JP5757523B2 - Concentration measuring method, concentration management method, and concentration measuring apparatus for monovalent copper - Google Patents
Concentration measuring method, concentration management method, and concentration measuring apparatus for monovalent copper Download PDFInfo
- Publication number
- JP5757523B2 JP5757523B2 JP2011166680A JP2011166680A JP5757523B2 JP 5757523 B2 JP5757523 B2 JP 5757523B2 JP 2011166680 A JP2011166680 A JP 2011166680A JP 2011166680 A JP2011166680 A JP 2011166680A JP 5757523 B2 JP5757523 B2 JP 5757523B2
- Authority
- JP
- Japan
- Prior art keywords
- absorbance
- concentration
- copper
- solution
- monovalent copper
- 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.)
- Active
Links
Description
この発明は、銅めっき液中の一価銅の濃度を測定する方法、及び銅めっき液中の一価銅の濃度を管理する方法、並びにこれらに用いられる装置に関する。特に、水溶性のキレート剤を使用して銅めっき液中の一価銅濃度を測定する方法と、その銅めっき液中の一価銅濃度を管理する方法、並びにこれらに用いられる装置に関する。 The present invention relates to a method for measuring the concentration of monovalent copper in a copper plating solution, a method for managing the concentration of monovalent copper in a copper plating solution, and an apparatus used therefor. In particular, the present invention relates to a method for measuring a monovalent copper concentration in a copper plating solution using a water-soluble chelating agent, a method for managing the monovalent copper concentration in the copper plating solution, and an apparatus used in these methods.
プリント回路基板の製造においては、ファイン化及び多層化に対応すべく、より高度のめっきプロセス制御が求められている。例えば硫酸銅電気めっき浴において、めっき液中の銅が電解で溶解・析出するときに、一価の銅イオンが発生する。そのため、めっき条件によっては不均化反応（２Ｃｕ＋→Ｃｕ２＋＋Ｃｕ）により銅パーティクルを生成し、これがスライムとなり、めっき表面にざらつきを生じる。この対策のために光沢剤が使用されるが、この光沢剤の過剰添加を招く原因のひとつになる。また、プリント回路基板のスルーホールやビアを銅めっきによって構成する場合は、層の厚さが一定とならず電気特性にも影響を与えるという問題がある。即ち、銅めっき液中の一価銅濃度はめっき製品の不良率に直接影響する。 In the production of printed circuit boards, a higher level of plating process control is required to cope with finer and multilayered structures. For example, in a copper sulfate electroplating bath, monovalent copper ions are generated when copper in the plating solution is dissolved and precipitated by electrolysis. For this reason, depending on the plating conditions, copper particles are generated by a disproportionation reaction (2Cu + → Cu 2+ + Cu), which becomes slime and causes roughness on the plating surface. A brightening agent is used for this measure, which is one of the causes of excessive addition of the brightening agent. In addition, when the through holes and vias of the printed circuit board are formed by copper plating, there is a problem that the layer thickness is not constant and the electrical characteristics are affected. That is, the monovalent copper concentration in the copper plating solution directly affects the defective rate of the plated product.
この問題を解決すべく、特許文献１には、ネオクプロイン試薬を硫酸銅めっき液に添加し、めっき液の吸光度によりめっき液中の一価銅濃度をモニターしつつめっき浴を行う方法が開示されている。この方法の測定原理を示す。まず、ネオクプロイン試薬が一価銅と選択的に反応し、燈色のＣｕ＋−ネオクプロイン錯体を精製する。この錯体はメンブランフィルターに補足され二価銅と分離される。この補足された錯体を有機溶媒により溶出し、その吸光度を測定することにより一価銅の濃度を測定する。 In order to solve this problem, Patent Document 1 discloses a method of adding a neocuproine reagent to a copper sulfate plating solution and performing a plating bath while monitoring the concentration of monovalent copper in the plating solution based on the absorbance of the plating solution. Yes. The measurement principle of this method is shown. First, the neocuproine reagent selectively reacts with monovalent copper to purify the amber Cu + -neocuproine complex. This complex is captured by a membrane filter and separated from divalent copper. The concentration of monovalent copper is measured by eluting the captured complex with an organic solvent and measuring the absorbance.
また特許文献１の方法以外にも、従来よりクプロイン試薬、バソクプロイン試薬を用いて同様の方法で一価銅の濃度を測定する技術が従来から知られており、用いられている。 In addition to the method of Patent Document 1, conventionally, a technique for measuring the concentration of monovalent copper by a similar method using a cuproin reagent and a bathocuproine reagent has been known and used.
しかしながら、クプロイン、ネオクプロイン、バソクプロインのいずれも非水溶性であるため、各錯体を有機溶媒により溶出させる必要がある。実際の生産現場であるめっき浴工程の管理において、このような有機溶媒による溶出を一定期間毎に行うことは極めて煩雑である。また、錯体の補足作業も必要となるため、工程を複雑化、高コスト化させてしまうという問題があった。 However, since all of cuproin, neocuproin, and bathocuproin are insoluble in water, it is necessary to elute each complex with an organic solvent. In the management of the plating bath process, which is an actual production site, it is extremely complicated to perform elution with such an organic solvent at regular intervals. Further, since supplementary work for the complex is required, there is a problem that the process becomes complicated and expensive.
本発明はこのような背景のもとになされたものであり、その目的は、簡易かつ高精度な一価銅の濃度測定方法及び濃度管理方法、並びにこれらに用いられる濃度測定装置を提供することにある。 The present invention has been made based on such a background, and an object of the present invention is to provide a simple and highly accurate method for measuring the concentration of monovalent copper, a concentration management method, and a concentration measuring device used in these methods. It is in.
本発明は以下の手段により上記課題を解決する。なお後述する発明を実施するための最良の形態の説明及び図面で使用した符号を参考のために括弧書きで付記するが、本発明の構成要素は該付記したものには限定されない。 The present invention solves the above problems by the following means. The reference numerals used in the description of the best mode for carrying out the invention and the drawings to be described later are appended in parentheses for reference, but the constituent elements of the present invention are not limited to the appended description.
本発明１の一価銅の濃度測定方法は、銅めっき液（例えば硫酸銅めっき液）を含むｐＨ４〜１０のサンプル溶液及びバソクプロインジスルホン酸二ナトリウム試薬を混合した吸光度測定用溶液を調整する調整工程と、前記調整工程において調整された吸光度測定用溶液の吸光度（例えば波長４８５ｎｍにおける吸光度）を測定する吸光度測定工程と、前記吸光度測定工程において測定された吸光度に基づいて、前記銅めっき液中の一価銅濃度を測定する（一価銅濃度と吸光度との関係をあらわす検量線において、測定された吸光度に対応する一価銅濃度を特定する）濃度測定工程と、を含むことを特徴とする。 A method for measuring the concentration of monovalent copper of the present invention 1 is adjusted to adjust the sample solution and bathocuproine disulfonic acid disodium reagent mixing absorbance measurement solution pH4~10 containing copper plating solution (e.g., copper sulfate plating solution) An absorbance measurement step for measuring the absorbance of the absorbance measurement solution adjusted in the adjustment step (for example, absorbance at a wavelength of 485 nm), and the absorbance in the copper plating solution based on the absorbance measured in the absorbance measurement step. And a concentration measuring step of measuring a monovalent copper concentration (specifying a monovalent copper concentration corresponding to the measured absorbance in a calibration curve representing a relationship between the monovalent copper concentration and the absorbance). .
本発明２の一価銅の濃度測定方法は、本発明１の濃度測定方法であって、前記銅めっき液は硫酸銅めっき液であり、前記調整工程において、前記硫酸銅めっき液を含むｐＨ４〜７（好ましくはｐＨ４〜５．５）のサンプル溶液及びバソクプロインジスルホン酸二ナトリウム試薬を混合した吸光度測定用溶液を調整することを特徴とする。 The monovalent copper concentration measurement method of the present invention 2 is the concentration measurement method of the present invention 1, wherein the copper plating solution is a copper sulfate plating solution, and the adjustment step includes a pH of 4 to 4 containing the copper sulfate plating solution. 7 (preferably PH4～5.5) and adjusting the sample solution and bathocuproine disulfonic acid disodium reagents were mixed for absorbance measurement solution.
本発明３の一価銅の濃度測定方法は、本発明１又は２の濃度測定方法であって、前記銅めっき液には、一価銅と錯体を形成する物質（例えばポリエチレングリコール等）が含まれ、前記吸光度測定工程において、吸光度の収束前の時点（例えば吸光度の上昇開始から２分後）における吸光度を測定し、 前記濃度測定工程において、前記吸光度測定工程において測定した吸光度に基づいて、吸光度の収束後の時点における前記銅めっき液中の一価銅濃度を推定することを特徴とする。 The monovalent copper concentration measurement method of the present invention 3 is the concentration measurement method of the present invention 1 or 2, wherein the copper plating solution contains a substance that forms a complex with monovalent copper (for example, polyethylene glycol). In the absorbance measurement step, the absorbance at the time before the convergence of the absorbance (for example, 2 minutes after the start of the increase in absorbance) is measured. In the concentration measurement step, the absorbance is measured based on the absorbance measured in the absorbance measurement step. The concentration of monovalent copper in the copper plating solution at the time after the convergence of is estimated.
本発明４の一価銅の濃度測定方法は、本発明１又は２の濃度測定方法であって、前記銅めっき液には、一価銅と錯体を形成する物質（例えばポリエチレングリコール等）が含まれ、前記吸光度測定工程において、吸光度の上昇開始から収束前の時点までの所定期間（例えば吸光度の上昇開始から２分間）における吸光度を測定し、前記吸光度測定工程において測定された所定期間における吸光度の時間変動を示す第２吸光度曲線（例えば今回取得した吸光度曲線）を取得する第２吸光度曲線取得工程と、前記濃度測定工程において、一価銅濃度の異なる銅めっき液各々に関する吸光度の上昇開始から収束後の時点までの全体期間（例えば吸光度の上昇開始から１２０分間）における時間変動を示す第１吸光度曲線（例えば吸光度曲線１〜１８）各々と、前記第２吸光度曲線取得手段により取得した第２吸光度曲線とを、前記所定期間内において各々比較し、当該第２吸光度曲線に近似する第１吸光度曲線を特定し、当該特定した第１吸光度曲線に基づいて、前記銅めっき液中の一価銅濃度を推定することを特徴とする。 The monovalent copper concentration measurement method of the present invention 4 is the concentration measurement method of the present invention 1 or 2, wherein the copper plating solution contains a substance that forms a complex with monovalent copper (such as polyethylene glycol). In the absorbance measurement step, the absorbance in a predetermined period (for example, 2 minutes from the start of absorbance increase) from the start of absorbance increase to the time before convergence is measured, and the absorbance in the predetermined period measured in the absorbance measurement step is measured. In the second absorbance curve acquisition step for acquiring a second absorbance curve (for example, the absorbance curve acquired this time) indicating the time variation and the concentration measurement step, convergence starts from the start of the increase in absorbance for each of the copper plating solutions having different monovalent copper concentrations. A first absorbance curve (for example, absorbance curves 1 to 18) showing a time variation in the entire period (for example, 120 minutes from the start of increase in absorbance) up to a later time point Each is compared with the second absorbance curve acquired by the second absorbance curve acquisition means within the predetermined period, the first absorbance curve that approximates the second absorbance curve is specified, and the specified first A monovalent copper concentration in the copper plating solution is estimated based on an absorbance curve.
本発明５の一価銅の濃度管理方法は、本発明１ないし４から選択される１の一価銅の濃度測定方法によって測定された一価銅濃度を管理する一価銅の濃度管理方法であって、前記一価銅濃度が所定値以上であるときに、前記銅めっき液に対して一価銅濃度を低減させる処理（例えばバブリング）を行うことを特徴とする。 The monovalent copper concentration management method of the present invention 5 is a monovalent copper concentration management method for managing the monovalent copper concentration measured by one monovalent copper concentration measurement method selected from the present inventions 1 to 4. And when the said monovalent copper density | concentration is more than predetermined value, the process (for example, bubbling) which reduces a monovalent copper density | concentration with respect to the said copper plating solution is performed.
本発明６の一価銅の濃度測定装置（１）は、銅めっき液を含むｐＨ４〜１０のサンプル溶液及びバソクプロインジスルホン酸二ナトリウム試薬を混合した吸光度測定用溶液を収容する収容手段（例えば測定セル３１）と、前記収容手段に収容された吸光度測定用溶液の吸光度（例えば波長４８５ｎｍにおける吸光度）を測定する吸光度測定手段（例えば制御部３７）と、を有することを特徴とする。 Concentration measuring apparatus of the monovalent copper of the present invention 6 (1), containment means (e.g. measuring for housing the sample solution and bathocuproine disulfonic acid disodium reagent mixing absorbance measurement solution pH4~10 containing copper plating solution Cell 31) and absorbance measurement means (for example, control unit 37) for measuring the absorbance (for example, absorbance at a wavelength of 485 nm) of the absorbance measurement solution accommodated in the accommodation means.
本発明７の一価銅の濃度測定装置（１）は、電解めっき槽（１０）内の銅めっき液をサンプリングするサンプリング手段（例えばサンプリング部２０）と、前記サンプリング手段によりサンプリングされた銅めっき液を含むｐＨ４〜１０のサンプル溶液及びバソクプロインジスルホン酸二ナトリウム試薬を混合した吸光度測定用溶液を調整する調整手段（例えば測定セル３１）と、前記調整手段により調整された吸光度測定用溶液の吸光度（例えば波長４８５ｎｍにおける吸光度）を測定する吸光度測定手段（例えば制御部３７）と、前記吸光度測定手段により測定された吸光度に基づいて、前記銅めっき液中の一価銅濃度を測定する（一価銅濃度と吸光度との関係をあらわす検量線において、測定された吸光度に対応する一価銅濃度を特定する）濃度測定手段（例えばシステム制御部４０）と、を有することを特徴とする。 The monovalent copper concentration measuring device (1) of the present invention 7 includes sampling means (for example, a sampling unit 20) for sampling the copper plating solution in the electrolytic plating tank (10), and the copper plating solution sampled by the sampling means. pH4~10 of the sample solution and bathocuproine disulfonic acid disodium adjusting means reagent for adjusting the mixture absorbance measurement solution containing (e.g. measuring cell 31) and said adjusted by adjustment means absorbance the absorbance of solution for measurement ( For example, based on the absorbance measured by the absorbance measuring means (for example, the control unit 37) for measuring absorbance at a wavelength of 485 nm and the absorbance measuring means, the monovalent copper concentration in the copper plating solution is measured (monovalent copper). Specify the concentration of monovalent copper corresponding to the measured absorbance in the calibration curve representing the relationship between concentration and absorbance That) the density measuring device (e.g., the system control unit 40), and having a.
本発明では、キレート試薬として水に易溶であるバソクプロインジスルホン酸二ナトリウム（Bathocuproinedisulfonic acid, disodium salt）（以下「ＢＣＳ」と略記する。）試薬を使用している。これによれば有機溶媒による溶出が不要であり、錯体の補足が不要であるため、銅めっき液中の一価銅濃度の測定が容易化される。 In the present invention, using bathocuproine disulfonic acid disodium (hereinafter abbreviated as "BCS".) (Bathocuproinedisulfonic acid, disodium salt ) reagent readily soluble in water as a chelating agent. According to this, since elution with an organic solvent is unnecessary and supplementation of a complex is unnecessary, measurement of the monovalent copper concentration in the copper plating solution is facilitated.
［１：銅めっき液］
以下の例では、銅めっき液として硫酸銅めっき液を用いる。但し、本発明は硫酸銅めっき液に限らず、酸性浴及びアルカリ浴に使用される銅めっき液全般を対象とするものである。例えばシアン化銅めっき液やピロ燐酸銅めっき液等も対象となる。通常、銅めっき液のｐＨはＢＣＳ試薬で測定可能なｐＨ域４〜１０から外れている場合が多いが、各種銅めっき液を中和してＢＣＳ試薬と混合することで測定が可能となる。また、後述する実施形態に示すように、緩衝液を用いることによりｐＨ調整を容易化することができる。短時間でのｐＨ調整が可能となり、一価銅濃度を継続的にモニタリングする場合等に有用である。
[1: Copper plating solution]
In the following example, a copper sulfate plating solution is used as the copper plating solution. However, the present invention is not limited to the copper sulfate plating solution, and is intended for all copper plating solutions used in acidic baths and alkaline baths. For example, a copper cyanide plating solution and a copper pyrophosphate plating solution are also targeted. Usually, the pH of the copper plating solution is often out of the pH range of 4 to 10 which can be measured with the BCS reagent, but the measurement can be performed by neutralizing various copper plating solutions and mixing with the BCS reagent. Moreover, as shown in an embodiment described later, pH adjustment can be facilitated by using a buffer solution. The pH can be adjusted in a short time, which is useful for continuously monitoring the monovalent copper concentration.
［２：キレート試薬］
本例では、キレート試薬としてＢＣＳ試薬を用いる。ＢＣＳはＣｕ（I）と選択的に橙黄色の錯体を形成することより、銅の比色試薬として使用される。バソクプロインをスルホン化して水溶性としたもので、水に易溶であるものを使用する。後述する実験では、図１に示すＢＣＳを使用する。ＢＣＳは水溶液中、ｐＨ４〜１０でＣｕ（I）に対しＢＣＳ２分子で１：２の組成の橙黄色のキレートを形成する（λmax＝４８５ｎｍ，ε=１．２×１０４）。重金属イオン類が共存してもＣｕ（I）としか選択的に錯形成しない。一方、抽出操作を必要としないため、操作が簡便で分析に便利である。
[2: Chelating reagent]
In this example, a BCS reagent is used as the chelating reagent. BCS is used as a colorimetric reagent for copper by selectively forming an orange-yellow complex with Cu (I). Bathocuproine is sulfonated to be water-soluble and easily soluble in water. In the experiment described later, the BCS shown in FIG. 1 is used. BCS forms an orange-yellow chelate having a composition of 1: 2 with 2 molecules of BCS against Cu (I) at pH 4 to 10 in an aqueous solution (λmax = 485 nm, ε = 1.2 × 10 4 ). Even if heavy metal ions coexist, they are selectively complexed only with Cu (I). On the other hand, since no extraction operation is required, the operation is simple and convenient for analysis.
（検量線の作成）
硫酸銅めっき溶液を還元することにより一価銅標準溶液を調整し、ＢＣＳ試薬の検量線を作成した。ＢＣＳ試薬はｐＨ４〜１０の領域でほぼ一定の吸光度が得られるが、ｐＨ４〜７、好ましくはｐＨ４〜５．５で安定な吸光度を示すので、ｐＨをこの範囲内に調整した。ＢＣＳ（株式会社同仁化学研究所製、所在地：熊本県）を用いて、モル濃度１０−２ｍｏｌ／ｄｍ３のＢＣＳ水溶液を調整した。試薬特級硫酸銅（II）５水和物を用いてモル濃度１０−３ｍｏｌ／ｄｍ３の硫酸銅水溶液を調整した。この水溶液を分取し（０〜２．５ｍＬ）、還元剤である１０％塩酸ヒドロキシルアミン５ｍＬと２％クエン酸５ｍＬを加え、２５％アンモニア水でｐＨを７〜８に調整した。これに６０％過塩素酸を加えてｐＨ４〜５の一価銅標準溶液を調整後、モル濃度１０−２ｍｏｌ／ｄｍ３のＢＣＳ水溶液を５ｍＬ添加し、水を加えて全量１００ｍＬの吸光度測定用溶液を調整した。
(Create a calibration curve)
A monovalent copper standard solution was prepared by reducing the copper sulfate plating solution, and a calibration curve for the BCS reagent was prepared. The BCS reagent has a substantially constant absorbance in the pH range of 4 to 10, but shows a stable absorbance at pH 4 to 7, preferably pH 4 to 5.5. Therefore, the pH was adjusted within this range. A BCS aqueous solution having a molar concentration of 10 −2 mol / dm 3 was prepared using BCS (manufactured by Dojindo Laboratories, Inc., location: Kumamoto Prefecture). A copper sulfate aqueous solution having a molar concentration of 10 −3 mol / dm 3 was prepared using reagent-grade copper (II) sulfate pentahydrate. This aqueous solution was fractionated (0 to 2.5 mL), 5 mL of 10% hydroxylamine hydrochloride as a reducing agent and 5 mL of 2% citric acid were added, and the pH was adjusted to 7 to 8 with 25% aqueous ammonia. 60% perchloric acid was added to this to prepare a monovalent copper standard solution with a pH of 4-5, 5 mL of a BCS aqueous solution with a molar concentration of 10 −2 mol / dm 3 was added, and water was added for absorbance measurement of 100 mL in total. The solution was adjusted.
このようにして得られた吸光度測定用溶液の吸光度を、分光光度計Ｕ−３３１０（株式会社日立製作所製、所在地：東京都）を用いて測定した。硫酸銅水溶液を加えていない吸光度測定用溶液（上記硫酸銅水溶液の分取量が０のもの）をブランク溶液とした。また、上記硫酸銅水溶液の分取量を異ならせた多くの吸光度測定用溶液を用意した。これら各吸光度測定用溶液に関して、波長４００ｎｍ〜６００ｎｍ付近の吸光度を測定した。測定結果のうち、代表的なものを図２に示す。図２には、Ｃｕ（I）のイオン濃度が０ｍｏｌ／ｄｍ３であるブランク溶液の吸光度曲線（ａ）、及びＣｕ（I）のイオン濃度が各々０．６×１０−５ｍｏｌ／ｄｍ３、３．０×１０−５ｍｏｌ／ｄｍ３、５．０×１０−５ｍｏｌ／ｄｍ３である吸光度測定用溶液の吸光度曲線（ｂ）、（ｃ）、（ｄ）を示す。 The absorbance of the solution for measuring absorbance thus obtained was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd., location: Tokyo). A solution for measuring absorbance without adding an aqueous copper sulfate solution (with a fraction of the aqueous copper sulfate solution of 0) was used as a blank solution. In addition, many solutions for measuring absorbance were prepared by varying the amount of the aqueous copper sulfate solution. With respect to each of these absorbance measurement solutions, the absorbance at a wavelength of about 400 nm to 600 nm was measured. A representative one of the measurement results is shown in FIG. In FIG. 2, the absorbance curve (a) of the blank solution in which the ion concentration of Cu (I) is 0 mol / dm 3 , and the ion concentration of Cu (I) is 0.6 × 10 −5 mol / dm 3 , respectively. Absorbance curves (b), (c) and (d) of the solution for measuring absorbance of 3.0 × 10 −5 mol / dm 3 and 5.0 × 10 −5 mol / dm 3 are shown.
吸光度が最大となる４８５ｎｍの波長において、図３に示すように一価銅濃度０〜５．０×１０−５ｍｏｌ／ｄｍ３の範囲で吸光度との関係を示す直線の検量線（ｒ２値０．９９９９）が得られた。そのモル吸光度係数は１．２６×１０４であり、試薬のモル吸光度係数１．２×１０４（４８５ｎｍ）とほぼ一致した。この結果から、ＢＣＳを使用した吸光度測定によって、硫酸銅水溶液中のＣｕ（I）のイオン濃度を高精度に定量することが可能であることを確認した。ここで、吸光度は上昇を開始してから１分以内で一定の値を示した。即ち、呈色反応が生じてから１分以内に収束し、１時間経過後でも変化は認められなかった。なお本例では波長が４８５ｎｍである光の吸光度を測定しているが、直線の検量線を取得可能な他の波長を用いるようにしても良い。ここで本実施の形態において「吸光度が収束する」とは、所定時間あたりの吸光度の上昇値が、一定値以下（例えば１０分あたり０．０１以下）となることを意味するものとする。また、図３に示すように、一価銅濃度と吸光度は１対１に対応していることから、本実施の形態において吸光度を測定することは、これに対応する一価銅濃度の測定も兼ねているものとする。 As shown in FIG. 3, at a wavelength of 485 nm where the absorbance is maximum, a linear calibration curve (r 2 value) showing the relationship with the absorbance in the range of monovalent copper concentration of 0 to 5.0 × 10 −5 mol / dm 3. 0.9999) was obtained. The molar absorbance coefficient was 1.26 × 10 4 , which almost coincided with the molar absorbance coefficient of the reagent 1.2 × 10 4 (485 nm). From this result, it was confirmed that the ion concentration of Cu (I) in the aqueous copper sulfate solution can be quantified with high accuracy by measuring the absorbance using BCS. Here, the absorbance showed a constant value within 1 minute after starting to increase. That is, it converged within 1 minute after the color reaction occurred, and no change was observed even after 1 hour. In this example, the absorbance of light having a wavelength of 485 nm is measured. However, other wavelengths capable of acquiring a linear calibration curve may be used. Here, in the present embodiment, “absorbance converges” means that the increase in absorbance per predetermined time is equal to or less than a certain value (for example, 0.01 or less per 10 minutes). Further, as shown in FIG. 3, since the monovalent copper concentration and the absorbance have a one-to-one correspondence, the measurement of the absorbance in the present embodiment also means the measurement of the monovalent copper concentration corresponding to this. It shall also serve as
［３．呈色用緩衝液］
硫酸銅めっき液は酸濃度が極めて高く、ＢＣＳ試薬による比色測定では、ｐＨを４以上に調整する必要がある。一方、ｐＨが７以上になると、水酸化銅の白色沈殿が生じてしまい、吸光度が不安定になるため、緩衝液を使用する必要がある。緩衝液によって硫酸銅めっき液をｐＨ４〜７程度に調整することが好ましく、ｐＨ４〜５．５に調整することが特に好ましい。後述する実験では銅イオンとの相互作用が小さく、比較的単純な酢酸−ＮａＯＨ系の緩衝液を用いた。
[3. Coloring buffer]
The copper sulfate plating solution has an extremely high acid concentration, and it is necessary to adjust the pH to 4 or more in the colorimetric measurement using the BCS reagent. On the other hand, when the pH is 7 or more, white precipitation of copper hydroxide occurs and the absorbance becomes unstable, so it is necessary to use a buffer solution. It is preferable to adjust the copper sulfate plating solution to about pH 4 to 7 with a buffer solution, and it is particularly preferable to adjust to pH 4 to 5.5. In the experiment described later, a relatively simple acetic acid-NaOH buffer solution having a small interaction with copper ions was used.
試薬として、１ｍｏｌ／ｄｍ３のＮａＯＨ水溶液、１ｍｏｌ／ｄｍ３の酢酸（容量分析用）、及び１０−２ｍｏｌ／ｄｍ３のＢＣＳ溶液を用いた。１００ｍＬビーカーに水２０ｍＬ、酢酸水溶液１０ｍＬ、めっき液１ｍＬ、ＢＣＳ溶液２ｍＬを加え、よく振り混ぜ、ｐＨを測定する。これに濁りや沈殿が生じないように徐々にＮａＯＨ水溶液を加え、ｐＨを４〜４．５（測定値は４．２３）に調整した。この際使用したＮａＯＨ水溶液の添加量は７．２ｍＬであった。この溶液を５０ｍＬメスフラスコに移して水で全量を５０ｍＬに希釈した。この溶液のｐＨを測定して、ｐＨが４以上であることを確認した。このように、５０ｍＬメスフラスコに、水２０ｍＬ、酢酸水溶液１０ｍＬ、ＮａＯＨ水溶液７．２ｍＬ、ＢＣＳ試薬２ｍＬを投入して、水で５０ｍＬに調整したものを呈色用緩衝液とした。 As reagents, 1 mol / dm 3 NaOH aqueous solution, 1 mol / dm 3 acetic acid (for volumetric analysis), and 10 −2 mol / dm 3 BCS solution were used. Add water (20 mL), acetic acid aqueous solution (10 mL), plating solution (1 mL), and BCS solution (2 mL) to a 100 mL beaker, shake well, and measure the pH. To this, an aqueous NaOH solution was gradually added so as not to cause turbidity or precipitation, and the pH was adjusted to 4 to 4.5 (measured value was 4.23). The amount of NaOH aqueous solution used at this time was 7.2 mL. This solution was transferred to a 50 mL volumetric flask and diluted to 50 mL with water. The pH of this solution was measured to confirm that the pH was 4 or higher. In this manner, 20 mL of water, 10 mL of acetic acid aqueous solution, 7.2 mL of NaOH aqueous solution, and 2 mL of BCS reagent were charged into a 50 mL volumetric flask and adjusted to 50 mL with water to obtain a color buffer.
なお、本実施形態においては緩衝液（上記呈色用緩衝液からＢＣＳ試薬を除いた溶液）とＢＣＳ試薬を混合したものを呈色用緩衝液とし、この呈色用緩衝液を硫酸銅めっき液と混合することによって吸光度測定用溶液を調整している。即ち、硫酸銅めっき液を含むｐＨ４〜５．５のサンプル溶液の調整及びバソクプロインジスルホン酸二ナトリウム試薬の混合を同時に行うようにしている。しかし、吸光度測定用溶液の調整方法はこの方法に限られるものではなく、例えば硫酸銅めっき液に緩衝液を混合してサンプル溶液を調整した後、調整したサンプル溶液にＢＣＳ試薬を混合するようにしても良く、硫酸銅めっき液にＢＣＳ試薬を混合した後、さらに緩衝液を混合するようにしても良い。 In this embodiment, a mixture of a buffer solution (a solution obtained by removing the BCS reagent from the color buffer solution) and a BCS reagent is used as a color buffer solution, and the color buffer solution is a copper sulfate plating solution. The solution for measuring the absorbance is prepared by mixing with. That is, to perform the mixing of the adjustment and bathocuproine disulfonic acid disodium reagent sample solution pH4~5.5 containing copper sulfate plating solution at the same time. However, the method for adjusting the absorbance measurement solution is not limited to this method. For example, after preparing a sample solution by mixing a buffer solution with a copper sulfate plating solution, a BCS reagent is mixed with the adjusted sample solution. Alternatively, after mixing the BCS reagent with the copper sulfate plating solution, a buffer solution may be further mixed.
［４．吸光度の測定］
呈色用緩衝液を分光光度計の参照用セルとサンプル用セルにそれぞれ２．５ｍＬ移した。サンプル用セルに硫酸銅めっき液５０μＬを注入して吸光度測定用溶液を調整した。その吸光度測定用溶液の１ｍＬ程度をピペットで吸い上げ、排出することで撹拌した。ここでセル中の硫酸銅めっき液は５１倍に希釈されたことになる。吸光度測定用溶液調整後２０分までの吸光度に関して、波長範囲３５０〜７００ｎｍ、スキャンスピード２００ｎｍ／ｍｉｎで吸収スペクトルを測定した。銅めっき液試料として、実際の硫酸銅電気めっき浴工程で使用されている添加剤成分の異なる２種類の硫酸銅めっき液（以下、Ａ液、Ｂ液と称する）を用意した。
[4. Absorbance measurement]
2.5 mL of the color buffer was transferred to the reference cell and the sample cell of the spectrophotometer. A solution for measuring absorbance was prepared by injecting 50 μL of a copper sulfate plating solution into the sample cell. About 1 mL of the absorbance measurement solution was sucked up with a pipette and stirred by discharging. Here, the copper sulfate plating solution in the cell was diluted 51 times. Absorbance spectra were measured at a wavelength range of 350 to 700 nm and a scan speed of 200 nm / min with respect to absorbance up to 20 minutes after preparation of the solution for absorbance measurement. As copper plating solution samples, two types of copper sulfate plating solutions (hereinafter referred to as A solution and B solution) having different additive components used in the actual copper sulfate electroplating bath process were prepared.
これらのＡ液及びＢ液について、それぞれ新液（Ａ−１液，Ｂ−１液）及び稼働液（Ａ−２液，Ｂ−２液）を用意した。新液であるＡ−１液を所定期間電気めっき浴工程で使用した後の状態のものがＡ−２液である。また、新液であるＢ−１液を所定期間電気めっき浴工程で使用した後の状態のものがＢ−２液である。各々に関して吸収スペクトルを測定した結果を図４に示す。新液と稼働液では吸収スペクトルに明確な差違が認められ、稼働液中には一価銅が比較的多量に存在していることが確認された。一方、新液中には一価銅は殆ど含まれていない。前述した検量線に基づいて、Ａ−２液中の一価銅濃度が１．２ｍｍｏｌ／ｄｍ３、Ｂ−２液中の一価銅濃度が０．２ｍｍｏｌ／ｄｍ３であることが確認された。 About these A liquid and B liquid, the new liquid (A-1 liquid, B-1 liquid) and the working liquid (A-2 liquid, B-2 liquid) were prepared, respectively. The A-2 solution is a state after the A-1 solution, which is a new solution, is used in the electroplating bath process for a predetermined period. Moreover, the thing of the state after using B-1 liquid which is a new liquid for an electroplating bath process for a predetermined period is B-2 liquid. The result of measuring the absorption spectrum for each is shown in FIG. A clear difference was observed in the absorption spectrum between the new solution and the working solution, and it was confirmed that a relatively large amount of monovalent copper was present in the working solution. On the other hand, the monovalent copper is hardly contained in the new solution. Based on the calibration curve described above, it was confirmed that the monovalent copper concentration in the A-2 solution was 1.2 mmol / dm 3 and the monovalent copper concentration in the B-2 solution was 0.2 mmol / dm 3 . .
図５には、Ａ−１液及びＡ−２液の吸光度の時間変化を示す。稼働液であるＡ−２液に関しては、吸光度は、上昇開始から１〜５分以内で急激に上昇し、その後も徐々に上昇していることが確認された。新液であるＡ−１液では、吸光度の値が小さく、時間変化はほとんど認められなかった。この吸光度測定用溶液調整直後の吸光度の時間変化については、Ｂ液でも同様の傾向が認められた。稼働液であるＡ−２液及びＢ−２液における吸光度の時間変化は、前述した一価銅標準溶液の吸光度の時間変化と比較して大きな差違があることが把握された。一価銅標準溶液では、吸光度の値は上昇開始から１分以内で一定となり、その後、１時間経過しても変化は生じなかった。なお、Ａ−２液に関しては、吸光度の上昇開始から１〜５分経過した後は上昇が徐々に緩やかになり、数時間経過した時点では吸光度の上昇が収束していた（１０分あたりの上昇値が０．０１以下となった）。このときの収束値（最終吸光度）は、０．３６であった。 In FIG. 5, the time change of the light absorbency of A-1 liquid and A-2 liquid is shown. Regarding the liquid A-2 which is the working liquid, it was confirmed that the absorbance rapidly increased within 1 to 5 minutes from the start of the increase and gradually increased thereafter. In the liquid A-1 which is a new liquid, the absorbance value was small, and almost no change with time was observed. With respect to the change in absorbance with time immediately after preparation of the solution for measuring absorbance, the same tendency was observed in solution B. It was understood that the time changes in absorbance in the working liquids A-2 and B-2 were significantly different from the changes in absorbance of the monovalent copper standard solution described above. In the monovalent copper standard solution, the absorbance value became constant within 1 minute from the start of the increase, and thereafter, no change occurred even after 1 hour. In addition, about the A-2 liquid, after 1 to 5 minutes passed from the start of the rise in absorbance, the rise gradually slowed down, and the rise in absorbance had converged at the time when several hours passed (rise per 10 minutes). The value became 0.01 or less). The convergence value (final absorbance) at this time was 0.36.
これらの実験結果より、一価銅を含む標準溶液に対しては１分程度で収束するＢＣＳ試薬の反応が、所謂稼働液に関しては、吸光度測定用溶液調整から長時間（上記の例では数時間）を経なければ当該稼働液の一価銅濃度を正確に測定することができないという問題があることがわかった。しかしながら一価銅濃度はめっき製品の不良率に直接影響する値であり、短時間でのフィードバックが必要なケースが多くある。この問題を解決すべく、本発明者らは、以下のように銅めっき液中の一価銅の状態分析を行った。 From these experimental results, the reaction of the BCS reagent that converges in about 1 minute with respect to a standard solution containing monovalent copper is a long time (several hours in the above example) from the adjustment of the solution for absorbance measurement. ), It was found that there was a problem that the monovalent copper concentration of the working fluid could not be measured accurately. However, the monovalent copper concentration is a value that directly affects the defect rate of the plated product, and there are many cases where feedback in a short time is required. In order to solve this problem, the present inventors analyzed the state of monovalent copper in the copper plating solution as follows.
［４．銅めっき液中の一価銅の状態分析］
銅めっき液中の一価銅の状態分析のために、銅めっき液の新液Ｂ−１と稼働液Ｂ−２について、プロトン核磁気共鳴（１Ｈ−ＮＭＲ（１H-Nuclear Magnetic Resonance Spectroscopy））及びマトリックス支援レーザー脱離イオン化質量分析（ＭＡＬＤＩ−ＭＳ（Matrix Assisted Laser Desorption/Ionization-Mass Spectrometry）による成分分析を行った。ＭＡＬＤＩ−ＭＳにはＡＸＩＭＡ−ＴＯＦ２（株式会社島津製作所製、所在地：京都府）を用い、マトリックスにはカーボンを用いた。試料としては、銅めっき液を中和し、遠心分離後、上澄み液を凍結乾燥したものを使用した。Ｂ−１液及びＢ−２液の１Ｈ−ＮＭＲによる成分分析によって、銅めっき液中にはポリエチレングリコール（ＰＥＧ（polyethylene glycol））が多量に存在することが確認された。ＰＥＧは通常、硫酸銅めっき液に抑制剤として添加されている。さらに、高分子量まで測定可能なＭＡＬＤＩ−ＭＳによる成分分析によって、鎖長の異なるＰＥＧが一価銅に配位した［Ｈ（ＯＣＨ２ＣＨ２）ｎＯＨ＋Ｃｕ］＋をｎ＝４〜４３で検出することができた。図６に示すように、［Ｈ（ＯＣＨ２ＣＨ２）ｎＯＨ＋Ｃｕ］＋（ｎ＝４〜４３）の各質量対電荷比（Mass/Charge）に対応する強度（Intensity）の上方に「○」を表示させた。ｎ＝４〜４３に対応する各位置に強度の明確なピークがあらわれている。このようにして、めっき液中のＣｕ（I）−ＰＥＧ錯体［Ｈ（ＯＣＨ２ＣＨ２）ｎＯＨ＋Ｃｕ］＋（ｎ＝４〜４３）の各々の存在比率を比較することができる。
[4. State analysis of monovalent copper in copper plating solution]
In order to analyze the state of monovalent copper in the copper plating solution, proton nuclear magnetic resonance ( 1 H-NMR ( 1 H-Nuclear Magnetic Resonance Spectroscopy)) was conducted on the new solution B-1 and working solution B-2 of the copper plating solution. ) And matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS) (Matrix Assisted Laser Desorption / Ionization-Mass Spectrometry). As a sample, the copper plating solution was neutralized, centrifuged, and the supernatant was freeze-dried.B-1 solution and B-2 solution the component analysis by 1 H-NMR, is in the copper plating solution was confirmed that the polyethylene glycol (PEG (polyethylene glycol)) is present in a large amount .PEG usually Is added as an inhibitor to the copper sulfate plating solution. Further, the component analysis by measurable MALDI-MS to high molecular weight, different PEG chain length is coordinated to monovalent copper [H (OCH 2 CH 2) n OH + Cu] + could be detected at n = 4 to 43. As shown in FIG. 6, each mass-to-charge ratio of [H (OCH 2 CH 2 ) n OH + Cu] + (n = 4 to 43) “◯” is displayed above the intensity corresponding to (Mass / Charge), and clear peaks of intensity appear at each position corresponding to n = 4 to 43. In this way, plating is performed. The abundance ratios of Cu (I) -PEG complex [H (OCH 2 CH 2 ) n OH + Cu] + (n = 4 to 43) in the liquid can be compared.
この結果は、一価銅がＰＥＧの配位した錯体として安定に存在することを示している。図７にはＣｕ（I）−ＰＥＧ錯体のモデルを示す。本手法のように、ＭＡＬＤＩ−ＭＳによるＰＥＧが添加された硫酸銅めっき液の成分分析において、［Ｈ（ＯＣＨ２ＣＨ２）ｎＯＨ＋Ｃｕ］＋の各質量対電荷比に対応する信号強度を特定可能な態様で表示することで、ｎの異なる、即ち鎖長の異なるＰＥＧに配位されたＣｕ（I）−ＰＥＧ錯体の各々の存在比率を把握することができる。硫酸銅電気めっき液の中には抑制剤としての高分子のＰＥＧ以外にも、平滑剤、促進剤など、比較的分子量の小さい有機成分が存在している。これらの銅めっき液中での作用については、現在でも検討が進められている。銅めっき液中の一価銅は、これらの分子量の小さい有機分子との錯体（以下「小錯体」と称す）や、分子量が比較的大きなＰＥＧ等との錯体（以下「大錯体」と称す）を形成することにより、比較的安定にめっき液中で存在していると推定される。 This result indicates that monovalent copper exists stably as a complex in which PEG is coordinated. FIG. 7 shows a model of the Cu (I) -PEG complex. As in this method, the signal intensity corresponding to each mass-to-charge ratio of [H (OCH 2 CH 2 ) n OH + Cu] + can be specified in the component analysis of the copper sulfate plating solution to which PEG is added by MALDI-MS By displaying in such a manner, it is possible to grasp the abundance ratio of each of the Cu (I) -PEG complexes coordinated to PEG having different n, that is, having different chain lengths. In the copper sulfate electroplating solution, there are organic components having a relatively small molecular weight, such as a smoothing agent and an accelerator, in addition to the high molecular weight PEG as an inhibitor. The action in these copper plating solutions is still under investigation. The monovalent copper in the copper plating solution is a complex with these organic molecules having a low molecular weight (hereinafter referred to as “small complex”) or a complex with a relatively large molecular weight such as PEG (hereinafter referred to as “large complex”). By forming the film, it is presumed that it exists in the plating solution relatively stably.
図５及び図６に示した実験データに基づいて、ＢＣＳ試薬による一価銅の呈色反応の時間変化のモデルを図８に示す。ＢＣＳ等のキレート試薬は、銅めっき液中の一価銅の錯体（前述したＰＥＧとの錯体等）と比較して、安定な錯体を形成するので呈色反応が進行する。ここで、小錯体の一価銅には容易にＢＣＳが接触できるのに対し、大錯体であるＣｕ（I）−ＰＥＧ錯体では、大きなＰＥＧ分子に一価銅が取り囲まれているため、立体障害によってＢＣＳが容易に一価銅に接触できずに呈色反応が抑制されていると考えられる。 Based on the experimental data shown in FIGS. 5 and 6, a model of the time change of the color reaction of monovalent copper by the BCS reagent is shown in FIG. 8. A chelating reagent such as BCS forms a stable complex as compared with a monovalent copper complex (such as a complex with PEG described above) in a copper plating solution, and thus a color reaction proceeds. Here, BCS can be easily contacted with monovalent copper of a small complex, whereas in a large complex Cu (I) -PEG complex, monovalent copper is surrounded by large PEG molecules. Therefore, it is considered that the color reaction is suppressed because the BCS cannot easily contact the monovalent copper.
このため、呈色反応の初期には、小錯体の一価銅とＢＣＳとの反応が早く、急激に呈色を示すが、大錯体の一価銅との反応は容易には進まないために、初期の反応が終わると徐々にしか呈色反応は進まないことになる。これが図５に示した吸光度の時間変化となってあらわれたと推定される。ＢＣＳによる呈色反応に時間変化が生じることは、一価銅の定量分析に相当の時間を要することになり、銅電気めっき浴工程を管理する際の問題点となる。そこで本発明者らは、呈色反応の時間変化を一価銅の小錯体と大錯体のモデルに基づいて検討した。 For this reason, in the initial stage of the color reaction, the reaction between the monovalent copper of the small complex and BCS is fast and shows a rapid coloration, but the reaction with the monovalent copper of the large complex does not proceed easily. When the initial reaction is completed, the color reaction only proceeds gradually. It is presumed that this appeared as a change in absorbance with time shown in FIG. The time change in the color reaction by BCS requires a considerable amount of time for quantitative analysis of monovalent copper, which is a problem in managing the copper electroplating bath process. Therefore, the present inventors examined the time change of the color reaction based on models of a monovalent copper small complex and a large complex.
図８（ａ）に示すように、ＢＣＳと混合させる前のめっき液中には、一価銅（Cu＋）、小錯体（small Cu(I) complex）、及び大錯体（Cu(I)-PEG complex）が混在している。この状態のめっき液にＢＣＳを混合させると、図８（ｂ）に示すように反応の初期段階で、錯体を形成していない一価銅にＢＣＳが配位し、比較的接触しやすい小錯体の一価銅にもＢＣＳが配位する。即ち、初期段階では錯体を形成していない一価銅及び小錯体の一価銅に容易にＢＣＳが配位することで急激な呈色反応が生じる。一方、大錯体に関しては、鎖長の長いＰＥＧが一価銅に配意しているためＢＣＳが一価銅に接触し難い。従って図８（ｃ）に示すように、錯体を形成していない一価銅及び小錯体の一価銅へのＢＣＳの配位が終了した後、一定時間を経てから大錯体の一価銅へのＢＣＳの配位が終了して呈色反応が終了すると推定される。 As shown in FIG. 8A, in the plating solution before being mixed with BCS, monovalent copper (Cu + ), small complex (small Cu (I) complex), and large complex (Cu (I) −). PEG complex). When BCS is mixed with the plating solution in this state, as shown in FIG. 8B, at the initial stage of the reaction, BCS is coordinated to monovalent copper that has not formed a complex, and a small complex that is relatively easy to contact. BCS also coordinates to monovalent copper. That is, in the initial stage, BCS easily coordinates to monovalent copper that has not formed a complex and monovalent copper of a small complex, thereby causing a rapid color reaction. On the other hand, for large complexes, BCS is difficult to contact monovalent copper because PEG having a long chain length is dedicated to monovalent copper. Therefore, as shown in FIG. 8C, after the coordination of BCS to the monovalent copper not forming the complex and the monovalent copper of the small complex is completed, after a certain period of time, to the monovalent copper of the large complex. It is presumed that the color reaction is completed after the coordination of the BCS.
図５に示したように、ＢＣＳと硫酸銅めっき液を混合させてから１〜５分以内に急激に吸光度が上昇し、その後徐々に吸光度の上昇が緩やかになり、数時間を経過すると吸光度の上昇が概ね収束する。これはまず、錯体を形成していない一価銅及び接触しやすい小錯体の一価銅へＢＣＳが配位し、この配位が概ね１〜５分程度で終了し、その後徐々に大錯体へのＢＣＳの配位が進行し、大錯体へのＢＣＳの配意が概ね数時間程度で終了するためと推定される。 As shown in FIG. 5, the absorbance rapidly increased within 1 to 5 minutes after mixing the BCS and the copper sulfate plating solution, and then the absorbance gradually increased. After several hours, the absorbance was decreased. The rise generally converges. First, BCS coordinates to monovalent copper that is not forming a complex and monovalent copper that is easy to contact, and this coordination is completed in about 1 to 5 minutes, and then gradually becomes a large complex. It is presumed that the coordination of BCS proceeds and the BCS coordination to the large complex is completed in about several hours.
なお、ポリエチレングリコールに限らず、一価銅と大錯体を形成しうる添加剤が存在する場合、同様に吸光度が上昇を開始してから数分後までは吸光度が急激に上昇し、その後徐々に吸光度の上昇が緩やかになり、数時間で収束に向かう現象が生じうる。 If there is an additive that can form a large complex with monovalent copper, not limited to polyethylene glycol, the absorbance increases rapidly until a few minutes after the start of the increase, and then gradually increases. The rise in absorbance becomes gradual, and a phenomenon of convergence may occur in a few hours.
ここで、一価銅と大錯体を形成する物質としては、銅めっき液に添加剤として含まれるポリマー等がある。例えば、銅めっき液に添加剤として含まれるポリオキシエチレン系又はポリオキシプロピレン系のノニオン系界面活性剤（ポリエチレングリコール）であり、具体的には、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシエチレンオレインエーテル等が挙げられる。また、ポリビニールアルコール、カルボキシメチルセルロース等が一価銅と大錯体を形成しうる。但し、これらの物質に限定されるものではなく、ポリマー以外の物質、界面活性剤以外の物質であって一価銅と錯体を形成するものが該当する。 Here, as a substance which forms a large complex with monovalent copper, there are a polymer and the like contained as an additive in a copper plating solution. For example, a polyoxyethylene-based or polyoxypropylene-based nonionic surfactant (polyethylene glycol) contained as an additive in a copper plating solution, specifically, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene Examples include ethylene olein ether. In addition, polyvinyl alcohol, carboxymethyl cellulose and the like can form a large complex with monovalent copper. However, it is not limited to these substances, and substances other than polymers and substances other than surfactants that form a complex with monovalent copper are applicable.
このようにポリエチレングリコールのような大錯体形成原因物質が存在することが、呈色反応が生じてから一定時間吸光度が収束せずに上昇を続ける原因であることを解明した。また、この大錯体形成原因物質による影響は初期の反応後に、徐々に増加するものでありその増加量は同一の稼働液においては安定していることがわかった。本発明では、収束前の吸光度に基づいて一価銅の濃度を測定することを可能としている。 Thus, it has been clarified that the presence of a large complex formation-causing substance such as polyethylene glycol is a cause that the absorbance does not converge for a certain period of time after the color reaction occurs and continues to rise. It was also found that the effect of the large complex formation causative substance gradually increases after the initial reaction, and the increase amount is stable in the same working liquid. In the present invention, the concentration of monovalent copper can be measured based on the absorbance before convergence.
［５．実証実験］
図９は、硫酸銅電気めっき浴工程で使用されている硫酸銅めっき液の吸光度を長期間モニタリングした結果を示す図である。一価銅の分析について、実際にプリント回路基板の硫酸銅電気めっき浴工程で使用されている硫酸銅めっき液（前述したＡ液）のモニタリングを実施した。生産ラインに使用されている硫酸銅めっき液についてほぼ１ヶ月の期間、生産ライン稼働中又は稼働直後の一価銅濃度、及び休止期間終了直前（稼働開始直前）の吸光度を測定した。通常、生産ライン稼働中に電解めっき槽に流している電流は、週末等の休暇時等に停止させている。図中のＯＮで示す期間は電流を流している期間（稼働期間）であり、図中のＯＦＦで示す期間は電流を停止している期間（休止期間）である。休止期間においてめっき浴は電気的に休止した状態に保たれている。図中の曲線ａは、吸光度の上昇開始から２０分後の吸光度を示しており、曲線ｂは、吸光度の上昇開始から２分後の吸光度を示している。曲線ｃは前記両吸光度の差、即ち吸光度の上昇開始から２分〜２０分迄の１８分間に上昇した吸光度を示している。
[5. Demonstration experiment]
FIG. 9 is a diagram showing the results of long-term monitoring of the absorbance of the copper sulfate plating solution used in the copper sulfate electroplating bath process. About the analysis of monovalent copper, the copper sulfate plating solution (A liquid mentioned above) currently used in the copper sulfate electroplating bath process of a printed circuit board was actually implemented. For the copper sulfate plating solution used in the production line, the monovalent copper concentration during the operation of the production line or immediately after the operation of the production line, and the absorbance immediately before the end of the suspension period (immediately before the start of operation) were measured. Usually, the current flowing through the electrolytic plating tank during the operation of the production line is stopped during a holiday such as a weekend. The period indicated by ON in the figure is a period during which current is flowing (operation period), and the period indicated by OFF in the figure is a period during which current is stopped (rest period). In the rest period, the plating bath is kept in an electrically rested state. Curve a in the figure shows the absorbance 20 minutes after the start of the increase in absorbance, and curve b shows the absorbance 2 minutes after the start of the increase in absorbance. A curve c shows the difference between the two absorbances, that is, the absorbance increased for 18 minutes from the start of the increase in absorbance to 2 to 20 minutes.
まず図９に示すようにモニタリング０日目に、稼働を終えた直後の硫酸銅めっき液の吸光度を測定した結果、吸光度の上昇開始から２０分後の吸光度ａが０．２０、同２分後の吸光度ｂが０．１４、両者の差ｃが０．０６であった。次に、モニタリング３日目に休止期間（ｏｆｆ期間）終了直前（ｏｎ期間開始直前）の吸光度を測定した結果、吸光度の上昇開始から２０分後の吸光度ａが０．２１、同２分後の吸光度ｂが０．１５、両者の差ｃが０．０６であった。次に、モニタリング５日目に稼働中（ｏｎ期間中）の吸光度を測定した結果、吸光度の上昇開始から２０分後の吸光度ａが０．２０、同２分後の吸光度ｂが０．１４、両者の差ｃが０．０６であった。次に、モニタリング１０日目に休止期間（ｏｆｆ期間）終了直前（ｏｎ期間開始直前）の吸光度を測定した結果、吸光度の上昇開始から２０分後の吸光度ａが０．２１、同２分後の吸光度ｂが０．１５、両者の差ｃが０．０６であった。 First, as shown in FIG. 9, on the 0th day of monitoring, the absorbance of the copper sulfate plating solution immediately after the operation was measured. As a result, the absorbance a after 20 minutes from the start of the increase in absorbance was 0.20, and 2 minutes later. The absorbance b was 0.14, and the difference c between the two was 0.06. Next, as a result of measuring the absorbance immediately before the end of the rest period (off period) on the third day of monitoring (immediately before the start of the on period), the absorbance a 20 minutes after the start of the increase in absorbance was 0.21, and the absorbance after 2 minutes Absorbance b was 0.15, and the difference c between the two was 0.06. Next, as a result of measuring the absorbance during operation (on period) on the fifth day of monitoring, the absorbance a after 20 minutes from the start of the increase in absorbance is 0.20, the absorbance b after 2 minutes is 0.14, The difference c between them was 0.06. Next, as a result of measuring the absorbance immediately before the end of the rest period (off period) on the 10th day of monitoring (immediately before the start of the on period), the absorbance a 20 minutes after the start of the increase in absorbance was 0.21, and the absorbance after 2 minutes Absorbance b was 0.15, and the difference c between the two was 0.06.
このようにして、稼働中又は稼働直後の吸光度、及び休止期間終了直前（稼働開始直前）の吸光度を交互に測定した結果、図９に示すように、休止期間終了直前（稼働開始直前）の吸光度ａは、その前後の稼働期間中又は稼働期間直後に測定された吸光度よりも高いという特徴がみられた。全ての測定データについてこの傾向があてはまる。また、最も長い最後の休止期間（モニタリング２１日目〜３１日目）において、吸光度の上昇値が最も高い。これは休止期間中には例外なく一価銅濃度が上昇したことを示すものである。従来より、硫酸銅電気めっき浴工程において稼働開始日はめっき不具合の発生頻度が比較的高いことが経験的に知られていた。図９に示す実験結果は、この事実を裏付けるものである。 As a result of alternately measuring the absorbance during operation or immediately after operation and the absorbance immediately before the end of the suspension period (immediately before the start of operation), as shown in FIG. 9, the absorbance immediately before the end of the suspension period (immediately before the start of operation) The characteristic that a was higher than the light absorbency measured during the operation period before and after that or immediately after the operation period was observed. This trend is true for all measured data. Moreover, in the longest last rest period (monitoring 21st day-31st day), the increase value of an absorbance is the highest. This indicates that the monovalent copper concentration increased without exception during the rest period. Conventionally, it has been empirically known that the frequency of occurrence of plating defects is relatively high on the operation start date in the copper sulfate electroplating bath process. The experimental results shown in FIG. 9 confirm this fact.
ここで呈色反応開始から２分後と２０分後の吸光度の差については、曲線ｃが示すように稼働期間、休止期間にかかわらず、モニタリング期間中ほぼ一定値であった。これは前述した大錯体において、一価銅は大きな有機分子（ＰＥＧ）に囲まれて比較的安定に存在しており、めっき浴の状態（ｏｎ、ｏｆｆ）に影響を受けにくいためと考えられる。一方、前述した小錯体では、立体障害が比較的小さいためにめっき浴中の溶存酸素などとの一価銅の反応が起こりやすく、その存在量については相対的にめっき浴の状態（ｏｎ、ｏｆｆ）の影響をうけやすいと考えられる。 Here, the difference in absorbance between 2 minutes and 20 minutes after the start of the color reaction was almost constant during the monitoring period regardless of the operation period and the rest period as shown by the curve c. This is considered to be because, in the large complex described above, monovalent copper is surrounded by large organic molecules (PEG) and exists relatively stably, and is not easily affected by the state of the plating bath (on, off). On the other hand, in the small complex described above, since the steric hindrance is relatively small, the reaction of monovalent copper with dissolved oxygen or the like in the plating bath tends to occur. ).
これらの実験結果と、「稼働開始日はめっき不具合の発生頻度が比較的高い」という事実を勘案すれば、生産ラインで使用されている硫酸銅めっき液に関しては、稼働条件に影響を受けやすい、吸光度の上昇開始から数分後（本例では２分後）の吸光度の測定が重要であり、且つ十分である。即ち、一価銅濃度は時間経過によって変動するが、吸光度が収束するのを待つことなく、収束前の時点の吸光度を測定すれば十分である。これにより、硫酸銅電気めっき浴における一価銅の濃度測定を短時間で行うことができる。 Considering these experimental results and the fact that the frequency of occurrence of plating defects is relatively high on the operation start date, the copper sulfate plating solution used in the production line is easily affected by operating conditions. It is important and sufficient to measure the absorbance several minutes after the start of the increase in absorbance (in this example, after 2 minutes). That is, although the monovalent copper concentration varies with time, it is sufficient to measure the absorbance before the convergence without waiting for the absorbance to converge. Thereby, the density | concentration measurement of the monovalent copper in a copper sulfate electroplating bath can be performed in a short time.
ここで呈色反応開始から２分後から２０分後までの期間に増加した吸光度は、曲線ｃが示すように稼働期間、休止期間にかかわらず、モニタリング期間中ほぼ一定値（０．０５）であった。さらに、呈色反応開始から２分後から２時間経過し、十分に収束しているときの吸光度変化量は０．１０であった、この結果より、吸光度の上昇開始から２分後から、収束時までの吸光度の上昇幅を予め取得しておくことで、上昇開始から２分後に測定した吸光度（例えば０．１５）に、上記取得した吸光度を加算した吸光度（例えば０．２５）を収束時の吸光度として推定し、これに基づいて一価銅濃度を推定することが可能である。 Here, the absorbance increased during the period from 2 minutes to 20 minutes after the start of the color reaction was almost constant (0.05) during the monitoring period regardless of the operation period and the rest period as shown by the curve c. there were. Furthermore, after 2 minutes from the start of the color reaction, 2 hours have passed and the amount of change in absorbance when fully converged was 0.10. From this result, convergence was observed from 2 minutes after the start of the increase in absorbance. By acquiring the increase in absorbance up to the time in advance, the absorbance (for example, 0.25) obtained by adding the acquired absorbance to the absorbance (for example, 0.15) measured 2 minutes after the start of the increase is converged. It is possible to estimate the monovalent copper concentration based on this.
ここで、吸光度の上昇開始から数分後（本例では２分後）の吸光度、即ち吸光度が収束していない期間において吸光度を測定する場合、一価銅を再酸化させるためのエアバブリングを行うか否かの判定基準を設けておくと良い。例えば本例の場合には、吸光度の上昇開始から２分後の吸光度が０．１５以上の場合には当該稼働液に対してエアバブリングを行うようにすると良い。吸光度の上昇が収束し実際の一価銅濃度を測定することができるまで、反応開始後２時間程度を要することがある。しかしここで、２分後から２時間後の吸光度変化量についてその間の上昇幅が０．１０であることを予め取得しておくとき、２分後の吸光度が０．１５を超えている場合、２時間経過時の吸光度は０．２５を超えていると推定することができる。即ち、吸光度の上昇開始から数分後の基準値（本例では２分後の０．１５）を設定することで、当該基準値に基づいてエアバブリングの有無を判定可能であるため、吸光度の収束を待つことなく一価銅の濃度管理を迅速に行うことが可能となる。 Here, when measuring the absorbance after a few minutes (in this example, 2 minutes) after the start of the increase in absorbance, that is, when the absorbance is not converged, air bubbling is performed to reoxidize monovalent copper. It is good to set a criterion for determining whether or not. For example, in the case of this example, when the absorbance after 2 minutes from the start of the increase in absorbance is 0.15 or more, air bubbling may be performed on the working fluid. It may take about 2 hours after the start of the reaction until the increase in absorbance converges and the actual monovalent copper concentration can be measured. However, here, when the amount of change in absorbance after 2 minutes to 2 hours after that is obtained in advance that the increase width is 0.10, when the absorbance after 2 minutes exceeds 0.15, It can be estimated that the absorbance after 2 hours exceeds 0.25. That is, by setting a reference value several minutes after the start of the increase in absorbance (0.15 after 2 minutes in this example), it is possible to determine the presence or absence of air bubbling based on the reference value. It is possible to quickly control the concentration of monovalent copper without waiting for convergence.
［６．一価銅濃度測定装置］
図１０は、めっき液の吸光度（Ｔ値）を、数分以内に急激に増大する成分（Ｆ値）と、数十分以上かけて緩やかに増大する成分（Ｈ値）に分けたモデルを示す図である。図１０に示すように、本発明者らは錯体の形成に伴う吸光度（以下Ｔ値と称する）の時間変化は、数分以内に急激に増大する成分（以下Ｆ値と称する）と、数十分かけて緩やかに増大する成分（以下Ｈ値と称する）に分けられると推定している。そして、前者は錯体を形成しない一価銅及び小錯体の一価銅とＢＣＳとの反応、後者は大錯体の一価銅とＢＣＳとの反応に各々対応すると推定した。また、図９に示した実験結果により、吸光度変化が急激な成分（Ｆ値）は電解めっき槽の稼働状態に影響され、吸光度変化が緩やかな成分（Ｈ値）は電解めっき槽の稼働状態にかかわらずほぼ一定であった。これらの結果を踏まえて本発明者らは図１１に示す一価銅濃度測定装置を構築した。
[6. Monovalent copper concentration measuring device]
FIG. 10 shows a model in which the absorbance (T value) of the plating solution is divided into a component that rapidly increases within a few minutes (F value) and a component that gradually increases over several tens of minutes (H value). FIG. As shown in FIG. 10, the present inventors have observed that the time change of the absorbance (hereinafter referred to as T value) accompanying the formation of the complex is several tens of minutes with a component (hereinafter referred to as F value) that rapidly increases within several minutes. It is estimated that it is divided into components that gradually increase over time (hereinafter referred to as H value). It was estimated that the former corresponds to the reaction of monovalent copper that does not form a complex and the monovalent copper of a small complex with BCS, and the latter corresponds to the reaction of the monovalent copper of a large complex with BCS. Further, according to the experimental results shown in FIG. 9, the component (F value) having a rapid change in absorbance is affected by the operating state of the electrolytic plating tank, and the component (H value) having a gentle change in absorbance is in the operating state of the electrolytic plating tank. Regardless, it was almost constant. Based on these results, the present inventors constructed a monovalent copper concentration measuring apparatus shown in FIG.
（一価銅濃度測定装置の構成）
図１１は、一価銅濃度測定装置の一例を示す機能ブロック図である。この一価銅濃度測定装置１は、電解めっき槽１０から硫酸銅めっき液をサンプリングし、測定セル３１に供給するサンプリング部２０と、前述した呈色用緩衝液を測定セル３１に供給する呈色用緩衝液供給部２１と、分光光度計３０を有し、分光光度計３０の制御部３７と接続されるシステム制御部４０を含む装置である。
(Configuration of monovalent copper concentration measuring device)
FIG. 11 is a functional block diagram showing an example of a monovalent copper concentration measuring apparatus. The monovalent copper concentration measuring apparatus 1 samples a copper sulfate plating solution from the electrolytic plating tank 10 and supplies the sampling cell 20 to the measurement cell 31 and the color buffer for supplying the color buffer solution described above to the measurement cell 31. This is a device including a system control unit 40 that has a buffer solution supply unit 21 and a spectrophotometer 30 and is connected to a control unit 37 of the spectrophotometer 30.
電解めっき槽１０は、槽内の硫酸銅めっき液にエアバブリングを行うバブリング装置１４を底部に備えている。本例では、このバブリング装置１４もシステム制御部４０と接続されている。また、電解めっき槽１０には循環路１１が設けられている。この循環路１１の経路に設けられたポンプ１３によって漕内の硫酸銅めっき液が循環路１１内を循環しており、その流量はバルブ１２によって調節される。さらにこの循環路１１は、循環路１１内を流れる硫酸銅めっき液をサンプリングするためのサンプリング部２０を介して測定セル３１と接続されている。例えば、サンプリング部２０は硫酸銅めっき液に対して耐蝕性を有し、一定量をサンプリングするチュービングポンプと、サンプリングした硫酸銅めっき液に固形分が混入するのを防ぐための耐蝕性のフィルター等から構成される。 The electrolytic plating tank 10 includes a bubbling device 14 that performs air bubbling on the copper sulfate plating solution in the tank at the bottom. In this example, the bubbling device 14 is also connected to the system control unit 40. The electrolytic plating tank 10 is provided with a circulation path 11. The copper sulfate plating solution in the basket is circulated in the circulation path 11 by a pump 13 provided in the circulation path 11, and the flow rate is adjusted by a valve 12. Further, the circulation path 11 is connected to the measurement cell 31 via a sampling unit 20 for sampling the copper sulfate plating solution flowing in the circulation path 11. For example, the sampling unit 20 has corrosion resistance to the copper sulfate plating solution, a tubing pump that samples a certain amount, and a corrosion resistant filter for preventing the solid content from being mixed into the sampled copper sulfate plating solution. Consists of
分光光度計３０は、吸光度測定用溶液の吸光度を測定するための手段である。例えば、図１１に示すように、吸光度測定用溶液が収容される測定セル３１と、測定セル３１内の吸光度測定用溶液の吸光度を測定する測定部とから構成される。暗所内に設置される測定セル３１内では、サンプリング部２０によりサンプリングされた所定量の硫酸銅めっき液と、呈色用緩衝液供給部２１から供給された適正量の呈色用緩衝液が混合されることで吸光度測定用溶液が調整される。ここで用いられる呈色用緩衝液は、例えば酢酸−ＮａＯＨ系の緩衝液にＢＣＳ試薬を混合して希釈したｐＨ４〜５．５のものである。 The spectrophotometer 30 is a means for measuring the absorbance of the absorbance measurement solution. For example, as shown in FIG. 11, the measurement cell 31 is configured to store an absorbance measurement solution, and a measurement unit that measures the absorbance of the absorbance measurement solution in the measurement cell 31. In a measurement cell 31 installed in a dark place, a predetermined amount of copper sulfate plating solution sampled by the sampling unit 20 and an appropriate amount of color buffer solution supplied from the color buffer solution supply unit 21 are mixed. As a result, the absorbance measurement solution is adjusted. The color buffer used here is, for example, one having a pH of 4 to 5.5 obtained by diluting an acetic acid-NaOH buffer solution with a BCS reagent.
分光光度計３０の測定部は、例えばランプよりなる発光源３２と、この発光源３２からの光を分光するための分光部をなす例えば回折格子３３と、この回折格子３３から出射スリット３４を通った単色光の中から例えば波長４８５ｎｍの単色光を取り出す光学フィルター３５と、この光学フィルター３５より測定セル３１内を透過した光を検知して電気信号に変換するための検知器３６と、この信号を増幅して当該波長の吸光度を演算する制御部３７とからなる。測定された当該波長の吸光度は表示部３８に表示され、システム制御部４０に送信される。システム制御部４０は、バブリング装置１４及び分光光度計３０の制御部３７との間で制御信号等の送受を行う。 The measuring unit of the spectrophotometer 30 includes, for example, a light emitting source 32 formed of a lamp, a diffraction grating 33 that forms a spectral unit for splitting light from the light emitting source 32, and an output slit 34 from the diffraction grating 33. An optical filter 35 for extracting, for example, monochromatic light having a wavelength of 485 nm from the monochromatic light, a detector 36 for detecting the light transmitted through the measuring cell 31 from the optical filter 35 and converting it into an electrical signal, and this signal And a control unit 37 that calculates the absorbance at the wavelength. The measured absorbance of the wavelength is displayed on the display unit 38 and transmitted to the system control unit 40. The system control unit 40 transmits and receives control signals and the like between the bubbling device 14 and the control unit 37 of the spectrophotometer 30.
（一価銅濃度測定装置の作用）
休止期間が明けて硫酸銅電気めっき浴工程を実行する前に、循環路１１内を流れる硫酸銅めっき液をサンプリング部２０によってサンプリングし、サンプリング部２０から所定量の硫酸銅めっき液を測定セル３１に供給する。一方、呈色用緩衝液供給部２１からは所定量の呈色用緩衝液を測定セル３１に供給する。呈色用緩衝液が測定セル３１に供給されることで吸光度測定用溶液が調整され、呈色反応が生じる。本例では呈色用緩衝液の供給時点からの吸光度を計測するものとする。測定セル３１は、上下方向の振動を発生するための撹拌機能付き恒温槽（図示せず）内に設置されている。撹拌による振動で吸光度測定用溶液が撹拌され、恒温槽によって一定温度に保たれている。測定部において吸光度測定用溶液の吸光度の測定が行われる。この吸光度は例えば以下のようにして測定される。
(Operation of monovalent copper concentration measuring device)
Before the suspension period ends and the copper sulfate electroplating bath process is performed, the copper sulfate plating solution flowing in the circulation path 11 is sampled by the sampling unit 20, and a predetermined amount of copper sulfate plating solution is measured from the sampling unit 20 in the measurement cell 31. To supply. On the other hand, a predetermined amount of the color buffer solution is supplied from the color buffer solution supply unit 21 to the measurement cell 31. By supplying the color buffer solution to the measurement cell 31, the absorbance measurement solution is adjusted, and a color reaction occurs. In this example, the absorbance from the time of supplying the color buffer is measured. The measurement cell 31 is installed in a constant temperature bath (not shown) with a stirring function for generating vertical vibrations. The solution for measuring absorbance is stirred by vibration by stirring, and is kept at a constant temperature by a thermostatic bath. In the measurement unit, the absorbance of the absorbance measurement solution is measured. This absorbance is measured, for example, as follows.
発光源３２より発光した光は、光路中に設けられた回折格子３３、出射スリット３４、及び光学フィルター３５を介して、４００〜６００ｎｍのうちの特定波長（４８５ｎｍ）の単色光とされた後、測定セル３１を透過する。この測定セル３１を透過した透過光は検知器３６によって検知されて電気信号に変換され、制御部３７で増幅されて吸光度が演算される。この吸光度は表示部３８に表示することが可能である。また、演算された吸光度はシステム制御部４０に送信され、システム制御部４０に記憶されている一価銅濃度と吸光度の関係を示す検量線（例えば図３）に基づいて、一価銅濃度が演算される。演算された一価銅濃度はシステム制御部４０に測定日時と共に記憶され、当該システム制御部４０のディスプレイに表示される。 The light emitted from the light emission source 32 is converted to monochromatic light having a specific wavelength (485 nm) of 400 to 600 nm through the diffraction grating 33, the exit slit 34, and the optical filter 35 provided in the optical path. It passes through the measurement cell 31. The transmitted light that has passed through the measurement cell 31 is detected by the detector 36, converted into an electric signal, amplified by the control unit 37, and the absorbance is calculated. This absorbance can be displayed on the display unit 38. Further, the calculated absorbance is transmitted to the system control unit 40, and the monovalent copper concentration is calculated based on a calibration curve (for example, FIG. 3) indicating the relationship between the monovalent copper concentration and the absorbance stored in the system control unit 40. Calculated. The calculated monovalent copper concentration is stored in the system control unit 40 together with the measurement date and time, and is displayed on the display of the system control unit 40.
ここで分光光度計３０においては、測定された吸光度を逐次システム制御部４０に送信している。例えば１０秒毎に測定した吸光度をシステム制御部４０に送信している。この吸光度の送信は、吸光度の上昇が収束するまでの期間（例えば１２０分間）継続される。そして、システム制御部４０は分光光度計から受信した１２０分間の測定データを記憶装置に蓄積している。システム制御部４０は測定毎に、吸光度測定用溶液調整時、即ち吸光度の上昇開始時から吸光度が収束するまでの期間の吸光度曲線を記憶している。例えば図１２に示す例では、最終吸光度（吸光度の上昇が収束した時点における当該吸光度の値であり、例えば吸光度測定用溶液調整時から１２０分後における吸光度の値）が異なる複数（本例では１８）の硫酸銅めっき液の吸光度曲線を記憶している。 Here, the spectrophotometer 30 sequentially transmits the measured absorbance to the system control unit 40. For example, the absorbance measured every 10 seconds is transmitted to the system control unit 40. This transmission of absorbance is continued for a period (for example, 120 minutes) until the rise in absorbance converges. The system control unit 40 accumulates 120 minutes of measurement data received from the spectrophotometer in the storage device. For each measurement, the system control unit 40 stores an absorbance curve for the period from when the absorbance measurement solution is adjusted, that is, when the absorbance starts to rise until the absorbance converges. For example, in the example shown in FIG. 12, the final absorbance (the absorbance value at the time when the rise in absorbance has converged, for example, the absorbance value after 120 minutes from the preparation of the absorbance measurement solution) is different (18 in this example). ) Of the copper sulfate plating solution.
また、本装置においては、吸光度の上昇が収束することを待つことなく、収束前の時点の吸光度に基づいて一価銅濃度を推定し、濃度管理を行うことができる。これは前述したように、めっき不具合に影響するのは呈色用緩衝液を混合後、数分で急激に変化する成分であることによる。測定された吸光度が基準値を超えているとエアバブリング命令を送信し、これを受信したバブリング装置１４はエアバブリングを行って一価銅を再酸化させて、吸光度（即ち一価銅濃度）を低減させる。 Further, in this device, the concentration control can be performed by estimating the monovalent copper concentration based on the absorbance before the convergence without waiting for the increase in absorbance to converge. As described above, this affects the plating failure because it is a component that changes rapidly within a few minutes after mixing the coloring buffer solution. When the measured absorbance exceeds the reference value, an air bubbling command is transmitted, and the bubbling device 14 that has received the command performs air bubbling to re-oxidize the monovalent copper to obtain the absorbance (ie, the monovalent copper concentration). Reduce.
エアバブリングから一定時間経過すると、硫酸銅めっき液を再度サンプリングして吸光度を計測する。計測された吸光度が基準値以下になるまで上記処理を繰り返す。このように、一価銅濃度測定装置によって一価銅濃度を短時間で計測し、基準値以上であればエアバブリングによって一価銅濃度を低減させ、硫酸銅電気めっき浴工程を実行可能な状態にすることで、濃度管理を行っている。特に、一価銅濃度を測定するに際しては、呈色用緩衝液を混合後、数分経過した時点の一価銅濃度を測定すればよく、時間変動が収束するまでの間待機する必要がない。本装置では短時間に複数回の測定が要求されるケースが多いため、その効果は特に大きく、休日明けなどに硫酸銅電気めっき浴工程を早期に再開することが可能である。 After a certain period of time has passed since air bubbling, the copper sulfate plating solution is sampled again and the absorbance is measured. The above process is repeated until the measured absorbance is below the reference value. In this way, the monovalent copper concentration is measured in a short time by the monovalent copper concentration measuring device, and if it exceeds the reference value, the monovalent copper concentration is reduced by air bubbling and the copper sulfate electroplating bath process can be executed. By doing so, concentration control is performed. In particular, when measuring the monovalent copper concentration, it is only necessary to measure the monovalent copper concentration when a few minutes have elapsed after mixing the coloring buffer solution, and there is no need to wait until the time variation converges. . Since this apparatus often requires a plurality of measurements in a short time, the effect is particularly great, and the copper sulfate electroplating bath process can be restarted early at the end of the holiday.
（一価銅濃度の推定）
上記のようにして、吸光度の上昇開始から数分後の吸光度を測定することで、エアバブリング等の要否を判断することができるが、最終的な一価銅濃度、即ち吸光度の上昇が収束した時点における一価銅濃度を取得するには、あくまで吸光度の収束を待たなければならないという問題がある。本システムでは、前述したシステム制御部４０に記憶している吸光度曲線を利用して、吸光度の上昇が収束していない期間において、当該吸光度測定用溶液の最終的な一価銅濃度を推定することを可能とした。これによって、例えば吸光度測定用溶液調整から数分程度で当該吸光度測定用溶液の最終的な一価銅濃度を取得することが可能となる。
(Estimation of monovalent copper concentration)
As described above, it is possible to determine the necessity of air bubbling by measuring the absorbance after several minutes from the start of the increase in absorbance, but the final monovalent copper concentration, that is, the increase in absorbance converges. In order to obtain the monovalent copper concentration at that time, there is a problem that it is necessary to wait for the absorbance to converge. In the present system, the final monovalent copper concentration of the absorbance measurement solution is estimated in a period in which the increase in absorbance has not converged, using the absorbance curve stored in the system control unit 40 described above. Made possible. Thus, for example, the final monovalent copper concentration of the absorbance measurement solution can be obtained within a few minutes after the absorbance measurement solution adjustment.
図１２（ａ）に示すように、システム制御部４０の記憶装置には、吸光光度計３０によって計測された複数の吸光度曲線が記憶されている。これらは、添加剤成分が共通する特定の硫酸銅めっき液（例えば前述したＡ液）であって、一価銅濃度が異なるものについて測定された吸光度曲線である。本例では吸光度曲線１〜１８を記憶しており、各々の吸光度曲線は、吸光度測定用溶液調整時から吸光度収束時（本例では１２０分）までの各サンプリングポイント（例えば１０秒毎）において測定された吸光度に基づいて構築されている。本例における各吸光度曲線１〜１８の最終吸光度は０．３６〜０．０２（０．０２刻み）であるものとする。ここで、新たにサンプリングした硫酸銅めっき液について、測定セル３１において吸光度測定用溶液を調整したものとする。このとき吸光度測定用溶液調整後から吸光度の上昇が収束していない期間（本例では２分後）までの吸光度を測定し、システム制御部４０は、当該期間における吸光度曲線を取得する（図１２（ｂ）の「今回取得した吸光度曲線」参照）。 As shown in FIG. 12A, the storage device of the system control unit 40 stores a plurality of absorbance curves measured by the absorptiometer 30. These are absorbance curves measured for specific copper sulfate plating solutions having common additive components (for example, the above-described A solution) having different monovalent copper concentrations. In this example, absorbance curves 1 to 18 are stored, and each absorbance curve is measured at each sampling point (for example, every 10 seconds) from when the solution for absorbance measurement is adjusted to when the absorbance converges (in this example, 120 minutes). Constructed based on the measured absorbance. The final absorbance of each absorbance curve 1 to 18 in this example is 0.36 to 0.02 (in increments of 0.02). Here, it is assumed that the absorbance measurement solution is adjusted in the measurement cell 31 for the newly sampled copper sulfate plating solution. At this time, the absorbance is measured from the time when the absorbance measurement solution is adjusted to the time when the increase in absorbance has not converged (after 2 minutes in this example), and the system control unit 40 acquires the absorbance curve during that period (FIG. 12). (Refer to “absorbance curve acquired this time” in (b)).
次いで、システム制御部４０は、今回取得した吸光度曲線における吸光度測定用溶液調整後から所定時間後（本例では２分後）の吸光度（本例では０．１１）と、既に記憶している吸光度曲線１〜１８における当該所定時間後（本例では２分後）の吸光度とを比較し、最も近似する吸光度及び次に近似する吸光度となる吸光度曲線を各々特定する。本例では、吸光度測定用溶液調整後から２分後の吸光度が０．１０、０．１２である吸光度曲線９、１０が各々特定されることになる。次いでシステム制御部４０は、特定した吸光度曲線９、１０の最終吸光度を参照し（本例では０．２０、０．１８）、これらの中間値（本例では０．１９）を今回取得した吸光度曲線の最終吸光度として推定する。さらに、検量線を参照し、推定した最終吸光度に対応する一価銅濃度を特定し、当該一価銅濃度を推定値としてディスプレイ等の表示手段に表示する。このようにして吸光度測定用溶液調整後の、吸光度が収束していない早い段階で、当該吸光度測定用溶液の最終的な一価銅濃度を推定することができる。 Next, the system control unit 40 absorbs the absorbance (0.11 in this example) after a predetermined time (in this example, 2 minutes) after the absorbance measurement solution adjustment in the absorbance curve acquired this time, and the absorbance already stored. The absorbance after the predetermined time in the curves 1 to 18 (after 2 minutes in this example) is compared, and the absorbance curve that is the closest absorbance and the next approximate absorbance is specified. In this example, the absorbance curves 9 and 10 having the absorbances of 0.10 and 0.12 after 2 minutes from the preparation of the solution for absorbance measurement are specified. Next, the system control unit 40 refers to the final absorbance of the identified absorbance curves 9 and 10 (in this example, 0.20, 0.18), and an intermediate value (0.19 in this example) is obtained this time. Estimated as the final absorbance of the curve. Furthermore, referring to the calibration curve, the monovalent copper concentration corresponding to the estimated final absorbance is specified, and the monovalent copper concentration is displayed as an estimated value on a display means such as a display. In this way, the final monovalent copper concentration of the absorbance measurement solution can be estimated at an early stage where the absorbance does not converge after adjusting the absorbance measurement solution.
なお、本実施形態においては、吸光度測定用溶液調整後から所定時間後の吸光度を比較することによって、今回取得した吸光度曲線に近似する吸光度曲線を特定しているが、吸光度測定用溶液調整後から当該所定時間までの複数のサンプリングポイントにおける２乗誤差の和が最小となる曲線を、近似する吸光度曲線として特定するようにしても良い。また、本実施形態のように近似する複数の吸光度曲線を特定せずに、今回取得した吸光度曲線に最も近似する吸光度曲線のみを１つ特定して、当該吸光度曲線の最終吸光度を、今回取得した吸光度曲線の最終吸光度として推定するようにしても良い。また、本実施形態では、一価銅濃度の異なる硫酸銅めっき液について吸光度を実測して得た吸光度曲線と、今回取得した吸光度曲線を比較する例について説明したが、今回取得した吸光度曲線の比較対象は、実測して得られた吸光度曲線に限らず理論値によって構成された吸光度曲線であっても良い。 In this embodiment, the absorbance curve approximated to the absorbance curve obtained this time is specified by comparing the absorbance after a predetermined time after the absorbance measurement solution adjustment, but after the absorbance measurement solution adjustment, A curve that minimizes the sum of square errors at a plurality of sampling points up to the predetermined time may be specified as an approximate absorbance curve. In addition, without specifying a plurality of approximate absorbance curves as in the present embodiment, only one absorbance curve closest to the currently obtained absorbance curve is identified, and the final absorbance of the absorbance curve is obtained this time. It may be estimated as the final absorbance of the absorbance curve. Further, in this embodiment, an example of comparing the absorbance curve obtained by actually measuring the absorbance of the copper sulfate plating solutions having different monovalent copper concentrations and the absorbance curve obtained this time has been described. The target is not limited to the absorbance curve obtained by actual measurement, but may be an absorbance curve constituted by theoretical values.
また、本実施形態においては、吸光度測定前に、予めＢＣＳ試薬と緩衝液を混合して呈色用緩衝液を作成しておき、サンプリング部２０によってサンプリングした硫酸銅めっき液と、呈色用緩衝液を測定セル３１内で混合することで吸光度測定用溶液を調整した。しかし、これに限らず、まず銅めっき液と緩衝液を混合しておく緩衝部を吸光光度計３０外部に設けておき、当該緩衝部において混合された混合液（無呈色）を測定セル３１に供給し、当該測定セル３１にキレート試薬としてＢＣＳ試薬を供給することで吸光度測定用溶液を調整するようにしても良い。また、測定セル３１の前段に吸光度測定用溶液調整部を設けておき、当該吸光度測定用溶液調整部においてサンプリングした硫酸銅めっき液と呈色用緩衝液を混合した直後に測定セル３１に供給するようにしても良い。また、銅めっき液のｐＨが当初から至適ｐＨである場合（例えばｐＨ４〜５．５程度の場合）には、緩衝液との混合は不要であり、ＢＣＳ試薬と銅めっき液を測定セル３１で混合することで吸光度を測定することができる。 In the present embodiment, before the absorbance measurement, a BCS reagent and a buffer solution are mixed in advance to prepare a coloration buffer solution, and the copper sulfate plating solution sampled by the sampling unit 20 and the coloration buffer are prepared. The solution for absorbance measurement was prepared by mixing the liquid in the measurement cell 31. However, the present invention is not limited to this. First, a buffer unit for mixing the copper plating solution and the buffer solution is provided outside the absorptiometer 30, and the mixed solution (non-colored) mixed in the buffer unit is used as the measurement cell 31. And the absorbance measuring solution may be adjusted by supplying a BCS reagent as a chelating reagent to the measurement cell 31. Further, an absorbance measurement solution adjustment unit is provided in the front stage of the measurement cell 31 and supplied to the measurement cell 31 immediately after mixing the copper sulfate plating solution and the coloration buffer solution sampled in the absorbance measurement solution adjustment unit. You may do it. In addition, when the pH of the copper plating solution is the optimum pH from the beginning (for example, when the pH is about 4 to 5.5), mixing with the buffer solution is unnecessary, and the BCS reagent and the copper plating solution are measured in the measurement cell 31. Absorbance can be measured by mixing with.
１…一価銅濃度測定装置
１０…電解めっき槽
１４…バブリング装置
２０…サンプリング部
２１…呈色用緩衝液供給部
３０…分光光度計
４０…システム制御部
DESCRIPTION OF SYMBOLS 1 ... Monovalent copper concentration measuring apparatus 10 ... Electrolytic plating tank 14 ... Bubbling apparatus 20 ... Sampling part 21 ... Coloring buffer supply part 30 ... Spectrophotometer 40 ... System control part
Claims (9)
前記調整工程において調整された吸光度測定用溶液の吸光度の収束前の時点における吸光度を測定する吸光度測定工程と、
前記吸光度測定工程において測定された吸光度に基づいて、前記銅めっき液中の一価銅濃度を推定する濃度推定工程と、
を含むことを特徴とする一価銅の濃度測定方法。 An adjusting step of adjusting the sample solution and bathocuproine disulfonic acid disodium reagent mixing absorbance measurement solution pH4~10 containing copper plating solution containing a substance which forms a monovalent copper complex,
An absorbance measurement step for measuring the absorbance at the time before convergence of the absorbance of the absorbance measurement solution adjusted in the adjustment step;
Based on the absorbance measured in the absorbance measurement step, a concentration estimation step for estimating the monovalent copper concentration in the copper plating solution,
A method for measuring the concentration of monovalent copper, comprising:
前記吸光度測定工程において、吸光度の上昇開始から収束前の時点までの所定期間における吸光度を測定し、
前記吸光度測定工程において測定された所定期間における吸光度の時間変動を示す吸光度曲線を取得する吸光度曲線取得工程をさらに含み、
前記濃度推定工程において、前記吸光度曲線取得工程において取得した吸光度曲線に基づいて、前記銅めっき液中の一価銅濃度を推定する、
ことを特徴とする一価銅の濃度測定方法。 A method for measuring the concentration of monovalent copper according to claim 1 ,
In the absorbance measurement step, the absorbance in a predetermined period from the start of increase in absorbance to the time before convergence is measured,
Further comprising an absorbance curve acquisition step of acquiring an absorbance curve indicating the time variation of absorbance in a predetermined period measured in the absorbance measurement step ;
In the concentration estimation step, based on the absorbance curve acquired in the absorbance curve acquisition step, estimate the monovalent copper concentration in the copper plating solution,
A method for measuring the concentration of monovalent copper.
前記銅めっき液は硫酸銅めっき液であり、
前記調整工程において、前記硫酸銅めっき液を含むｐＨ４〜７のサンプル溶液及びバソクプロインジスルホン酸二ナトリウム試薬を混合した吸光度測定用溶液を調整することを特徴とする一価銅の濃度測定方法。 A concentration measurement method monovalent copper according to claim 1 or 2,
The copper plating solution is a copper sulfate plating solution,
Wherein in the adjustment step, the concentration measurement method of monovalent copper, characterized by adjusting the sample solution and bathocuproine disulfonic acid disodium reagent mixing absorbance measurement solution pH4~7 containing the copper sulfate plating solution.
前記一価銅濃度が所定値以上であるときに、前記銅めっき液に対して一価銅濃度を低減させる処理を行うことを特徴とする一価銅の濃度管理方法。 A monovalent copper concentration management method for managing a monovalent copper concentration measured by the monovalent copper concentration measurement method according to claim 1, which is selected from claims 1 to 3 ,
A monovalent copper concentration management method, wherein when the monovalent copper concentration is equal to or higher than a predetermined value, a treatment for reducing the monovalent copper concentration is performed on the copper plating solution.
前記収容手段に収容された吸光度測定用溶液の吸光度の収束前の時点における吸光度を測定する吸光度測定手段と、
前記吸光度測定手段により測定された吸光度に基づいて、前記銅めっき液中の一価銅濃度を推定する濃度推定手段と、
を有することを特徴とする一価銅の濃度測定装置。 A containing means for containing a sample solution and bathocuproine disulfonic acid disodium reagent mixing absorbance measurement solution pH4~10 containing copper plating solution containing a substance which forms a monovalent copper complex,
Absorbance measuring means for measuring the absorbance at the time before the convergence of the absorbance of the absorbance measuring solution accommodated in the accommodating means,
Based on the absorbance measured by the absorbance measuring means, a concentration estimating means for estimating the monovalent copper concentration in the copper plating solution;
A device for measuring the concentration of monovalent copper, comprising:
前記サンプリング手段によりサンプリングされた銅めっき液を含むｐＨ４〜１０のサンプル溶液及びバソクプロインジスルホン酸二ナトリウム試薬を混合した吸光度測定用溶液を調整する調整手段と、
前記調整手段により調整された吸光度測定用溶液の吸光度の収束前の時点における吸光度を測定する吸光度測定手段と、
前記吸光度測定手段により測定された吸光度に基づいて、前記銅めっき液中の一価銅濃度を推定する濃度推定手段と、
を有することを特徴とする一価銅の濃度測定装置。 Sampling means for sampling a copper plating solution containing a substance that forms a complex with monovalent copper in an electrolytic plating tank,
And adjusting means for adjusting the sample solution and bathocuproine disulfonic acid disodium reagent mixing absorbance measurement solution pH4~10 containing sampled copper plating solution by the sampling means,
Absorbance measuring means for measuring the absorbance at the time before convergence of the absorbance of the absorbance measuring solution adjusted by the adjusting means;
Based on the absorbance measured by the absorbance measuring means, a concentration estimating means for estimating the monovalent copper concentration in the copper plating solution;
A device for measuring the concentration of monovalent copper, comprising:
前記吸光度測定手段は、前記吸光度測定用溶液の吸光度の上昇開始から収束前の時点までの所定期間における吸光度を測定し、The absorbance measurement means measures the absorbance in a predetermined period from the start of increase in absorbance of the absorbance measurement solution to the time before convergence,
前記吸光度測定手段により測定された所定期間における吸光度の時間変動を示す吸光度曲線を取得する吸光度曲線取得手段をさらに含み、 Further comprising an absorbance curve acquisition means for acquiring an absorbance curve indicating the time variation of absorbance in a predetermined period measured by the absorbance measurement means,
前記濃度推定手段は、前記吸光度曲線取得手段により取得した吸光度曲線に基づいて、前記銅めっき液中の一価銅濃度を推定する、 The concentration estimation means estimates a monovalent copper concentration in the copper plating solution based on the absorbance curve acquired by the absorbance curve acquisition means.
ことを特徴とする一価銅の濃度測定装置。A device for measuring the concentration of monovalent copper.
前記銅めっき液は硫酸銅めっき液であり、 The copper plating solution is a copper sulfate plating solution,
前記吸光度測定用溶液は、前記硫酸銅めっき液を含むｐＨ４〜７のサンプル溶液及びバソクプロインジスルホン酸二ナトリウム試薬を混合したものであることを特徴とする一価銅の濃度測定装置。 The concentration measuring apparatus for monovalent copper, wherein the solution for measuring absorbance is a mixture of a sample solution having a pH of 4 to 7 containing the copper sulfate plating solution and a disodium bathocuproine disulfonate.
前記一価銅濃度が所定値以上であるときに、前記銅めっき液に対して一価銅濃度を低減させる手段を更に有することを特徴とする一価銅の濃度測定装置。 The monovalent copper concentration measuring device further comprising means for reducing the monovalent copper concentration with respect to the copper plating solution when the monovalent copper concentration is a predetermined value or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011166680A JP5757523B2 (en) | 2011-07-29 | 2011-07-29 | Concentration measuring method, concentration management method, and concentration measuring apparatus for monovalent copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011166680A JP5757523B2 (en) | 2011-07-29 | 2011-07-29 | Concentration measuring method, concentration management method, and concentration measuring apparatus for monovalent copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013028850A JP2013028850A (en) | 2013-02-07 |
| JP5757523B2 true JP5757523B2 (en) | 2015-07-29 |
Family
ID=47786141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011166680A Active JP5757523B2 (en) | 2011-07-29 | 2011-07-29 | Concentration measuring method, concentration management method, and concentration measuring apparatus for monovalent copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5757523B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10450667B2 (en) | 2014-10-27 | 2019-10-22 | International Business Machines Corporation | System for treating solution for use in electroplating application and method for treating solution for use in electroplating application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3112553A1 (en) * | 1981-03-30 | 1982-10-14 | Siemens AG, 1000 Berlin und 8000 München | ANALYSIS DEVICE FOR DETERMINING THE COPPER CONTENT IN THE WASTEWATER, IN PARTICULAR OF GALVANIC SYSTEMS |
| JPH10227742A (en) * | 1997-02-13 | 1998-08-25 | Toppan Printing Co Ltd | Copper density analyzation method and device for ferric chloride etching liquid |
| JP3871018B2 (en) * | 2000-06-23 | 2007-01-24 | 上村工業株式会社 | Tin-copper alloy electroplating bath and plating method using the same |
| JP2003129287A (en) * | 2001-10-29 | 2003-05-08 | Applied Materials Inc | Electroplating process |
| JP2005187869A (en) * | 2003-12-25 | 2005-07-14 | Hitachi Aic Inc | Plating method and plating apparatus |
| JP2008144186A (en) * | 2006-12-05 | 2008-06-26 | Sumitomo Metal Mining Co Ltd | Acidic copper-plating method |
-
2011
- 2011-07-29 JP JP2011166680A patent/JP5757523B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013028850A (en) | 2013-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103604856B (en) | A kind of potentiometric titration method of mixed acid solution | |
| JP6179932B2 (en) | Metal complex quantification method and metal complex quantification apparatus in plating solution | |
| WO2003029779A3 (en) | Improved method for analysis of three organic additives in an acid copper plating bath | |
| Erbao et al. | Flow injection determination of adenine at trace level based on luminol–K2Cr2O7 chemiluminescence in a micellar medium | |
| US8118988B2 (en) | Analysis of copper ion and complexing agent in copper plating baths | |
| US20060133964A1 (en) | Closed loop automated matrix removal | |
| CN102680555A (en) | Method for measuring free acid concentration in acid liquid | |
| CN102207463A (en) | Method for determining content of phosphor and copper in ferrotitanium | |
| JP5757523B2 (en) | Concentration measuring method, concentration management method, and concentration measuring apparatus for monovalent copper | |
| JP2005520131A (en) | Automatic in-process specific mass spectrometry method and apparatus for characterizing components | |
| US5294554A (en) | Analysis of tin, lead or tin-lead alloy plating solution | |
| CN111157520B (en) | Quantitative detection reagent and detection method for sodium polydithio-dipropyl sulfonate in acid copper electroplating solution | |
| JP2007327797A (en) | High-frequency inductively coupled plasma emission spectrometric analysis method | |
| US20180135199A1 (en) | Analysis of silver ion and complexing agent in tin-silver electrodeposition solution | |
| Zheng et al. | Flow-injection chemiluminescence detecting sulfite with in situ electrogenerated Mn3+ as the oxidant | |
| CN115754072A (en) | Qualitative and quantitative method for sodium sulfopropane sulfonate brightener in acid copper electroplating solution | |
| JP6945525B2 (en) | Acetate complex and acetate quantification method | |
| Panichlertumpi et al. | Ultra-trace determination of Hg (II) in drinking water and local Thai liquors using homogeneous liquid–liquid extraction followed by fluorescence quenching of its ternary complex | |
| Noma et al. | Analysis of Cu (I) Complexes in Copper Sulfate Electroplating Solution By Using Reaction Kinetics with a Chelate Reagent | |
| CN109580567B (en) | Detect aquatic BF4-、H2PO4-And HSO4-Method (2) | |
| JP2013053338A (en) | Concentration measuring method for dye-based additive in copper sulfate plating solution, plating method, and plating device | |
| JP2005249552A (en) | Method for measuring concentration of persulfate | |
| JP2003021646A (en) | Zinc analytical method and analytical device for zinc electrolytic solution | |
| JP2000356631A (en) | Method and apparatus for measuring total organic carbon | |
| JP2024031708A (en) | Gold concentration measuring device and measuring method in gold-containing plating solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20131227 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131227 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20141222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150106 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150303 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150512 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150527 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5757523 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |