより埋
め込まれる過程を観察した。上記と同様な条件でめっき
を行い、めっき開始３０秒後、基板をめっき液中より取
り出し、穴断面を電子顕微鏡により観察した。その結
果、基板表面のめっき膜厚はほとんど増加していないの
に対し、穴内のめっき膜厚は表面のめっき膜厚の２倍程
度になっていることがわかった。上記添加剤を含むめっ
き液を用いることにより、本発明の作用機構である、穴
内のめっき反応の電流効率が、表面のめっき反応の電流
効率よりも高くなるという状況を発現できることが明ら
かとなった。 〔実施例３２〕めっき液に加える添加剤を９，１０−ア
ントラキノン−２−スルフォネイトとした以外は、すべ
て実施例２と同様な検討を行った。その結果、すべての
穴で銅が完全に埋め込まれており、ボイド等の欠陥は無
いことがわかった。以上より、本発明は微***への銅の
埋め込みに対し、非常に有効であることが分かった。更
に、銅めっきにより埋め込まれる過程を観察した。上記
と同様な条件でめっきを行い、めっき開始３０秒後、基
板をめっき液中より取り出し、穴断面を電子顕微鏡によ
り観察した。その結果、基板表面のめっき膜厚はほとん
ど増加していないのに対し、穴内のめっき膜厚は表面の
めっき膜厚の２倍程度になっていることがわかった。上
記添加剤を含むめっき液を用いることにより、本発明の
作用機構である、穴内のめっき反応の電流効率が、表面
のめっき反応の電流効率よりも高くなるという状況を発
現できることが明らかとなった。 〔実施例３３〕めっき液に加える添加剤を９，１０−ア
ントラキノン−１−スルフォネイトとした以外は、すべ
て実施例２と同様な検討を行った。その結果、すべての
穴で銅が完全に埋め込まれており、ボイド等の欠陥は無
いことがわかった。以上より、本発明は微***への銅の
埋め込みに対し、非常に有効であることが分かった。更
に、銅めっきにより埋め込まれる過程を観察した。上記
と同様な条件でめっきを行い、めっき開始３０秒後、基
板をめっき液中より取り出し、穴断面を電子顕微鏡によ
り観察した。その結果、基板表面のめっき膜厚はほとん
ど増加していないのに対し、穴内のめっき膜厚は表面の
めっき膜厚の２倍程度になっていることがわかった。上
記添加剤を含むめっき液を用いることにより、本発明の
作用機構である、穴内のめっき反応の電流効率が、表面
のめっき反応の電流効率よりも高くなるという状況を発
現できることが明らかとなった。 〔実施例３４〕めっき液に加える添加剤を９，１０−ア
ントラキノン−１，８−ジスルフォネイトとした以外
は、すべて実施例２と同様な検討を行った。その結果、
すべての穴で銅が完全に埋め込まれており、ボイド等の
欠陥は無いことがわかった。以上より、本発明は微***
への銅の埋め込みに対し、非常に有効であることが分か
った。更に、銅めっきにより埋め込まれる過程を観察し
た。上記と同様な条件でめっきを行い、めっき開始３０
秒後、基板をめっき液中より取り出し、穴断面を電子顕
微鏡により観察した。その結果、基板表面のめっき膜厚
はほとんど増加していないのに対し、穴内のめっき膜厚
は表面のめっき膜厚の２倍程度になっていることがわか
った。上記添加剤を含むめっき液を用いることにより、
本発明の作用機構である、穴内のめっき反応の電流効率
が、表面のめっき反応の電流効率よりも高くなるという
状況を発現できることが明らかとなった。 〔実施例３５〕めっき液に加える添加剤を９，１０−ア
ントラキノン−１，５−ジスルフォネイトとした以外
は、すべて実施例２と同様な検討を行った。その結果、
すべての穴で銅が完全に埋め込まれており、ボイド等の
欠陥は無いことがわかった。以上より、本発明は微***
への銅の埋め込みに対し、非常に有効であることが分か
った。更に、銅めっきにより埋め込まれる過程を観察し
た。上記と同様な条件でめっきを行い、めっき開始３０
秒後、基板をめっき液中より取り出し、穴断面を電子顕
微鏡により観察した。その結果、基板表面のめっき膜厚
はほとんど増加していないのに対し、穴内のめっき膜厚
は表面のめっき膜厚の２倍程度になっていることがわか
った。上記添加剤を含むめっき液を用いることにより、
本発明の作用機構である、穴内のめっき反応の電流効率
が、表面のめっき反応の電流効率よりも高くなるという
状況を発現できることが明らかとなった。 〔実施例３６〕めっき液に加える添加剤を５，８−キノ
リンキノンとした以外は、すべて実施例２と同様な検討
を行った。その結果、すべての穴で銅が完全に埋め込ま
れており、ボイド等の欠陥は無いことがわかった。以上
より、本発明は微***への銅の埋め込みに対し、非常に
有効であることが分かった。更に、銅めっきにより埋め
込まれる過程を観察した。上記と同様な条件でめっきを
行い、めっき開始３０秒後、基板をめっき液中より取り
出し、穴断面を電子顕微鏡により観察した。その結果、
基板表面のめっき膜厚はほとんど増加していないのに対
し、穴内のめっき膜厚は表面のめっき膜厚の２倍程度に
なっていることがわかった。上記添加剤を含むめっき液
を用いることにより、本発明の作用機構である、穴内の
めっき反応の電流効率が、表面のめっき反応の電流効率
よりも高くなるという状況を発現できることが明らかと
なった。 〔実施例３７〕めっき液に加える添加剤を１，４−ベン
ゾキノンとし、そのめっき液中の濃度を０.０００１mol
／ｌとした以外はすべて実施例２と同様な検討を行っ
た。ここでは、めっき液中の添加剤濃度が０.０００１m
ol／ｌと低いため、スターラーを用いてめっき液を撹拌
し、基板表面への添加剤の供給がスムーズになるよう、
調整した。その結果、すべての穴で銅が完全に埋め込ま
れており、ボイド等の欠陥は無いことがわかった。尚、
撹拌の有無で結果を比較したところ、撹拌した基板の方
ではボイドは無く、良好な結果であったが、撹拌しない
場合には、ボイドの発生が確認された。また、めっき液
の撹拌をスターラーではなく、エアーを用いて行った。
めっき液中に、φ０.５mm の穴を５mmピッチであけた、
外形φ５mmのテフロンチューブを入れ、空気を毎分５リ
ットル吹き込んだ。気泡によりめっき液は激しく撹拌さ
れた。この状態で検討した結果、すべての穴で銅が完全
に埋め込まれており、ボイド等の欠陥は無いことがわか
った。以上より、本発明は微***への銅の埋め込みに対
し、非常に有効であることが分かった。更に、銅めっき
により埋め込まれる過程を観察した。上記と同様な条件
でめっきを行い、めっき開始３０秒後、基板をめっき液
中より取り出し、穴断面を電子顕微鏡により観察した。
その結果、基板表面のめっき膜厚はほとんど増加してい
ないのに対し、穴内のめっき膜厚は表面のめっき膜厚の
２倍程度になっていることがわかった。上記添加剤を含
むめっき液を用いることにより、本発明の作用機構であ
る、穴内のめっき反応の電流効率が、表面のめっき反応
の電流効率よりも高くなるという状況を発現できること
が明らかとなった。 〔実施例３８〕めっき液に加える添加剤を１，４−ベン
ゾキノンとし、そのめっき液中の濃度を１.０mol／ｌと
した以外はすべて実施例２と同様な検討を行った。その
結果、すべての穴で銅が完全に埋め込まれており、ボイ
ド等の欠陥は無いことがわかった。以上より、本発明は
微***への銅の埋め込みに対し、非常に有効であること
が分かった。更に、銅めっきにより埋め込まれる過程を
観察した。上記と同様な条件でめっきを行い、めっき開
始３０秒後、基板をめっき液中より取り出し、穴断面を
電子顕微鏡により観察した。その結果、基板表面のめっ
き膜厚はほとんど増加していないのに対し、穴内のめっ
き膜厚は表面のめっき膜厚の２倍程度になっていること
がわかった。上記添加剤を含むめっき液を用いることに
より、本発明の作用機構である、穴内のめっき反応の電
流効率が、表面のめっき反応の電流効率よりも高くなる
という状況を発現できることが明らかとなった。 〔実施例３９〕φ８インチの基板２を用いた。めっき液
は、上記電気銅めっき液に添加剤として過酸化水素を
０.０１mol／ｌの濃度になるように加えたものを用い
た。基板を超純水にて洗浄後、過酸化水素を添加した総
量４０リットルの電気銅めっき液中に浸清し、電流密度
０.８Ａ／ｄｍ2で、５分間めっきを行った。この時、め
っき液はめっき槽外部のろ過フィルターとの間を、毎分
５０リットルの循環量で循環しており、この循環流によ
りめっき液は十分に撹拌されている。５分のめっき後、
基板をめっき液より取り出し、幅０.２μｍ の溝へのめ
っき銅埋め込み性を評価した。１００本以上の溝を断面
観察した結果、すべての溝で銅が完全に埋め込まれてお
り、ボイド等の欠陥は無いことがわかった。以上の結果
より、本発明は微小溝への銅の埋め込みに対し、非常に
有効であることが分かった。更に、銅めっきにより埋め
込まれる過程を観察した。上記と同様な条件でめっきを
行い、めっき開始３０秒後、基板をめっき液中より取り
出し、溝断面を電子顕微鏡により観察した。その結果、
基板表面のめっき膜厚はほとんど増加していないのに対
し、溝内のめっき膜厚は表面のめっき膜厚の２倍程度に
なっていることがわかった。上記添加剤を含むめっき液
を用いることにより、本発明の作用機構である、溝内の
めっき反応の電流効率が、表面のめっき反応の電流効率
よりも高くなるという状況を発現できることが明らかと
なった。 〔実施例４０〕φ８インチの基板２を用いた。上記電気
銅めっき液に、１，４−ベンゾキノンを０.０１mol／ｌ
の濃度になるように加えたものをめっき液として用い
た。基板を超純水にて洗浄後、種々のベンゾキノン類を
添加した総量４０リットルの電気銅めっき液中に浸清
し、電流密度０.８Ａ／ｄｍ2で、５分間めっきを行っ
た。この時、めっき液はめっき槽外部のろ過フィルター
との間を、毎分５０リットルの循環量で循環しており、
この循環流によりめっき液は十分に撹拌されている。５
分のめっき後、基板をめっき液より取り出し、幅０.２
μｍ の溝へのめっき銅埋め込み性を評価した。１００
本以上の溝を断面観察した結果、すべての溝で銅が完全
に埋め込まれており、ボイド等の欠陥は無いことがわか
った。以上の結果より、本発明は微小溝への銅の埋め込
みに対し、非常に有効であることが分かった。更に、銅
めっきにより埋め込まれる過程を観察した。上記と同様
な条件でめっきを行い、めっき開始３０秒後、基板をめ
っき液中より取り出し、溝断面を電子顕微鏡により観察
した。その結果、基板表面のめっき膜厚はほとんど増加
していないのに対し、溝内のめっき膜厚は表面のめっき
膜厚の２倍程度になっていることがわかった。上記添加
剤を含むめっき液を用いることにより、本発明の作用機
構である、溝内のめっき反応の電流効率が、表面のめっ
き反応の電流効率よりも高くなるという状況を発現でき
ることが明らかとなった。 〔実施例４１〕φ８インチの基板３を用いた。上記電気
銅めっき液に、１，４−ベンゾキノンを０.０１mol／ｌ
の濃度になるように加えたものをめっき液として用い
た。基板を超純水にて洗浄後、１，４−ベンゾキノンを
添加した総量４０リットルの電気銅めっき液中に浸清
し、電流密度０.８Ａ／ｄｍ2で、５分間めっきを行っ
た。この時、めっき液はめっき槽外部のろ過フィルター
との間を、毎分５０リットルの循環量で循環しており、
この循環流によりめっき液は十分に撹拌されている。５
分のめっき後、基板をめっき液より取り出し、幅０.２
μｍ の溝さらにその下層の穴へのめっき銅埋め込み性
を評価した。１００カ所以上の溝とその下層の穴の断面
を観察した結果、すべての溝とその下層の穴は銅で完全
に埋め込まれており、ボイド等の欠陥は無いことがわか
った。以上の結果より、本発明は微小溝とその下層に形
成された穴への銅の埋め込みに対し、非常に有効である
ことが分かった。更に、銅めっきにより埋め込まれる過
程を観察した。上記と同様な条件でめっきを行い、めっ
き開始３０秒後、基板をめっき液中より取り出し、溝と
その下層に形成された穴の断面を電子顕微鏡により観察
した。その結果、基板表面のめっき膜厚はほとんど増加
していないのに対し、溝およびその下層に形成された穴
内のめっき膜厚は表面のめっき膜厚の２倍程度になって
いることがわかった。上記添加剤を含むめっき液を用い
ることにより、本発明の作用機構である、溝，穴内のめ
っき反応の電流効率が、表面のめっき反応の電流効率よ
りも高くなるという状況を発現できることが明らかとな
った。 〔実施例４２〕基板４を用いて、ビルドアップ方式の高
密度プリント基板への応用を検討した。基板４表面に感
光性の絶縁層を形成した。その絶縁層の厚みは５０μｍ
であり、所定の露光・現像処理により、φ１００μｍの
ビアホールを形成した。更に、絶縁層表面を過マンガン
酸を含有するアルカリ処理液で処理し、粗面化した後、
Ｐｄコロイドを含有する無電解めっき用の触媒処理プロ
セスで、所定の触媒処理を施した後、無電解銅めっきを
約２μｍの厚みになるように施した。この無電解銅めっ
き層をシード層として、電気銅めっきを行った。上記電
気銅めっき液に、１，４−ベンゾキノンを０.０１mol／
ｌの濃度になるように加えたものをめっき液として用い
た。基板を超純水にて洗浄後、１，４−ベンゾキノンを
添加した総量１００リットルの電気銅めっき液中に浸清
し、電流密度１.５Ａ／ｄｍ2 で、６０分間めっきを行
った。この時、めっき液はめっき槽外部のろ過フィルタ
ーとの間を、毎分１２０リットルの循環量で循環してお
り、この循環流によりめっき液は十分に撹拌されてい
る。めっき後基板を取り出し、断面を顕微鏡観察した。
その結果、ビアホール底部付近のめっき膜厚が、基板表
面のめっき膜厚の１.５ 倍程度になっており、十分な接
続が確保できた。以上の結果より、本発明により、ビル
ドアップ基板のビアホール接続に対し、ビアホール内部
のめっき膜厚を厚くでき、ビアホール接続信頼性の高い
基板が確保できることが明らかとなった。更に、本発明
によりビアホール接続を行い、２層のビルドアップ層を
形成した基板に、ＬＳＩをベアチップ実装した場合の断
面模式図を図６に示した。本発明により、高密度な配線
を、信頼性良く形成することが可能となり、図示したよ
うな構成の電子部品が容易に形成可能となった。 〔実施例４３〕１００mm角の大きさの基板５表面に、エ
ポキシを主成分とする厚さ２５μｍの熱硬化性接着フィ
ルムをはさみ、厚み２５μｍのポリイミドフィルム（片
面銅箔付き、日立化成工業社製：ＭＣＦ−５０００ Ｉ)
を加熱圧着した。銅箔の厚みは１２μｍで、接着フィル
ムとは反対側にくるようにした。接着後、銅箔表面に感
光性を有するエッチングレジスト（東京応化製：ＯＦＰ
Ｒ−８００）を形成し、所定の露光，現像工程によりビ
アホールを形成したい部分のレジストを除去する。次い
で、銅箔をエッチングによりパターニングし、その後、
所定の剥離液を用いてエッチングレジストを剥離した。
次に、ビアホールを加工した。ビアホール加工にはエキ
シマレーザを用いた。幅２０mmのレーザ光を、基板表面
より照射した。基板表面の銅箔がマスクになり、銅箔の
パターニングされた部分のみが加工される、いわゆるコ
ンフォーマルマスク法でビアホールを形成した。この時
形成したビアホールは、大きさφ５０μｍ，２mmピッチ
で合計２５００穴である。その後、基板全面に銅をスパ
ッタ法により、厚み約２μｍ形成した。このスパッタで
形成した銅をシード層として、電気銅めっきを行った。
上記電気銅めっき液に、１，４−ベンゾキノンを０.０
１mol／ｌの濃度になるように加えたものをめっき液と
して用いた。基板を超純水にて洗浄後、１，４−ベンゾ
キノンを添加した総量１００リットルの電気銅めっき液
中に浸清し、電流密度１.５Ａ／ｄｍ2で、６０分間めっ
きを行った。この時、めっき液はめっき槽外部のろ過フ
ィルターとの間を、毎分１２０リットルの循環量で循環
しており、この循環流によりめっき液は十分に撹拌され
ている。めっき後基板を取り出し、断面を顕微鏡観察し
た。その結果、めっき液中での還元電位が銅の電析の電
位よりも貴な１，４−ベンゾキノンを含むめっき液を用
いた場合には、ビアホール底部付近のめっき膜厚が、基
板表面のめっき膜厚の１.５ 倍程度になっており、十分
な接続が確保できた。以上の結果より、本発明により、
ビルドアップ基板のビアホール接続に対し、ビアホール
内部のめっき膜厚を厚くでき、ビアホール接続信頼性の
高い基板が確保できることが明らかとなった。 〔実施例４４〕１００mm角の大きさの基板６表面に、エ
ポキシを主成分とする厚さ２５μｍの熱硬化性接着フィ
ルムをはさみ、厚み２５μｍのポリイミドフィルム（片
面銅箔付き、日立化成工業社製：ＭＣＦ−５０００ Ｉ)
を加熱圧着した。銅箔の厚みは１２μｍで、接着フィル
ムとは反対側にくるようにした。接着後、銅箔表面に感
光性を有するエッチングレジスト（東京応化製：ＯＦＰ
Ｒ−８００）を形成し、所定の露光，現像工程によりビ
アホールを形成したい部分のレジストを除去する。次い
で、銅箔をエッチングによりパターニングし、その後、
所定の剥離液を用いてエッチングレジストを剥離した。
次に、ビアホールを加工した。ビアホール加工にはエキ
シマレーザを用いた。幅２０mmのレーザ光を、基板表面
より照射した。基板表面の銅箔がマスクになり、銅箔の
パターニングされた部分のみが加工される、いわゆるコ
ンフォーマルマスク法でビアホールを形成した。この時
形成したビアホールは、大きさφ５０μｍ，２mmピッチ
で合計２５００穴である。その後、ビアホール底部の３
層導体の最上面にあるクロム層を、１８％塩酸水溶液に
より除去した。次に、基板全面に銅をスパッタ法によ
り、厚み約２μｍ形成した。このスパッタで形成した銅
をシード層として、電気銅めっきを行った。上記電気銅
めっき液に、１，４−ベンゾキノンを０.０１mol／ｌの
濃度になるように加えたものをめっき液として用いた。
基板を超純水にて洗浄後、１，４−ベンゾキノンを添加
した総量１００リットルの電気銅めっき液中に浸清し、
電流密度１.５Ａ／ｄｍ2で、６０分間めっきを行った。
この時、めっき液はめっき槽外部のろ過フィルターとの
間を、毎分１２０リットルの循環量で循環しており、こ
の循環流によりめっき液は十分に撹拌されている。めっ
き後基板を取り出し、断面を顕微鏡観察した。その結
果、めっき液中での還元電位が銅の電析の電位よりも貴
な１，４−ベンゾキノンを含むめっき液を用いた場合に
は、ビアホール底部付近のめっき膜厚が、基板表面のめ
っき膜厚の１.５ 倍程度になっており、十分な接続が確
保できた。以上の結果より、本発明により、ビルドアッ
プ基板のビアホール接続に対し、ビアホール内部のめっ
き膜厚を厚くでき、ビアホール接続信頼性の高い基板が
確保できることが明らかとなった。 〔実施例４５〕基板４を用いて、ビルドアップ方式の高
密度プリント基板への応用を検討した。基板４表面に感
光性の絶縁層を形成した。その絶縁層の厚みは５０μｍ
であり、所定の露光・現像処理により、φ１００μｍの
ビアホールを形成した。更に、絶縁層表面を過マンガン
酸を含有するアルカリ処理液で処理し、粗面化した後、
Ｐｄコロイドを含有する無電解めっき用の触媒処理プロ
セスで、所定の触媒処理を施した後、次亜リン酸を還元
剤とした無電解ニッケルめっきを約２μｍの厚みになる
ように施した。この無電解ニッケルめっき層をシード層
として、電気ニッケルめっきを行った。上記電気ニッケ
ルめっき液に、１，４−ベンゾキノンを０.０１mol／ｌ
の濃度になるように加えたものをめっき液として用い
た。基板を超純水にて洗浄後、１，４−ベンゾキノンを
添加した総量１００リットルの電気ニッケルめっき液中
に浸清し、電流密度１.５Ａ／ｄｍ2で、６０分間めっき
を行った。この時、めっき液はめっき槽外部のろ過フィ
ルターとの間を、毎分１２０リットルの循環量で循環し
ており、この循環流によりめっき液は十分に撹拌されて
いる。めっき後基板を取り出し、断面を顕微鏡観察し
た。その結果、めっき液中での還元電位がニッケルの電
析の電位よりも貴な１，４−ベンゾキノンを含むめっき
液を用いた場合には、ビアホール底部付近のめっき膜厚
が、基板表面のめっき膜厚の１.５ 倍程度になってお
り、十分な接続が確保できた。以上の結果より、本発明
により、ビルドアップ基板のビアホール接続に対し、ビ
アホール内部のめっき膜厚を厚くでき、ビアホール接続
信頼性の高い基板が確保できることが明らかとなった。
更に、本発明によりビアホール接続を行い、２層のビル
ドアップ層を形成した基板に、ＬＳＩをベアチップ実装
した場合の断面模式図を図６に示した。本発明により、
高密度な配線を、信頼性良く形成することが可能とな
り、図示したような構成の電子部品が容易に形成可能と
なった。BEST MODE FOR CARRYING OUT THE INVENTION
A substrate and a processing solution were used.・ [Substrate 1] SiO on silicon substrateTwo1 μm insulation layer
Formed and this SiOTwoConventional dry etching of insulating layer
Thus, a hole having a diameter of 0.2 μm and a depth of 1 μm was machined. Next
Then, a barrier layer of Ta is formed by a sputtering method on the side wall of the hole.
Formed to a thickness of 30 nm, and copper
The seed layer was formed to have a thickness of 30 nm on the side wall of the hole.
Board.・ [Substrate 2] SiO on silicon substrateTwo1 μm insulation layer
Formed and this SiOTwoConventional dry etching of insulating layer
Thus, a groove having a width of 0.2 μm and a depth of 1 μm was processed. Next
Then, a barrier layer of Ta is formed by a sputtering method on the side wall of the groove.
Formed to a thickness of 30 nm, and copper
The seed layer was formed to have a thickness of 30 nm on the side wall of the groove.
Board.・ [Substrate 3] SiO on silicon substrateTwo1 μm insulation layer
Formed and this SiOTwoConventional dry etching of insulating layer
Thus, a hole having a diameter of 0.2 μm and a depth of 1 μm was machined. Next
And then SiOTwoAn insulating layer is formed to a thickness of 1 μm and this SiOTwo
The width of the insulating layer is 0.2 μm,
A 1 μm deep groove was machined. In this board, the upper part
The groove of the layer and the hole of the lower layer are connected,
It is in the form of a loose dual damascene. Then
A barrier layer of Ta is formed on the side walls of the holes and grooves by the putter method.
It is formed so as to have a thickness of 30 nm.
A metal layer was formed so as to have a thickness of 30 nm between the hole and the groove sidewall.
substrate.・ [Substrate 4] 18 μm thick copper on a glass epoxy substrate
Apply an etching resist to the surface of the copper-clad laminate with foil.
Then, a copper pattern was formed by etching. That
After that, after etching resist is removed, surface of copper pattern is formed.
So-called brown oxide that chemically oxidizes and roughens
Treated substrate.・ [Substrate 5] A copper sheet is placed on the surface of the ceramic green sheet.
Screens are screen-printed in a predetermined pattern and 15 layers are laminated
Then, the co-fired ceramic wiring board.・ [Substrate 6] On the polyimide surface by sputtering
Chromium is 0.05 μm thick, then copper is 5.0 μm thick
m and chromium to a thickness of 0.05 μm,
Chrome / copper by etching
/ A substrate on which a three-layer conductor pattern of chrome is formed.・ [Electric copper plating solution] Copper sulfate ・ ・ ・ 75g / l Concentrated sulfuric acid ・ ・ ・ 100ml / l Additives ・ ・ ・ ・ Description in each example ・ [Electric nickel plating solution] Nickel sulfate ・ ・ ・ 280g / l Nickel chloride: 45 g / l Boric acid: 40 g / l Additive: described in each Example [Example 1] A substrate 1 having a diameter of 8 inches was used. Plating solution
Uses hydrogen peroxide as an additive to the electrolytic copper plating solution.
Use the solution added to a concentration of 0.01 mol / l.
Was. After cleaning the substrate with ultrapure water,
Immerse in 40 liters of electrolytic copper plating solution,
0.8A / dmTwoFor 5 minutes. At this time
The plating solution flows between the filtration filter and the outside of the plating tank every minute.
It circulates at a circulating volume of 50 liters.
The plating solution is sufficiently stirred. After 5 minutes of plating,
Remove the substrate from the plating solution and fit it into a φ0.2μm hole.
The copper embedding property was evaluated. Cross section of more than 100 holes
As a result of observation, copper was completely embedded in all holes.
It was found that there were no defects such as voids. Above result
Therefore, the present invention is very effective in embedding copper in micro holes.
It turned out to be effective. In addition, fill with copper plating
Observed the process of getting stuck. Plating under the same conditions as above
30 seconds after plating starts, remove the substrate from the plating solution
It was taken out and the hole cross section was observed with an electron microscope. as a result,
Although the plating film thickness on the substrate surface has hardly increased
And the thickness of the plating in the hole is about twice the thickness of the plating on the surface.
It turned out that it was. Plating solution containing the above additives
By using, the action mechanism of the present invention,
The current efficiency of the plating reaction is the current efficiency of the surface plating reaction
It is clear that it is possible to express a situation where it is higher than
became. Example 2 A substrate 1 having a diameter of 8 inches was used. Plating solution
Is 1,4-benzoic acid as an additive to the electrolytic copper plating solution.
Quinone added to a concentration of 0.01 mol / l
Was used. After cleaning the substrate with ultrapure water, add benzoquinone
Immersed in a total of 40 liters of electrolytic copper plating solution
Current density 0.8A / dmTwoFor 5 minutes. This
The plating solution is between the filtration filter outside the plating tank
Is circulated at a circulation rate of 50 liters per minute.
The plating solution is sufficiently stirred by the reflux. 5 minutes
After removing the substrate from the plating solution,
The ability to embed plated copper in the holes was evaluated. 100 holes or more
As a result of cross-sectional observation of the holes, copper is completely embedded in all holes
It was found that there were no defects such as voids. Less than
From the above results, the present invention is suitable for embedding copper into micro holes.
And found to be very effective. In addition, copper plating
The process of embedding was observed. Same conditions as above
30 seconds after the start of plating, the substrate is plated with a plating solution.
It was taken out from the inside and the hole cross section was observed with an electron microscope.
As a result, the plating thickness on the substrate surface has almost increased.
In contrast, the plating thickness in the hole is
It turned out that it became about twice. Including the above additives
By using a plating solution,
Current efficiency of the plating reaction in the hole
That the current efficiency is higher than the current efficiency
Became clear. Example 3 The additive to be added to the plating solution was methyl-1,4
-The same as in Example 2 except that benzoquinone was used.
Study was carried out. As a result, all holes are completely filled with copper
It was found that there were no defects such as voids.
As described above, the present invention is applicable to the non-embedding of copper into micro holes.
It has always proven effective. Furthermore, by copper plating
The process of embedding was observed. Under the same conditions as above
30 seconds after starting plating, remove the substrate from the plating solution
It was taken out and the cross section of the hole was observed with an electron microscope. The result
As a result, the plating film thickness on the substrate surface has hardly increased
On the other hand, the plating thickness in the hole is about twice the plating thickness on the surface
I knew it was getting better. Including the above additives
By using a liquid, a hole, which is an action mechanism of the present invention,
The current efficiency of the plating reaction in
It is clear that a situation where efficiency is higher than that can be expressed
It was ok. Example 4 The additive added to the plating solution was 2,5-dimethyl
Examples except for the use of 1,4-benzoquinone
The same examination was performed as in 2. The result is copper in every hole
Completely buried and free from defects such as voids
all right. As described above, the present invention embeds copper in micro holes.
Was found to be very effective. In addition, copper
The process of embedding was observed. Same as above
Plating is performed under the conditions.
Take out of the solution and observe the cross section of the hole with an electron microscope.
Was. As a result, the plating film thickness on the substrate surface almost increased
The thickness of the plating film in the hole is not
It was found that the thickness was about twice as large. The above additives
Mechanism of the present invention by using a plating solution containing
The current efficiency of the plating reaction in the hole is
A situation where the current efficiency is higher than the current efficiency of the reaction can be expressed
It became clear. Example 5 The additive to be added to the plating solution was 2,3-dimethyl
Examples except for the use of 1,4-benzoquinone
The same examination was performed as in 2. The result is copper in every hole
Completely buried and free from defects such as voids
all right. As described above, the present invention embeds copper in micro holes.
Was found to be very effective. In addition, copper
The process of embedding was observed. Same as above
Plating is performed under the conditions.
Take out of the solution and observe the cross section of the hole with an electron microscope.
Was. As a result, the plating film thickness on the substrate surface almost increased
The thickness of the plating film in the hole is not
It was found that the thickness was about twice as large. The above additives
Mechanism of the present invention by using a plating solution containing
The current efficiency of the plating reaction in the hole is
A situation where the current efficiency is higher than the current efficiency of the reaction can be expressed
It became clear. Example 6 The additive to be added to the plating solution was trimethyl-
Except for using 1,4-benzoquinone,
A similar study was performed. The result is complete copper in all holes
It is clear that there are no defects such as voids
Was. As described above, the present invention is applicable to the embedding of copper into minute holes.
And found to be very effective. In addition, copper plating
The process of embedding was observed. Same conditions as above
30 seconds after the start of plating, the substrate is plated with a plating solution.
It was taken out from the inside and the hole cross section was observed with an electron microscope.
As a result, the plating thickness on the substrate surface has almost increased.
In contrast, the plating thickness in the hole is
It turned out that it became about twice. Including the above additives
By using a plating solution,
Current efficiency of the plating reaction in the hole
That the current efficiency is higher than the current efficiency
Became clear. Example 7 The additive to be added to the plating solution was 2-methyl-5
Isopropyl-1,4-benzoquinone
The same study as in Example 2 was performed. As a result,
Copper is completely buried in all holes, voids and other defects
Was not found. From the above, the present invention is applicable to micro holes.
Proved to be very effective for copper embedding
Was. In addition, observe the process of embedding by copper plating.
Was. Plating is performed under the same conditions as above, and plating starts 30
Seconds later, the substrate is taken out of the plating solution, and the cross section of the hole is observed with an electron microscope.
Observed with a microscope. As a result, the plating film thickness on the substrate surface
Does not increase, whereas the plating thickness in the hole
Shows that the thickness is about twice the thickness of the plating on the surface
Was. By using a plating solution containing the above additive,
Current efficiency of plating reaction in a hole, which is the mechanism of action of the present invention
, But higher than the current efficiency of the plating reaction on the surface
It became clear that the situation could be expressed. Example 8 The additive to be added to the plating solution was hydroxy-
Except for using 1,4-benzoquinone,
A similar study was performed. The result is complete copper in all holes
It is clear that there are no defects such as voids
Was. As described above, the present invention is applicable to the embedding of copper into minute holes.
And found to be very effective. In addition, copper plating
The process of embedding was observed. Same conditions as above
30 seconds after the start of plating, the substrate is plated with a plating solution.
It was taken out from the inside and the hole cross section was observed with an electron microscope.
As a result, the plating thickness on the substrate surface has almost increased.
In contrast, the plating thickness in the hole is
It turned out that it became about twice. Including the above additives
By using a plating solution,
Current efficiency of the plating reaction in the hole
That the current efficiency is higher than the current efficiency
Became clear. Example 9 The additive to be added to the plating solution was 2,5-dihydric
Except for Roxy-1,4-benzoquinone, all
The same study as in Example 2 was performed. As a result, in every hole
Make sure that copper is completely embedded and free from defects such as voids.
I understood. As described above, the present invention provides a method for embedding copper in micro holes.
It was found to be very effective for Furthermore,
The process of embedding by copper plating was observed. Same as above
Plating is performed under the same conditions.
Take out from the plating solution and observe the cross section of the hole with an electron microscope.
I thought. As a result, the plating thickness on the substrate surface almost increased.
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Above
By using a plating solution containing an additive, the operation of the present invention
The current efficiency of the plating reaction in the hole, which is a mechanism,
The situation that the current efficiency becomes higher than the current efficiency
It became clear that it could come. Example 10 The additive to be added to the plating solution was 2,5-diphenyl.
Droxy-3,6-dichloro-1,4-benzoquinone and
Except for this, the same examination as in Example 2 was performed. So
As a result, copper is completely embedded in all holes,
It was found that there was no defect such as an id. From the above, the present invention
Is very effective for embedding copper in micro holes.
I understood. In addition, the process of embedding by copper plating
Was observed. Plating under the same conditions as above
30 seconds after the start, remove the substrate from the plating solution
Was observed with an electron microscope. As a result,
Although the thickness of the coating film has hardly increased,
The plating film thickness is about twice the plating film thickness on the surface.
I understood. Use plating solution containing the above additives
Thus, the action mechanism of the present invention, the plating reaction in the hole
The current efficiency is higher than the current efficiency of the plating reaction on the surface.
It became clear that the situation that can be expressed. Example 11 The additive to be added to the plating solution was 2,5-dimethyl
Except for toxic-1,4-benzoquinone, all
The same study as in Example 2 was performed. As a result, in every hole
Make sure that copper is completely embedded and free from defects such as voids.
I understood. As described above, the present invention provides a method for embedding copper in micro holes.
It was found to be very effective for Furthermore,
The process of embedding by copper plating was observed. Same as above
Plating is performed under the same conditions.
Take out from the plating solution and observe the cross section of the hole with an electron microscope.
I thought. As a result, the plating thickness on the substrate surface almost increased.
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Above
By using a plating solution containing an additive, the operation of the present invention
The current efficiency of the plating reaction in the hole, which is a mechanism,
The situation that the current efficiency becomes higher than the current efficiency
It became clear that it could come. Example 12 The additive to be added to the plating solution was 2,6-dimethyl
Except for toxic-1,4-benzoquinone, all
The same study as in Example 2 was performed. As a result, in every hole
Make sure that copper is completely embedded and free from defects such as voids.
I understood. As described above, the present invention provides a method for embedding copper in micro holes.
It was found to be very effective for Furthermore,
The process of embedding by copper plating was observed. Same as above
Plating is performed under the same conditions.
Take out from the plating solution and observe the cross section of the hole with an electron microscope.
I thought. As a result, the plating thickness on the substrate surface almost increased.
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Above
By using a plating solution containing an additive, the operation of the present invention
The current efficiency of the plating reaction in the hole, which is a mechanism,
The situation that the current efficiency becomes higher than the current efficiency
It became clear that it could come. Example 13 The additive added to the plating solution was 2,5-die
Except for toxic-1,4-benzoquinone, all
The same study as in Example 2 was performed. As a result, in every hole
Make sure that copper is completely embedded and free from defects such as voids.
I understood. As described above, the present invention provides a method for embedding copper in micro holes.
It was found to be very effective for Furthermore,
The process of embedding by copper plating was observed. Same as above
Plating is performed under the same conditions.
Take out from the plating solution and observe the cross section of the hole with an electron microscope.
I thought. As a result, the plating thickness on the substrate surface almost increased.
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Above
By using a plating solution containing an additive, the operation of the present invention
The current efficiency of the plating reaction in the hole, which is a mechanism,
The situation that the current efficiency becomes higher than the current efficiency
It became clear that it could come. Example 14 The additives added to the plating solution were chloro-1,
All the same as in Example 2 except that 4-benzoquinone was used.
Study was conducted. As a result, copper is completely buried in all holes.
It is found that there are no defects such as voids
Was. As described above, the present invention is applicable to the embedding of copper into minute holes.
And found to be very effective. In addition, copper plating
The process of embedding was observed. Same conditions as above
30 seconds after the start of plating, the substrate is plated with a plating solution.
It was taken out from the inside and the hole cross section was observed with an electron microscope.
As a result, the plating thickness on the substrate surface has almost increased.
In contrast, the plating thickness in the hole is
It turned out that it became about twice. Including the above additives
By using a plating solution,
Current efficiency of the plating reaction in the hole
That the current efficiency is higher than the current efficiency
Became clear. [Example 15] An additive to be added to a plating solution was 2,3-dic
Except for lolo-1,4-benzoquinone
The same examination as in Example 2 was performed. As a result, copper in all holes
Is completely embedded and has no defects such as voids
I understood. As described above, the present invention embeds copper into micro holes.
It turned out to be very effective. Furthermore, copper
The process of embedding by plating was observed. Same as above
Plating under various conditions, 30 seconds after plating starts,
Take out from the plating solution and observe the cross section of the hole with an electron microscope
did. As a result, the plating thickness on the substrate surface almost increased
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Addition above
Of the present invention by using a plating solution containing an agent
The current efficiency of the plating reaction in the hole,
The current efficiency of the reaction
It became clear that. Example 16 The additive to be added to the plating solution was 2,5-dic
Except for lolo-1,4-benzoquinone
The same examination as in Example 2 was performed. As a result, copper in all holes
Is completely embedded and has no defects such as voids
I understood. As described above, the present invention embeds copper into micro holes.
It turned out to be very effective. Furthermore, copper
The process of embedding by plating was observed. Same as above
Plating under various conditions, 30 seconds after plating starts,
Take out from the plating solution and observe the cross section of the hole with an electron microscope
did. As a result, the plating thickness on the substrate surface almost increased
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Addition above
Of the present invention by using a plating solution containing an agent
The current efficiency of the plating reaction in the hole,
The current efficiency of the reaction
It became clear that. Example 17 The additive to be added to the plating solution was 2,6-dic
Except for lolo-1,4-benzoquinone
The same examination as in Example 2 was performed. As a result, copper in all holes
Is completely embedded and has no defects such as voids
I understood. As described above, the present invention embeds copper into micro holes.
It turned out to be very effective. Furthermore, copper
The process of embedding by plating was observed. Same as above
Plating under various conditions, 30 seconds after plating starts,
Take out from the plating solution and observe the cross section of the hole with an electron microscope
did. As a result, the plating thickness on the substrate surface almost increased
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Addition above
Of the present invention by using a plating solution containing an agent
The current efficiency of the plating reaction in the hole,
The current efficiency of the reaction
It became clear that. Example 18 The additives added to the plating solution were bromo-1,
All the same as in Example 2 except that 4-benzoquinone was used.
Study was conducted. As a result, copper is completely buried in all holes.
It is found that there are no defects such as voids
Was. As described above, the present invention is applicable to the embedding of copper into minute holes.
And found to be very effective. In addition, copper plating
The process of embedding was observed. Same conditions as above
30 seconds after the start of plating, the substrate is plated with a plating solution.
It was taken out from the inside and the hole cross section was observed with an electron microscope.
As a result, the plating thickness on the substrate surface has almost increased.
In contrast, the plating thickness in the hole is
It turned out that it became about twice. Including the above additives
By using a plating solution,
Current efficiency of the plating reaction in the hole
That the current efficiency is higher than the current efficiency
Became clear. Example 19 The additive added to the plating solution was 2,5-dibu
Performed except for Lomo-1,4-benzoquinone
The same examination as in Example 2 was performed. As a result, copper in all holes
Is completely embedded and has no defects such as voids
I understood. As described above, the present invention embeds copper into micro holes.
It turned out to be very effective. Furthermore, copper
The process of embedding by plating was observed. Same as above
Plating under various conditions, 30 seconds after plating starts,
Take out from the plating solution and observe the cross section of the hole with an electron microscope
did. As a result, the plating thickness on the substrate surface almost increased
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Addition above
Of the present invention by using a plating solution containing an agent
The current efficiency of the plating reaction in the hole,
The current efficiency of the reaction
It became clear that. Example 20 The additive to be added to the plating solution was 2-chloro-
Everything except 5-methyl-1,4-benzoquinone
The same study as in Example 2 was conducted. As a result, all
Copper is completely buried in the hole, no defects such as voids
I understood that. As described above, the present invention provides the
It was found to be very effective for embedding. Change
Next, the process of embedding by copper plating was observed. the above
Plating is performed under the same conditions as in
Remove the plate from the plating solution, and examine the cross section of the hole with an electron microscope.
Was observed. As a result, the plating film thickness on the substrate surface is almost
While the plating thickness in the hole is
It was found that the thickness was about twice as large as the plating film thickness. Up
By using the plating solution containing the additive, the present invention
The mechanism of action, the current efficiency of the plating reaction in the hole,
The current efficiency of the plating reaction
It became clear that it could be realized. Example 21 The additive to be added to the plating solution was 1,2-ben
Except for using zoquinone, the same examination as in Example 2 was performed.
went. As a result, copper is completely embedded in all holes
It was found that there were no defects such as voids. That's it
Therefore, the present invention is very effective for embedding copper in micro holes.
It turned out to be effective. In addition, embedded by copper plating
Observed the process of putting. Perform plating under the same conditions as above.
30 seconds after plating starts, remove substrate from plating solution
Then, the hole cross section was observed with an electron microscope. As a result,
Although the plating film thickness on the plate surface has hardly increased
And the thickness of the plating in the hole is about twice the thickness of the plating on the surface.
It turned out that it was. Plating solution containing the above additives
By using, the action mechanism of the present invention,
The current efficiency of the plating reaction is the current efficiency of the surface plating reaction
It is clear that it is possible to express a situation where it is higher than
became. Example 22 The additive added to the plating solution was methyl-1,
All the same as Example 2 except that 2-benzoquinone was used.
Study was conducted. As a result, copper is completely buried in all holes.
It is found that there are no defects such as voids
Was. As described above, the present invention is applicable to the embedding of copper into minute holes.
And found to be very effective. In addition, copper plating
The process of embedding was observed. Same conditions as above
30 seconds after the start of plating, the substrate is plated with a plating solution.
It was taken out from the inside and the hole cross section was observed with an electron microscope.
As a result, the plating thickness on the substrate surface has almost increased.
In contrast, the plating thickness in the hole is
It turned out that it became about twice. Including the above additives
By using a plating solution,
Current efficiency of the plating reaction in the hole
That the current efficiency is higher than the current efficiency
Became clear. [Example 23] The additive to be added to the plating solution was 4-carboxy.
Except for using 1,2-benzoquinone, all examples were used.
The same examination was performed as in 2. The result is copper in every hole
Completely buried and free from defects such as voids
all right. As described above, the present invention embeds copper in micro holes.
Was found to be very effective. In addition, copper
The process of embedding was observed. Same as above
Plating is performed under the conditions.
Take out of the solution and observe the cross section of the hole with an electron microscope.
Was. As a result, the plating film thickness on the substrate surface almost increased
The thickness of the plating film in the hole is not
It was found that the thickness was about twice as large. The above additives
Mechanism of the present invention by using a plating solution containing
The current efficiency of the plating reaction in the hole is
A situation where the current efficiency is higher than the current efficiency of the reaction can be expressed
It became clear. [Example 24] The additive to be added to the plating solution was 4-carboe.
Except for toxic-1,2-benzoquinone, all
The same study as in Example 2 was performed. As a result, in every hole
Make sure that copper is completely embedded and free from defects such as voids.
I understood. As described above, the present invention provides a method for embedding copper in micro holes.
It was found to be very effective for Furthermore,
The process of embedding by copper plating was observed. Same as above
Plating is performed under the same conditions.
Take out from the plating solution and observe the cross section of the hole with an electron microscope.
I thought. As a result, the plating thickness on the substrate surface almost increased.
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Above
By using a plating solution containing an additive, the operation of the present invention
The current efficiency of the plating reaction in the hole, which is a mechanism,
The situation that the current efficiency becomes higher than the current efficiency
It became clear that it could come. Example 25 An additive to be added to a plating solution was 3-hydroxy
Except for using 1,2-benzoquinone, all examples were used.
The same examination was performed as in 2. The result is copper in every hole
Completely buried and free from defects such as voids
all right. As described above, the present invention embeds copper in micro holes.
Was found to be very effective. In addition, copper
The process of embedding was observed. Same as above
Plating is performed under the conditions.
Take out of the solution and observe the cross section of the hole with an electron microscope.
Was. As a result, the plating film thickness on the substrate surface almost increased
The thickness of the plating film in the hole is not
It was found that the thickness was about twice as large. The above additives
Mechanism of the present invention by using a plating solution containing
The current efficiency of the plating reaction in the hole is
A situation where the current efficiency is higher than the current efficiency of the reaction can be expressed
It became clear. Example 26 The additive to be added to the plating solution was 3-hydroxy
Except that it was used as c-5-carboxy-1,2-benzoquinone
Were all examined in the same manner as in Example 2. as a result,
Copper is completely buried in all holes and voids etc.
No defects were found. As described above, the present invention
Proved to be very effective for embedding copper in copper
Was. In addition, observe the process of embedding by copper plating.
Was. Plating is performed under the same conditions as above, and plating starts 30
Seconds later, the substrate is taken out of the plating solution, and the cross section of the hole is observed with an electron microscope.
Observed with a microscope. As a result, the plating film thickness on the substrate surface
Does not increase, whereas the plating thickness in the hole
Shows that the thickness is about twice the thickness of the plating on the surface
Was. By using a plating solution containing the above additive,
Current efficiency of plating reaction in a hole, which is the mechanism of action of the present invention
, But higher than the current efficiency of the plating reaction on the surface
It became clear that the situation could be expressed. [Example 27] The additive to be added to the plating solution was tetrachloro
Example 2 except that -1,2-benzoquinone was used.
A similar study was conducted. As a result, copper is completed in all holes.
It is clear that there are no voids or other defects
won. As described above, the present invention relates to the embedding of copper into micro holes.
On the other hand, it turned out to be very effective. In addition, copper
The process of embedding was observed. Article similar to the above
30 seconds after starting plating, plating the substrate
Remove from the liquid, observe the cross section of the hole with an electron microscope.
Was. As a result, the plating film thickness on the substrate surface almost increased
The thickness of the plating film in the hole is not
It was found that the thickness was about twice as large. The above additives
Mechanism of the present invention by using a plating solution containing
The current efficiency of the plating reaction in the hole is
A situation where the current efficiency is higher than the current efficiency of the reaction can be expressed
It became clear. [Example 28] The additive added to the plating solution was tetrabromo.
Example 2 except that -1,2-benzoquinone was used.
A similar study was conducted. As a result, copper is completed in all holes.
It is clear that there are no voids or other defects
won. As described above, the present invention relates to the embedding of copper into micro holes.
On the other hand, it turned out to be very effective. In addition, copper
The process of embedding was observed. Article similar to the above
30 seconds after starting plating, plating the substrate
Remove from the liquid, observe the cross section of the hole with an electron microscope.
Was. As a result, the plating film thickness on the substrate surface almost increased
The thickness of the plating film in the hole is not
It was found that the thickness was about twice as large. The above additives
Mechanism of the present invention by using a plating solution containing
The current efficiency of the plating reaction in the hole is
A situation where the current efficiency is higher than the current efficiency of the reaction can be expressed
It became clear. [Example 29] The additive added to the plating solution was 1,4-naph
Except for using toquinone, the same study as in Example 2 was performed.
went. As a result, copper is completely embedded in all holes
It was found that there were no defects such as voids. That's it
Therefore, the present invention is very effective for embedding copper in micro holes.
It turned out to be effective. In addition, embedded by copper plating
Observed the process of putting. Perform plating under the same conditions as above.
30 seconds after plating starts, remove substrate from plating solution
Then, the hole cross section was observed with an electron microscope. As a result,
Although the plating film thickness on the plate surface has hardly increased
And the thickness of the plating in the hole is about twice the thickness of the plating on the surface.
It turned out that it was. Plating solution containing the above additives
By using, the action mechanism of the present invention,
The current efficiency of the plating reaction is the current efficiency of the surface plating reaction
It is clear that it is possible to express a situation where it is higher than
became. Example 30 The additive to be added to the plating solution was 1,4-naph
Except for toquinone-2-sulfonate, all
The same study as in Example 2 was performed. As a result, in every hole
Make sure that copper is completely embedded and free from defects such as voids.
I understood. As described above, the present invention provides a method for embedding copper in micro holes.
It was found to be very effective for Furthermore,
The process of embedding by copper plating was observed. Same as above
Plating is performed under the same conditions.
Take out from the plating solution and observe the cross section of the hole with an electron microscope.
I thought. As a result, the plating thickness on the substrate surface almost increased.
The thickness of the plating in the hole is
It was found that the thickness was about twice as large as the film thickness. Above
By using a plating solution containing an additive, the operation of the present invention
The current efficiency of the plating reaction in the hole, which is a mechanism,
The situation that the current efficiency becomes higher than the current efficiency
It became clear that it could come. [Example 31] An additive to be added to a plating solution was 9,10-A
All tests were performed in the same manner as in Example 2 except for using anthraquinone.
讨 was carried out. As a result, copper is completely embedded in all holes
It was found that there were no defects such as voids. Less than
As can be seen from the above, the present invention is very effective in embedding copper into micro holes.
Was found to be effective. In addition, copper plating
The process of being immersed was observed. Plating under the same conditions as above
30 seconds after starting plating, remove the substrate from the plating solution.
Then, the hole cross section was observed with an electron microscope. The result
As a result, the plating film thickness on the substrate surface has hardly increased
On the other hand, the plating thickness in the hole is about twice the plating thickness on the surface
I knew it was getting better. Including the above additives
By using a liquid, a hole, which is an action mechanism of the present invention,
The current efficiency of the plating reaction in
It is clear that a situation where efficiency is higher than that can be expressed
It was ok. [Example 32] The additive added to the plating solution was 9,10-A
Except for the use of untraquinone-2-sulfonate,
The same study as in Example 2 was conducted. As a result, all
Copper is completely buried in the hole, no defects such as voids
I understood that. As described above, the present invention provides the
It was found to be very effective for embedding. Change
Next, the process of embedding by copper plating was observed. the above
Plating is performed under the same conditions as in
Remove the plate from the plating solution, and examine the cross section of the hole with an electron microscope.
Was observed. As a result, the plating film thickness on the substrate surface is almost
While the plating thickness in the hole is
It was found that the thickness was about twice as large as the plating film thickness. Up
By using the plating solution containing the additive, the present invention
The mechanism of action, the current efficiency of the plating reaction in the hole,
The current efficiency of the plating reaction
It became clear that it could be realized. [Example 33] The additive to be added to the plating solution was 9,10-A
Except for the use of untraquinone-1-sulfonate,
The same study as in Example 2 was conducted. As a result, all
Copper is completely buried in the hole, no defects such as voids
I understood that. As described above, the present invention provides the
It was found to be very effective for embedding. Change
Next, the process of embedding by copper plating was observed. the above
Plating is performed under the same conditions as in
Remove the plate from the plating solution, and examine the cross section of the hole with an electron microscope.
Was observed. As a result, the plating film thickness on the substrate surface is almost
While the plating thickness in the hole is
It was found that the thickness was about twice as large as the plating film thickness. Up
By using the plating solution containing the additive, the present invention
The mechanism of action, the current efficiency of the plating reaction in the hole,
The current efficiency of the plating reaction
It became clear that it could be realized. [Example 34] 9,10-A
Except that it was untraquinone-1,8-disulfonate
Were all examined in the same manner as in Example 2. as a result,
Copper is completely buried in all holes and voids etc.
No defects were found. As described above, the present invention
Proved to be very effective for embedding copper in copper
Was. In addition, observe the process of embedding by copper plating.
Was. Plating is performed under the same conditions as above, and plating starts 30
Seconds later, the substrate is taken out of the plating solution, and the cross section of the hole is observed with an electron microscope.
Observed with a microscope. As a result, the plating film thickness on the substrate surface
Does not increase, whereas the plating thickness in the hole
Shows that the thickness is about twice the thickness of the plating on the surface
Was. By using a plating solution containing the above additive,
Current efficiency of plating reaction in a hole, which is the mechanism of action of the present invention
, But higher than the current efficiency of the plating reaction on the surface
It became clear that the situation could be expressed. [Example 35] The additive to be added to the plating solution was 9,10-A
Except that it was untraquinone-1,5-disulfonate
Were all examined in the same manner as in Example 2. as a result,
Copper is completely buried in all holes and voids etc.
No defects were found. As described above, the present invention
Proved to be very effective for embedding copper in copper
Was. In addition, observe the process of embedding by copper plating.
Was. Plating is performed under the same conditions as above, and plating starts 30
Seconds later, the substrate is taken out of the plating solution, and the cross section of the hole is observed with an electron microscope.
Observed with a microscope. As a result, the plating film thickness on the substrate surface
Does not increase, whereas the plating thickness in the hole
Shows that the thickness is about twice the thickness of the plating on the surface
Was. By using a plating solution containing the above additive,
Current efficiency of plating reaction in a hole, which is the mechanism of action of the present invention
, But higher than the current efficiency of the plating reaction on the surface
It became clear that the situation could be expressed. Example 36 The additive added to the plating solution was 5,8-quino
The same examination as in Example 2 except that the quinquinone was used
Was done. As a result, copper is completely embedded in all holes
And no defects such as voids were found. that's all
Therefore, the present invention is very effective in embedding copper in micro holes.
It turned out to be effective. In addition, fill with copper plating
Observed the process of getting stuck. Plating under the same conditions as above
30 seconds after plating starts, remove the substrate from the plating solution
It was taken out and the hole cross section was observed with an electron microscope. as a result,
Although the plating film thickness on the substrate surface has hardly increased
And the thickness of the plating in the hole is about twice the thickness of the plating on the surface.
It turned out that it was. Plating solution containing the above additives
By using, the action mechanism of the present invention,
The current efficiency of the plating reaction is the current efficiency of the surface plating reaction
It is clear that it is possible to express a situation where it is higher than
became. [Example 37] The additive to be added to the plating solution was 1,4-ben
Zoquinone and its concentration in the plating solution is 0.0001 mol
The same examination as in Example 2 was conducted except that the value was / l.
Was. Here, the additive concentration in the plating solution is 0.0001 m
ol / l, stirring the plating solution using a stirrer
So that the supply of the additive to the substrate surface is smooth
It was adjusted. As a result, copper is completely embedded in all holes
And no defects such as voids were found. still,
Comparing the results with and without stirring,
No voids and good results but no agitation
In some cases, the occurrence of voids was confirmed. Also, plating solution
Was performed using air instead of a stirrer.
Holes of φ0.5mm were drilled at 5mm pitch in the plating solution.
Insert a Teflon tube with an outer diameter of 5 mm, and supply
I blew the turtle. Plating solution is vigorously stirred by bubbles
Was. As a result of examination in this state, copper is completely in all holes
It is clear that there are no defects such as voids
Was. As described above, the present invention is applicable to the embedding of copper into minute holes.
And found to be very effective. In addition, copper plating
The process of embedding was observed. Same conditions as above
30 seconds after the start of plating, the substrate is plated with a plating solution.
It was taken out from the inside and the hole cross section was observed with an electron microscope.
As a result, the plating thickness on the substrate surface has almost increased.
In contrast, the plating thickness in the hole is
It turned out that it became about twice. Including the above additives
By using a plating solution,
Current efficiency of the plating reaction in the hole
That the current efficiency is higher than the current efficiency
Became clear. [Example 38] The additive added to the plating solution was 1,4-ben
Zoquinone, and its concentration in the plating solution was 1.0 mol / l.
The same examination as in Example 2 was conducted except for the above. That
As a result, copper is completely embedded in all holes,
It was found that there was no defect such as a defect. From the above, the present invention
Very effective for embedding copper in micro holes
I understood. In addition, the process of embedding by copper plating
Observed. Plating under the same conditions as above
After 30 seconds, the substrate is taken out of the plating solution, and the hole
Observed with an electron microscope. As a result, the board surface
Although the film thickness has hardly increased,
Thickness is about twice the thickness of plating on the surface
I understood. Using a plating solution containing the above additives
Thus, the electric action of the plating reaction in the hole, which is the action mechanism of the present invention, is described.
Flow efficiency is higher than current efficiency of surface plating reaction
It became clear that the situation could be expressed. [Embodiment 39] A substrate 2 having a diameter of 8 inches was used. Plating solution
Uses hydrogen peroxide as an additive to the electrolytic copper plating solution.
Use the solution added to a concentration of 0.01 mol / l.
Was. After cleaning the substrate with ultrapure water,
Immerse in 40 liters of electrolytic copper plating solution,
0.8A / dmTwoFor 5 minutes. At this time
The plating solution flows between the filtration filter and the outside of the plating tank every minute.
It circulates at a circulating volume of 50 liters.
The plating solution is sufficiently stirred. After 5 minutes of plating,
Remove the substrate from the plating solution and fit it into a groove with a width of 0.2 μm.
The copper embedding property was evaluated. Cross section of more than 100 grooves
As a result of observation, copper was completely embedded in all grooves.
It was found that there were no defects such as voids. Above result
Therefore, the present invention is very effective in embedding copper in micro grooves.
It turned out to be effective. In addition, fill with copper plating
Observed the process of getting stuck. Plating under the same conditions as above
30 seconds after plating starts, remove the substrate from the plating solution
It was taken out and the groove cross section was observed with an electron microscope. as a result,
Although the plating film thickness on the substrate surface has hardly increased
The thickness of the plating in the groove is about twice the thickness of the plating on the surface.
It turned out that it was. Plating solution containing the above additives
By using, the action mechanism of the present invention,
The current efficiency of the plating reaction is the current efficiency of the surface plating reaction
It is clear that it is possible to express a situation where it is higher than
became. [Embodiment 40] A substrate 2 having a diameter of 8 inches was used. Above electricity
0.01 mol / l of 1,4-benzoquinone in copper plating solution
Is used as the plating solution.
Was. After washing the substrate with ultrapure water, various benzoquinones
Infiltration into the added 40 liter electrolytic copper plating solution
And the current density is 0.8 A / dmTwoAnd plating for 5 minutes
Was. At this time, the plating solution is applied to the filtration filter outside the plating tank.
Is circulating at a circulation rate of 50 liters per minute,
The plating solution is sufficiently stirred by this circulation flow. 5
After plating for a minute, the substrate is taken out of the plating solution and the width is 0.2 mm.
The embedding property of the plated copper into the μm groove was evaluated. 100
As a result of cross-sectional observation of more than one groove, copper was completely completed in all grooves
It is clear that there are no defects such as voids
Was. Based on the above results, the present invention shows that copper is
It turned out to be very effective. Furthermore, copper
The process of embedding by plating was observed. Same as above
Plating under various conditions, 30 seconds after plating starts,
Take out from the plating solution and observe the groove cross section with an electron microscope
did. As a result, the plating thickness on the substrate surface almost increased
The plating thickness in the groove is
It was found that the thickness was about twice as large as the film thickness. Addition above
Of the present invention by using a plating solution containing an agent
The current efficiency of the plating reaction in the groove, which is
The current efficiency of the reaction
It became clear that. Example 41 A substrate 3 having a diameter of 8 inches was used. Above electricity
0.01 mol / l of 1,4-benzoquinone in copper plating solution
Is used as the plating solution.
Was. After washing the substrate with ultrapure water, 1,4-benzoquinone was removed.
Infiltration into the added 40 liter electrolytic copper plating solution
And the current density is 0.8 A / dmTwoAnd plating for 5 minutes
Was. At this time, the plating solution is applied to the filtration filter outside the plating tank.
Is circulating at a circulation rate of 50 liters per minute,
The plating solution is sufficiently stirred by this circulation flow. 5
After plating for a minute, the substrate is taken out of the plating solution and the width is 0.2 mm.
Embedding of plated copper into μm grooves and holes underneath
Was evaluated. Cross section of more than 100 grooves and holes underneath
As a result of observation, all the grooves and the underlying holes were completely
It is clear that there are no defects such as voids
Was. Based on the above results, the present invention shows that
Very effective for embedding copper in formed holes
I understood that. In addition, overfilling by copper plating
The process was observed. Plating under the same conditions as above
30 seconds after starting, remove the substrate from the plating solution and
Observe the cross section of the hole formed in the lower layer with an electron microscope
did. As a result, the plating thickness on the substrate surface almost increased
The hole and the hole formed underneath it
The plating thickness in the inside is about twice the plating thickness on the surface
I knew it was there. Using a plating solution containing the above additives
By this, the action mechanism of the present invention, that is,
Current efficiency of the plating reaction is better than the current efficiency of the plating reaction on the surface.
It is clear that the situation where
Was. [Embodiment 42] The height of the build-up method
The application to the density printed circuit board was studied. Feeling on the surface of substrate 4
A light insulating layer was formed. The thickness of the insulating layer is 50 μm
With a predetermined exposure and development process,
Via holes were formed. In addition, the surface of the insulating layer
After treatment with an alkaline treatment solution containing an acid and roughening,
Catalyst treatment pro for electroless plating containing Pd colloid
After subjecting the catalyst to a specific treatment, the electroless copper plating
It was applied to a thickness of about 2 μm. This electroless copper
The copper layer was used as a seed layer to perform electrolytic copper plating. Above
0.01 mol / l of 1,4-benzoquinone was added to the copper plating solution.
l to be used as the plating solution.
Was. After washing the substrate with ultrapure water, 1,4-benzoquinone was removed.
Infiltration into the added 100 liter electrolytic copper plating solution
And a current density of 1.5 A / dmTwoAnd plating for 60 minutes
Was. At this time, the plating solution is applied to the filtration filter outside the plating tank.
Circulate at a rate of 120 liters per minute.
Therefore, the plating solution is sufficiently stirred by this circulation flow.
You. After plating, the substrate was taken out and the cross section was observed under a microscope.
As a result, the plating film thickness near the bottom of the via hole was
About 1.5 times the plating thickness of the surface.
The continuation was secured. Based on the above results, the present invention
The inside of a via hole is
Plating thickness can be increased, and via hole connection reliability is high
It became clear that the substrate could be secured. Furthermore, the present invention
To connect via holes and build up two layers
Disconnection when LSI is mounted on the formed board with bare chip
FIG. 6 shows a schematic surface view. According to the present invention, high-density wiring
Can be formed with high reliability, as shown in the figure.
An electronic component having such a configuration can be easily formed. Embodiment 43 The surface of the substrate 5 having a size of 100 mm square is
A thermosetting adhesive film with a thickness of 25 μm containing
And a 25 μm thick polyimide film (piece
With surface copper foil, manufactured by Hitachi Chemical: MCF-5000 I)
Was heat-pressed. The thickness of the copper foil is 12μm and the adhesive fill
On the other side of the game. After bonding, feel on the copper foil surface
Etching resist with optical properties (Tokyo Ohka: OFP
R-800), and a predetermined exposure and development process
The resist where the hole is to be formed is removed. Next
In, the copper foil is patterned by etching, and then
The etching resist was stripped using a predetermined stripping solution.
Next, a via hole was formed. Excess for via hole processing
Shima laser was used. Laser light of 20mm width is applied to the substrate surface
Irradiation. The copper foil on the board surface serves as a mask,
Only the patterned part is processed.
Via holes were formed by the informal mask method. At this time
The formed via hole has a size of φ50 μm and a pitch of 2 mm.
2,500 holes in total. Then, spat copper over the entire surface of the board.
A thickness of about 2 μm was formed by a sputtering method. With this spatter
Using the formed copper as a seed layer, electrolytic copper plating was performed.
1,4-benzoquinone was added to the above electrolytic copper plating solution at 0.0.
A solution added to a concentration of 1 mol / l was used as a plating solution.
Used. After washing the substrate with ultrapure water,
100 liter total copper plating solution with quinone added
Infiltration in the current density 1.5A / dmTwoSo, for 60 minutes
I went. At this time, the plating solution is filtered out of the plating tank.
Circulates at a rate of 120 liters per minute
The plating solution is sufficiently stirred by this circulation flow.
ing. After plating, remove the substrate and observe the cross section with a microscope.
Was. As a result, the reduction potential in the plating solution is
Use plating solution containing 1,4-benzoquinone, which is more noble than
The thickness of the plating near the bottom of the via hole
1.5 times the plating film thickness on the board surface
Connection was secured. From the above results, according to the present invention,
Via hole connection for via hole connection of build-up board
Internal plating thickness can be increased and via hole connection reliability
It became clear that a high substrate could be secured. Embodiment 44 The surface of the substrate 6 having a size of 100 mm square is
A thermosetting adhesive film with a thickness of 25 μm containing
And a 25 μm thick polyimide film (piece
With surface copper foil, manufactured by Hitachi Chemical: MCF-5000 I)
Was heat-pressed. The thickness of the copper foil is 12μm and the adhesive fill
On the other side of the game. After bonding, feel on the copper foil surface
Etching resist with optical properties (Tokyo Ohka: OFP
R-800), and a predetermined exposure and development process
The resist where the hole is to be formed is removed. Next
In, the copper foil is patterned by etching, and then
The etching resist was stripped using a predetermined stripping solution.
Next, a via hole was formed. Excess for via hole processing
Shima laser was used. Laser light of 20mm width is applied to the substrate surface
Irradiation. The copper foil on the board surface serves as a mask,
Only the patterned part is processed.
Via holes were formed by the informal mask method. At this time
The formed via hole has a size of φ50 μm and a pitch of 2 mm.
2,500 holes in total. Then, 3 at the bottom of the via hole
The chromium layer on the top surface of the layer conductor is immersed in 18% hydrochloric acid
More removed. Next, copper is sputtered on the entire surface of the substrate.
And a thickness of about 2 μm. Copper formed by this sputtering
Was used as a seed layer to perform electrolytic copper plating. Above copper
1,4-benzoquinone was added to the plating solution in an amount of 0.01 mol / l.
The solution added so as to have a concentration was used as a plating solution.
After washing the substrate with ultrapure water, add 1,4-benzoquinone
Immersed in a total of 100 liters of electrolytic copper plating solution,
Current density 1.5A / dmTwoThen, plating was performed for 60 minutes.
At this time, the plating solution is connected to the filtration filter outside the plating tank.
Circulating at a rate of 120 liters per minute.
The plating solution is sufficiently stirred by the circulating flow. Me
After that, the substrate was taken out and the cross section was observed under a microscope. The result
As a result, the reduction potential in the plating solution is more noble than the potential for copper deposition.
When using a plating solution containing 1,4-benzoquinone
Indicates that the plating thickness near the bottom of the via hole is
It is about 1.5 times the thickness of the
I was able to keep. Based on the above results, according to the present invention, build-up
For the via hole connection on the
A substrate with high via hole connection reliability
It became clear that it could be secured. [Embodiment 45] The height of the build-up method
The application to the density printed circuit board was studied. Feeling on the surface of substrate 4
A light insulating layer was formed. The thickness of the insulating layer is 50 μm
With a predetermined exposure and development process,
Via holes were formed. In addition, the surface of the insulating layer
After treatment with an alkaline treatment solution containing an acid and roughening,
Catalyst treatment pro for electroless plating containing Pd colloid
After subjecting the catalyst to a predetermined catalytic treatment, hypophosphorous acid is reduced.
Electroless nickel plating used as an agent to a thickness of about 2 μm
It was applied as follows. This electroless nickel plating layer is used as a seed layer.
, Electro-nickel plating was performed. The above electric nickel
0.01 mol / l 1,4-benzoquinone
Is used as the plating solution.
Was. After washing the substrate with ultrapure water, 1,4-benzoquinone was removed.
In a total of 100 liters of electro nickel plating solution added
And a current density of 1.5 A / dmTwoAnd plating for 60 minutes
Was done. At this time, the plating solution is filtered out of the plating tank.
Circulates at a rate of 120 liters per minute
The plating solution is sufficiently stirred by this circulation flow.
I have. After plating, remove the substrate and observe the cross section with a microscope.
Was. As a result, the reduction potential in the plating solution is
Plating containing 1,4-benzoquinone, which is nobler than the potential of deposition
When using a solution, the plating film thickness near the bottom of the via hole
Is about 1.5 times the plating thickness on the substrate surface.
As a result, a sufficient connection could be secured. Based on the above results, the present invention
The via hole connection of the build-up board
Thickness of plating inside the hole can be increased and via hole connection
It became clear that a highly reliable substrate could be secured.
Furthermore, via-hole connection is performed according to the present invention, and a two-layer building is formed.
Bare chip mounting of LSI on a substrate with a built-up layer
FIG. 6 shows a schematic cross-sectional view of the case. According to the present invention,
High-density wiring can be formed with high reliability.
Therefore, it is possible to easily form an electronic component having the configuration shown in the figure.
became.

【発明の効果】高アスペクト比の穴や溝を有する基板の
メタライズに、本発明のめっき液およびめっき方法を用
いた場合、穴や溝の内部のめっき膜厚を、表面に比べ厚
くすることができる。これにより、信頼性の高い配線や
層間接続導体を形成可能となる。When the plating solution and the plating method of the present invention are used for metallizing a substrate having holes and grooves with a high aspect ratio, the plating film inside the holes and grooves can be made thicker than the surface. it can. This makes it possible to form highly reliable wiring and interlayer connection conductors.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明を実施する場合の工程と、結果を示した
断面模式図。FIG. 1 is a schematic cross-sectional view showing steps in the case of carrying out the present invention and the results.

【図２】本発明を実施しない場合の断面模式図。FIG. 2 is a schematic cross-sectional view when the present invention is not performed.

【図３】本発明を実施しない場合の断面模式図。FIG. 3 is a schematic sectional view when the present invention is not implemented.

【図４】本発明を実施しない場合の断面模式図。FIG. 4 is a schematic sectional view when the present invention is not implemented.

【図５】本発明を実施する場合の工程と、結果を示した
断面模式図。FIG. 5 is a schematic cross-sectional view showing steps in the case of carrying out the present invention and the results.

【図６】本発明を適用した実装基板の断面模式図。FIG. 6 is a schematic cross-sectional view of a mounting board to which the present invention is applied.

【符号の説明】[Explanation of symbols]

１…シリコン基板、２，８，１５，１９，２４…絶縁
層、３…穴または溝、４…バリヤー層、５…シート層、
６，９，１６，２２，２６…めっき析出金属、７，１
０，１４，１８，２３…基板、２０，２５…ビアホー
ル、２１…無電解めっき層またはダイレクトプレーティ
ング前処理層、２７…ＬＳＩチップ、２８…はんだ、２
９…スルーホール、３０…配線、３１…ソルダーレジス
ト。。DESCRIPTION OF SYMBOLS 1 ... Silicon substrate, 2, 8, 15, 19, 24 ... Insulating layer, 3 ... Hole or groove, 4 ... Barrier layer, 5 ... Sheet layer,
6, 9, 16, 22, 26 ... Plating deposited metal, 7, 1
0, 14, 18, 23: substrate, 20, 25: via hole, 21: electroless plating layer or direct plating pre-treatment layer, 27: LSI chip, 28: solder, 2
9 ... Through hole, 30 ... Wiring, 31 ... Solder resist. .

───────────────────────────────────────────────────── フロントページの続き (72)発明者 深田 晋一 東京都青梅市今井2326番地 株式会社日立 製作所デバイス開発センタ内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinichi Fukada 2326 Imai, Ome-shi, Tokyo Inside the Device Development Center, Hitachi, Ltd.

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】めっき金属イオンの被めっき体上での還元
電位よりも、貴な電位で還元される物質を含むことを特
徴とするめっき液。1. A plating solution containing a substance which is reduced at a noble potential than a reduction potential of plating metal ions on a body to be plated. 【請求項２】請求項１において、前記貴な電位で還元さ
れる物質の濃度が０.０００１mol／ｌ〜１mol／ｌ であ
ることを特徴とするめっき液。2. The plating solution according to claim 1, wherein the concentration of the substance reduced at the noble potential is 0.0001 mol / l to 1 mol / l. 【請求項３】めっき液中の銅イオンの還元電位よりも貴
な電位で還元される物質を含むことを特徴とする銅めっ
き液。3. A copper plating solution comprising a substance which is reduced at a potential noble than the reduction potential of copper ions in the plating solution. 【請求項４】めっき層を有する部材において、前記めっ
き層はめっき液中に含まれるめっき金属よりも貴な電位
で還元される物質または該物質の還元体の、被めっき体
表面に析出しためっき金属中に含まれる量が１０ppm 以
下であることを特徴とする部材。4. A member having a plating layer, wherein the plating layer is formed by plating a substance reduced at a potential nobler than a plating metal contained in a plating solution or a reduced substance of the substance on a surface of a body to be plated. A member characterized in that the amount contained in the metal is 10 ppm or less. 【請求項５】めっき金属イオンの被めっき体上での還元
電位よりも、貴な電位で還元される物質を含むめっき液
中にガスを吹き込むか又は前記めっき液を機械的に撹拌
しながらめっきすることを特徴とするめっき方法。5. A plating method, wherein a gas is blown into a plating solution containing a substance which is reduced at a noble potential than a reduction potential of a plating metal ion on a body to be plated, or plating is performed while mechanically stirring the plating solution. Plating method. 【請求項６】めっき金属イオンの被めっき体上での還元
電位よりも、貴な電位で還元される物質を０.０００１m
ol／ｌ〜１mol／ｌ 含むめっき液中にガスを吹き込むか
又は前記めっき液を機械的に撹拌しながらめっきするこ
とを特徴とするめっき方法。6. A substance which is reduced at a noble potential than a reduction potential of plating metal ions on a body to be plated by 0.0001 m
A plating method, wherein gas is blown into a plating solution containing ol / l to 1 mol / l or plating is performed while mechanically stirring the plating solution. 【請求項７】めっき液中の銅イオンの還元電位よりも貴
な電位で還元される物質を含む銅めっき液中にガスを吹
き込むか又は前記めっき液を機械的に撹拌しながらめっ
きすることを特徴とするめっき方法。7. A method in which gas is blown into a copper plating solution containing a substance which is reduced at a potential nobler than the reduction potential of copper ions in the plating solution, or plating is performed while mechanically stirring the plating solution. Characteristic plating method.
JP10142560A 1998-05-25 1998-05-25 Plating liquid and plating Pending JPH11335888A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10142560A JPH11335888A (en) 1998-05-25 1998-05-25 Plating liquid and plating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10142560A JPH11335888A (en) 1998-05-25 1998-05-25 Plating liquid and plating

Publications (1)

Publication Number Publication Date
JPH11335888A true JPH11335888A (en) 1999-12-07

Family

ID=15318185

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPH11335888A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009057582A (en) * 2007-08-30 2009-03-19 Hitachi Cable Ltd Method for forming wiring and interlayer connection via
WO2010001554A1 (en) * 2008-06-30 2010-01-07 株式会社日立製作所 Electronic circuit component and method for manufacturing same

Citations (10)

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Publication number Priority date Publication date Assignee Title
JPS513331A (en) * 1974-06-25 1976-01-12 Lea Ronal Inc SHIANKABUTSUOFUKUMANAI KAIRYODENTOYOKU
JPS5675590A (en) * 1979-11-22 1981-06-22 Nisshin Steel Co Ltd Electroliytic copper plating method
JPS6369995A (en) * 1986-08-29 1988-03-30 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− Precipitation of metal in solid matrix under catalytic action
JPH01205090A (en) * 1988-02-12 1989-08-17 Nippon Steel Corp Production of plated steel sheet having superior spot weldability
JPH01252796A (en) * 1987-12-08 1989-10-09 Nippon Steel Corp Production of plated steel sheet having superior spot weldability
JPH0397887A (en) * 1989-09-08 1991-04-23 Bridgestone Bekaruto Steel Koode Kk Method for controlling composition of copper plating bath for copper plating method using insoluble anode
JPH073488A (en) * 1993-06-22 1995-01-06 Nippon Steel Corp Sulfuric acid bath for tin plating and tin plating method using the same
JPH0892794A (en) * 1994-09-27 1996-04-09 Kawasaki Steel Corp Supplying of nickel material into nickel-base plating solution
JPH09195081A (en) * 1996-01-10 1997-07-29 Sumitomo Metal Ind Ltd Cold rolled steel sheet excellent in uniformity in phosphating and its production
JPH1192987A (en) * 1997-09-18 1999-04-06 Terumo Corp Plating liquid and electroplating method and articles using the same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS513331A (en) * 1974-06-25 1976-01-12 Lea Ronal Inc SHIANKABUTSUOFUKUMANAI KAIRYODENTOYOKU
JPS5675590A (en) * 1979-11-22 1981-06-22 Nisshin Steel Co Ltd Electroliytic copper plating method
JPS6369995A (en) * 1986-08-29 1988-03-30 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− Precipitation of metal in solid matrix under catalytic action
JPH01252796A (en) * 1987-12-08 1989-10-09 Nippon Steel Corp Production of plated steel sheet having superior spot weldability
JPH01205090A (en) * 1988-02-12 1989-08-17 Nippon Steel Corp Production of plated steel sheet having superior spot weldability
JPH0397887A (en) * 1989-09-08 1991-04-23 Bridgestone Bekaruto Steel Koode Kk Method for controlling composition of copper plating bath for copper plating method using insoluble anode
JPH073488A (en) * 1993-06-22 1995-01-06 Nippon Steel Corp Sulfuric acid bath for tin plating and tin plating method using the same
JPH0892794A (en) * 1994-09-27 1996-04-09 Kawasaki Steel Corp Supplying of nickel material into nickel-base plating solution
JPH09195081A (en) * 1996-01-10 1997-07-29 Sumitomo Metal Ind Ltd Cold rolled steel sheet excellent in uniformity in phosphating and its production
JPH1192987A (en) * 1997-09-18 1999-04-06 Terumo Corp Plating liquid and electroplating method and articles using the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009057582A (en) * 2007-08-30 2009-03-19 Hitachi Cable Ltd Method for forming wiring and interlayer connection via
JP4682285B2 (en) * 2007-08-30 2011-05-11 日立電線株式会社 Method of forming wiring and interlayer connection via
WO2010001554A1 (en) * 2008-06-30 2010-01-07 株式会社日立製作所 Electronic circuit component and method for manufacturing same

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