JPH02254181A - Method for managing stabilizer of etching bath - Google Patents
Method for managing stabilizer of etching bathInfo
- Publication number
- JPH02254181A JPH02254181A JP7737489A JP7737489A JPH02254181A JP H02254181 A JPH02254181 A JP H02254181A JP 7737489 A JP7737489 A JP 7737489A JP 7737489 A JP7737489 A JP 7737489A JP H02254181 A JPH02254181 A JP H02254181A
- Authority
- JP
- Japan
- Prior art keywords
- stabilizer
- hydrogen peroxide
- concn
- concentration
- amount
- 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
Links
- 238000005530 etching Methods 0.000 title claims abstract description 41
- 239000003381 stabilizer Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 238000004448 titration Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 24
- 238000004458 analytical method Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000007726 management method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエツチング浴の管理方法に関し、特に安定剤の
管理方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for managing an etching bath, and more particularly to a method for managing a stabilizer.
一般に、エツチング浴は基本的に過酸化水素。 Generally, etching baths are basically hydrogen peroxide.
硫酸及び安定剤で構成されており、エツチング処理を行
うことにより過酸化水素濃度、硫酸濃度は低下し、一方
金属イオン濃度は増加する。この内、過酸化水素及び硫
酸が消耗すると、エツチング速度が低下するので、これ
らの濃度を一定に維持するため、一定時間毎にサンプリ
ングし過酸化水素を酸化還元滴定法で分析し、また硫酸
濃度を中和滴定法により分析して各々の含有量を管理し
ていたが、エツチング浴中の過酸化水素はエツチング処
理による浴中の金属イオン濃度の増加に伴い、金属イオ
ンとの接触により次のような自己分解反応を起こす。It is composed of sulfuric acid and a stabilizer, and by etching, the hydrogen peroxide concentration and sulfuric acid concentration decrease, while the metal ion concentration increases. When hydrogen peroxide and sulfuric acid are consumed, the etching rate decreases, so in order to maintain these concentrations constant, samples are taken at regular intervals and hydrogen peroxide is analyzed using redox titration, and the sulfuric acid concentration is The content of each substance was controlled by analyzing it by neutralization titration, but as the metal ion concentration in the etching bath increases, hydrogen peroxide in the etching bath comes into contact with the metal ions, resulting in the following: It causes a self-decomposition reaction.
Ｈ２Ｏ，→Ｈ２０＋ １／２０２
この自己分解反応は、安定剤濃度が低いほど急速に進行
し、過酸化水素を過剰に消耗するため、エツチング速度
の低下や過酸化水素使用量増大の原因となる。H2O,→H20+ 1/202 This self-decomposition reaction proceeds more rapidly as the concentration of the stabilizer is lower and excessively consumes hydrogen peroxide, causing a decrease in the etching rate and an increase in the amount of hydrogen peroxide used.
また、自己分解反応を抑えるために、安定剤濃度４高く
しすきると、エツチング速度が大幅に低ドする。Furthermore, if the stabilizer concentration is increased by 4 to suppress the autodecomposition reaction, the etching rate will be significantly reduced.
従ってエツチング浴中の金属イオン濃度の増加に伴う安
定剤の濃度管理は重要であるが、エツチング浴が含有す
る安定剤量は極めて微量であり直接的な分析定量が困難
であるため、従来は、過酸化水素の添加量に合せて所定
量の安定剤を添加していた。Therefore, it is important to control the stabilizer concentration as the metal ion concentration increases in the etching bath, but the amount of stabilizer contained in the etching bath is extremely small and direct analytical quantification is difficult. A predetermined amount of stabilizer was added in accordance with the amount of hydrogen peroxide added.
従来の管理方法では安定剤の量を定量的に知ることがで
きないため、安定剤濃度を適正濃度に管理することが困
難となり、安定剤が不足の場合は過酸化水素の自己分解
反応を抑制できず過酸化水素の過剰な消耗により、一定
のエツチング速度管理が困難となったり過酸化水素の使
用量が必要量」二に増加するという課題があった。With conventional management methods, it is not possible to quantitatively determine the amount of stabilizer, making it difficult to control the stabilizer concentration to an appropriate level.If stabilizer is insufficient, the self-decomposition reaction of hydrogen peroxide cannot be suppressed. However, due to excessive consumption of hydrogen peroxide, it became difficult to maintain a constant etching rate, and the amount of hydrogen peroxide used increased to the required amount.
更に、自己分解反応を防止するため、安定剤濃度が高め
になるように維持管理した場合は、安定剤が過剰となり
、エンチング速度が低下し易いという課題もあった。Furthermore, if the stabilizer concentration is maintained at a high level in order to prevent self-decomposition reactions, there is a problem that the stabilizer becomes excessive and the etching rate tends to decrease.
本発明の目的は前記課題を解決したエツチング浴の安定
剤の管理方法を提供することにある。An object of the present invention is to provide a method for managing stabilizers in an etching bath that solves the above-mentioned problems.
上述した従来のエツチング浴の安定剤の管理方法に対し
、本発明はエツチング浴からサンプリングしたエツチン
グ液の過酸化水素濃度を測定し、前記サンブリンク液に
一定量の金属イオンを添加し一定時間後に残存する過酸
化水素濃度を分析し、金属イオン添加前の濃度からの変
化量よりエツチング浴中の安定剤濃度を求め、不足する
安定剤の量をエツチング浴に補充するという相違点を有
する。In contrast to the conventional etching bath stabilizer control method described above, the present invention measures the hydrogen peroxide concentration of the etching solution sampled from the etching bath, adds a certain amount of metal ions to the sample solution, and then measures the concentration of the etching solution after a certain period of time. The difference is that the remaining hydrogen peroxide concentration is analyzed, the stabilizer concentration in the etching bath is determined from the amount of change from the concentration before metal ion addition, and the insufficient amount of stabilizer is replenished into the etching bath.
前記目的を達成するため、本発明に係るエツチング浴の
安定剤の管理方法は、エツチング浴から一定量のエツチ
ング液をサンプリングする工程と、前記サンプリング液
に含有する過酸化水素量を酸化還元滴定法により分析し
、過酸化水素の初期濃度を求める工程と、前記サンプリ
ング液の所定量に対し一定量の金属イオンを含有する溶
液を添加してから一定時間経過後に酸化還元滴定法によ
り分析し、過酸化水素の濃度を求める工程と、１涌記過
酸化水素初期濃度からの変化量に基づきエツチング浴に
含有する安定剤の濃度を求め、安定剤の設定濃度に対し
て不足する安定剤の量を演算し。In order to achieve the above object, the method for managing a stabilizer in an etching bath according to the present invention includes the steps of sampling a certain amount of etching solution from an etching bath, and measuring the amount of hydrogen peroxide contained in the sampling solution using a redox titration method. A step in which a solution containing a certain amount of metal ions is added to a predetermined amount of the sample solution, and after a certain period of time, an analysis is performed by redox titration method to determine the initial concentration of hydrogen peroxide. The process of determining the concentration of hydrogen oxide, the concentration of the stabilizer contained in the etching bath based on the amount of change from the initial concentration of hydrogen peroxide, and the amount of stabilizer that is insufficient for the set concentration of stabilizer is calculated. death.
安定剤の不足量をエツチング浴に補充する工程とを有す
るものである。and a step of replenishing the etching bath with the insufficient amount of stabilizer.
次に、本発明の実施例を第１開裂参照して説明する。 Next, embodiments of the present invention will be described with reference to the first cleavage.
第１図は本発明のエツチング浴の安定剤の管理方法を用
いたエツチング浴管理システムを示す図である。FIG. 1 is a diagram showing an etching bath management system using the etching bath stabilizer management method of the present invention.
図において、熱交換機３備えたエツチング槽１より一定
時間毎にサンプリングしたエツチング液中の金属イオン
濃度、過酸化水素濃度、硫酸濃度を自動分析装置５にて
分析し、それぞれの標準濃度に合せるための過酸化水素
及び硫酸の補充量をコントローラー６にて演算し、過酸
化水素タンク９ａ及び硫酸タンク８ａから定量ポンプ８
及び９で補充する。更に、前記サンプリングと同時に一
定量のエツチング液を反応セルフに注入した後、スタラ
ー１０で攪拌しながら金属イオン含有水溶液（例；銅ｉ
ｏｏ〜１１００００１）Ｐ又は、鉄１０〜１０１０００
ＰＰの一定量を金属溶液タンクｌｌａからポンプ１１で
添加し、一定時間経過後に自動分析袋ｗ５で過酸化水素
濃度を分析し、金属イオン添加前の初期濃度からの変化
量よりエツチング浴中の安定剤濃度をコントローラー６
にて演算し、不足する安定剤の添加量を安定剤タンク１
２ａから定量ポンプ１２にて補充する。循環槽４へ補充
さ九た薬液はエツチング液と十分混合された後、循環ポ
ンプ２にて、エツチング槽」−へ送り込まれる。In the figure, the metal ion concentration, hydrogen peroxide concentration, and sulfuric acid concentration in the etching solution sampled at regular intervals from an etching tank 1 equipped with a heat exchanger 3 are analyzed by an automatic analyzer 5 and adjusted to the respective standard concentrations. The controller 6 calculates the amount of hydrogen peroxide and sulfuric acid to be refilled, and the metering pump 8
and replenish at 9. Furthermore, after injecting a certain amount of etching solution into the reaction cell at the same time as the sampling, a metal ion-containing aqueous solution (e.g. copper i
oo~1100001) P or iron 10~101000
A certain amount of PP is added from the metal solution tank lla using the pump 11, and after a certain period of time, the hydrogen peroxide concentration is analyzed using an automatic analysis bag w5. Controller 6 for agent concentration
Calculate the insufficient amount of stabilizer added to stabilizer tank 1.
The metering pump 12 is used to replenish from 2a. The chemical solution replenished into the circulation tank 4 is thoroughly mixed with the etching solution, and then sent to the etching tank by the circulation pump 2.
上述した方法により、一定時間毎に分析を実施し、その
結果に基づき必要量の硫酸、過酸化水素及び安定剤の補
充を繰り返し、エツチング浴の管理を行うものである。According to the method described above, analysis is carried out at regular intervals, and based on the results, the required amounts of sulfuric acid, hydrogen peroxide, and stabilizer are repeatedly replenished to manage the etching bath.
前述したように、本発明は、エツチング浴中の・ ５
一
金属イオン濃度増加に伴う適正な安定剤濃度の維持管理
を可能にすることにより、
（１）過酸化水素の分解反応を抑制し、過酸化水素の使
用域を低減できる。As mentioned above, the present invention enables the maintenance and management of an appropriate stabilizer concentration as the concentration of metal ions increases in the etching bath, thereby (1) suppressing the decomposition reaction of hydrogen peroxide; The range of hydrogen peroxide usage can be reduced.
（２）過酸化水素濃度を−・定範囲に維持できることに
より、安定なエソチンゲスピートを得ることができる。(2) By being able to maintain the hydrogen peroxide concentration within a certain range, stable esotingespeate can be obtained.
という効果がある。There is an effect.
第１図は本発明の構成を示すブロック図である。
Ｊ エツチング槽 ２・・循環ポンプ；３・熱交
換機 ４・循環槽５・・自動分析装置
６・・・コントローラー７ 反応セル ８
・硫酸用定量ポンプ９ 過酸化水素用定量ポンプ １０
・スターター】１・・金属溶液添加用ポンプ
１２・・安定剤用定量ポンプ
特許出願人 富山日本電気株式会社FIG. 1 is a block diagram showing the configuration of the present invention. J Etching tank 2. Circulation pump; 3. Heat exchanger 4. Circulation tank 5. Automatic analyzer
6... Controller 7 Reaction cell 8
- Metering pump for sulfuric acid 9 Metering pump for hydrogen peroxide 10
・Starter] 1. Metal solution addition pump 12. Stabilizer metering pump Patent applicant: Toyama NEC Co., Ltd.
Claims (1)
リングする工程と、前記サンプリング液に含有する過酸
化水素量を酸化還元滴定法により分析し、過酸化水素の
初期濃度を求める工程と、前記サンプリング液の所定量
に対し一定量の金属イオンを含有する溶液を添加してか
ら一定時間経過後に酸化還元滴定法により分析し、過酸
化水素の濃度を求める工程と、前記過酸化水素初期濃度
からの変化量に基づきエッチング浴に含有する安定剤の
濃度を求め、安定剤の設定濃度に対して不足する安定剤
の量を演算し、安定剤の不足量をエッチング浴に補充す
る工程とを有することを特徴とするエッチング浴の安定
剤の管理方法。(1) A step of sampling a certain amount of etching solution from the etching bath, a step of analyzing the amount of hydrogen peroxide contained in the sampling solution by redox titration method, and determining an initial concentration of hydrogen peroxide, A step in which a solution containing a certain amount of metal ions is added to a predetermined amount of hydrogen peroxide and then analyzed by redox titration after a certain period of time to determine the concentration of hydrogen peroxide, and the change from the initial concentration of hydrogen peroxide. The step of determining the concentration of the stabilizer contained in the etching bath based on the amount, calculating the amount of the stabilizer that is insufficient with respect to the set concentration of the stabilizer, and replenishing the insufficient amount of the stabilizer to the etching bath. Characteristic method for managing stabilizers in etching baths.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7737489A JPH02254181A (en) | 1989-03-29 | 1989-03-29 | Method for managing stabilizer of etching bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7737489A JPH02254181A (en) | 1989-03-29 | 1989-03-29 | Method for managing stabilizer of etching bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02254181A true JPH02254181A (en) | 1990-10-12 |
Family
ID=13632125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7737489A Pending JPH02254181A (en) | 1989-03-29 | 1989-03-29 | Method for managing stabilizer of etching bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02254181A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993021359A1 (en) * | 1992-04-17 | 1993-10-28 | Nippondenso Co., Ltd. | Method of and apparatus for detecting concentration of chemical processing liquid and automatic control apparatus for the same method and apparatus |
| JP2010243200A (en) * | 2009-04-01 | 2010-10-28 | Adeka Corp | Measuring method of hydrogen peroxide concentration in hydrogen peroxide-containing aqueous solution |
-
1989
- 1989-03-29 JP JP7737489A patent/JPH02254181A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993021359A1 (en) * | 1992-04-17 | 1993-10-28 | Nippondenso Co., Ltd. | Method of and apparatus for detecting concentration of chemical processing liquid and automatic control apparatus for the same method and apparatus |
| US5450870A (en) * | 1992-04-17 | 1995-09-19 | Nippondenso Co., Ltd. | Method and an apparatus for detecting concentration of a chemical treating solution and an automatic control apparatus thereof |
| JP2010243200A (en) * | 2009-04-01 | 2010-10-28 | Adeka Corp | Measuring method of hydrogen peroxide concentration in hydrogen peroxide-containing aqueous solution |
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