TWI539146B - On - line concentration determination probe and concentration determination system - Google Patents
On - line concentration determination probe and concentration determination system Download PDFInfo
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Description
本發明係有關一種線上型藥液濃度之測定探針與濃度測定系統者，更詳言之，係有關分光學的在反應槽內測定濃厚的藥液濃度之探針及使用其探針之濃度測定系統。 The present invention relates to a measuring probe for a linear drug concentration and a concentration measuring system, and more specifically, a probe for measuring a concentrated concentration of a chemical solution in a reaction tank and a concentration of a probe using the same. Measuring system.
關於本發明，若對照發明的構成並詳細記述，係有關用以在反應槽內測定反應液的濃度之探針，特別是有關一種用以在反應槽內測定反應液之濃度的探針與使用該探針之濃度測定系統，在從光源所發出的光經由光纖導引至反應槽並經由光纖將透射反應槽內部的反應液之該光導引至受光元件之探針中，朝受光元件導引透射光用的光纖的核心徑係比導引從光源發出的光用的光纖的核心徑還大，以導引從光源發出的光用之光纖的和光源相反側之端部及朝受光元件導引透射光的和受光元件相反側之端部各自露出的核心面相面對且光纖前端突出之方式固定。 The present invention relates to a probe for measuring the concentration of a reaction liquid in a reaction tank, and more particularly to a probe for measuring the concentration of a reaction liquid in a reaction tank, and a description thereof. The probe concentration measuring system guides the light emitted from the light source to the reaction tank via the optical fiber, and guides the light of the reaction liquid inside the reaction reaction tank to the probe of the light receiving element via the optical fiber, and guides the light to the light receiving element. The core diameter of the optical fiber for transmitting light is larger than the core diameter of the optical fiber for guiding light emitted from the light source to guide the end portion of the optical fiber for emitting light from the light source opposite to the light source and toward the light receiving element. The core surface on which the end portion of the light-transmitting element and the light-receiving element are exposed is opposed to each other and the front end of the optical fiber is protruded.
無電解銅鍍敷、電解銅鍍敷可說是為確保多層印刷基板製造時之層間的連接而使之不間斷的工程。另一方面，基於此種化學反應的加工液係有必要恆定 的濃度管理，當逸脫適當的管理範圍時會成為銅鍍敷之異常析出或不析出等不良之原因。關於無電解銅鍍敷液的管理項目，例如在[非專利文獻1]的[電鍍研究會編，’94年6月日刊工業新聞社發行「無電解鍍敷基礎與應用(參照P122-124)」中有銅濃度、還元劑濃度、pH、錯化劑等。另一方面，在電解銅鍍敷的情況則有銅濃度、硫酸濃度、添加劑濃度等。此等當中，銅濃度係伴隨著反覆鍍敷作業而單方面地減少。銅濃度的測定一般是適用採用EDTA等之配位滴定(chelatometric)、分光學的手法。特別是分光學的手法在此等銅鍍敷液中為主流。然而，此等均係以從銅鍍敷反應槽取樣藥液而進行離線測定為前提，在分析值之即時性、分析頻率方面，係難以進行精細的管理。 Electroless copper plating and electrolytic copper plating can be said to be an uninterrupted process for ensuring the connection between layers when manufacturing a multilayer printed circuit board. On the other hand, it is necessary to constant the processing fluid based on this chemical reaction. The concentration management will become a cause of abnormal precipitation or non-precipitation of copper plating when it is removed from the proper management range. For the management project of the electroless copper plating liquid, for example, [Non-Patent Document 1] [Electrical Research Society, "94 June, Nikkan Kogyo Shimbun, "Non-electroless plating foundation and application (refer to P122-124) There are copper concentration, reductant concentration, pH, and distorting agent. On the other hand, in the case of electrolytic copper plating, there are copper concentration, sulfuric acid concentration, additive concentration, and the like. Among these, the copper concentration is unilaterally reduced with the reverse plating operation. The measurement of the copper concentration is generally carried out by a method of chelatometric or spectroscopy using EDTA or the like. In particular, the method of separating optics is the mainstream in such copper plating solutions. However, these are premised on the offline measurement by sampling the chemical solution from the copper plating reaction tank, and it is difficult to perform fine management in terms of the immediacy of the analysis value and the analysis frequency.
分光學的濃度測定係藉由使從光源發出的測定光照射於被測定物並接收透射被測定物的光而進行。當來自於光源之光強度設為IO，被測定物所吸收之光強度設為Ia，受光之光強度設為It時，IO=Ia+It的關係成立，考量Ia係按被測定物的種類、濃度而固有者，若特定物質所吸收之光強度為已知，則使用It可求其濃度。 The concentration measurement of the optical separation is performed by irradiating the measurement light emitted from the light source to the object to be measured and receiving the light transmitted through the object to be measured. When the light intensity from the light source is I O , the light intensity absorbed by the object to be measured is Ia, and the light intensity of the received light is set to It, the relationship of I O =Ia+It is established, and the measurement Ia is based on the object to be measured. The type and concentration are inherent, and if the intensity of light absorbed by a specific substance is known, the concentration can be determined using It.
通常透射被測定物之光強度It係以A=-log(It/Io)之算式換算後的吸光度A表示。 Generally, the light intensity It transmitted through the object to be measured is expressed by the absorbance A converted by the formula of A = -log (It / Io).
吸光度A在被測定物之濃度低的情況係相對於濃度呈線性的關係。惟，在被測定物是高濃度的情況則此關係會崩解。此外，為有效率地析出銅而將開頭所述的銅鍍敷液之濃度設成高濃度，照鍍敷液其原樣係難以進行基於吸光度的濃度測定。 The absorbance A is linear with respect to the concentration when the concentration of the object to be measured is low. However, if the measured object is at a high concentration, the relationship will collapse. Further, in order to efficiently precipitate copper, the concentration of the copper plating solution described at the beginning is set to a high concentration, and it is difficult to perform concentration measurement based on the absorbance as it is.
於是，在離線的濃度測定中，係稀釋所取樣之鍍敷液，通常稀釋成10~100倍。 Therefore, in the off-line concentration measurement, the sampled plating solution is diluted, and is usually diluted 10 to 100 times.
如此一來，如上述透過離線之濃度測定係變得有必要進行所謂取樣、測定操作之作業，在所謂銅鍍敷液濃度測定之即時性、高頻率進行分析這點上變得不利。 As described above, it is necessary to perform the so-called sampling and measurement operations as described above for the concentration measurement system that has passed through the off-line, and it is disadvantageous in that the copper plating solution concentration measurement is instantaneous and high frequency is analyzed.
為此，例如在[專利文獻1]的[特開2001-228079號公報]所記載之發明、[專利文獻2]的[專利第3609029號公報]所記載之發明可見，揭示一種將可進行朝向被測定物之光照射與透射光之受光的單元直接浸泡於反應槽作測定的手法。此處，被測定物的吸光度與光路長、濃度係成立所謂朗伯-比爾定律，A=α LC For example, the invention described in [Patent Document 1], and the invention described in [Patent Document 2] [Patent No. 3609029] can be seen to be able to be oriented. The light irradiated by the object to be measured and the unit that receives light by the transmitted light are directly immersed in the reaction tank for measurement. Here, the absorbance of the object to be measured, the length of the optical path, and the concentration system establish the so-called Lambert-Beer law, A=α LC
(此處α表示被測定物固有之吸光係數，L表示光路長，C表示濃度)，針對高濃度的藥液將光路長縮短而可獲得與稀釋相同之效果。在上述的文獻中，作成透過將光路長設為可變而能以線上方式分析高濃度的藥液。 (where α represents the absorption coefficient inherent to the object to be measured, L represents the optical path length, and C represents the concentration), and the optical path length is shortened for the high-concentration chemical solution, and the same effect as the dilution can be obtained. In the above-mentioned literature, it is possible to analyze a high-concentration chemical solution on-line by changing the optical path length to be variable.
又，雖不是吸光度測定，但在[專利文獻3]的[特開昭63-284454號公報]所記載之發明中，係在有關朝向被測定物之光照射、散射光受光方法方面是使用光纖，而在[專利文獻4]的[特開2000-304693號公報]所記載之發明中，係使用玻璃竿以謀求單元之簡化。 In the invention described in the Japanese Patent Laid-Open Publication No. SHO-63-284454, the optical fiber is irradiated toward the object to be measured, and the method of receiving light by the scattered light is an optical fiber. In the invention described in JP-A-2000-304693, a glass crucible is used to simplify the unit.
〔專利文獻〕 [Patent Document]
〔專利文獻1〕特開2001-228079號公報 [Patent Document 1] JP-A-2001-228079
〔專利文獻2〕專利第3609029號公報 [Patent Document 2] Patent No. 3609029
〔專利文獻3〕特開昭63-284454號公報 [Patent Document 3] JP-A-63-284454
〔專利文獻4〕特開2000-304693號公報 [Patent Document 4] JP-A-2000-304693
〔專利文獻5〕特開2008-116314號公報 [Patent Document 5] JP-A-2008-116314
〔非專利文獻〕 [Non-patent literature]
〔非專利文獻1〕電鍍研究會編，94年6月日刊工業新聞社發行「無電解鍍敷基礎與應用」(參照P122-124) [Non-Patent Document 1] Electroplating Research Society, published in June 1994, Nikkan Kogyo Shimbun issued "Basic and Application of Electroless Plating" (Refer to P122-124)
在[專利文獻]的[特開2001-228079號公報]所記載之發明中，為變更光路長而透過使單元具備導螺桿、馬達等之可動機構來實現發光側與受光側接液面間距離，但為使單元自體具有此種機構而讓單元複雜化。又，在為保護此等機構不受高反應性藥液所影響時必須有什麼樣的防水構造。又，因為是具可動性的零件，故有所謂因衝擊等致使接液面間距離變動，結果使光路長改變而無法進行正確的濃度測定之虞。 In the invention described in the Japanese Patent Laid-Open Publication No. 2001-228079, the distance between the light-emitting side and the light-receiving side liquid-contacting surface is achieved by changing the optical path length and providing the unit with a movable mechanism such as a lead screw or a motor. However, the unit is complicated in order for the unit to have such a mechanism. Moreover, what kind of waterproof structure is necessary to protect these mechanisms from high-reactivity liquid chemicals. Further, since it is a movable member, there is a case where the distance between the liquid receiving surfaces is changed by an impact or the like, and as a result, the optical path length is changed and the accurate concentration measurement cannot be performed.
又，在[專利文獻2]的[專利第3609029號公報]所記載之發明中，有必要就光路長以可使之擁有幾個變化的方式加工玻璃單元，玻璃單元變複雜的形狀，加工 性會產生問題。特別是，在高濃度的藥液中必須將光路長設定為100μm以下，會增加玻璃加工之難度。 Further, in the invention described in [Patent Document No. 3,609,029], it is necessary to process the glass unit in such a manner that the optical path length can be changed several times, and the glass unit becomes complicated in shape and processed. Sex will cause problems. In particular, it is necessary to set the optical path length to 100 μm or less in a high concentration chemical solution, which increases the difficulty in glass processing.
又，在此等前述的2個文獻所記載之發明中，因為其形狀的複雜度之緣故，有可能透射光測定部的液流相對於槽整體變慢，而未必成為代表槽整體的藥液濃度之濃度。 Further, in the invention described in the above two documents, the flow of the transmitted light measuring unit may be slow with respect to the entire groove due to the complexity of the shape, and may not necessarily be a liquid medicine representing the entire groove. The concentration of the concentration.
為因應此等課題，在專利文獻3所記載之發明中，透過利用光纖從位在反應槽外部的發光部朝反應槽，從反應槽朝位在反應槽外部的受光部導光而簡化單元。 In order to cope with such a problem, in the invention described in Patent Document 3, the unit is simplified by guiding the light from the light-emitting portion located outside the reaction vessel to the reaction vessel from the reaction vessel toward the light-receiving portion outside the reaction vessel by the optical fiber.
然而，由於該文獻所記載之發明係有關濁度測定之手法，所以未必需要接收所有在反應槽內散射的光。通常作為光纖的導光部之核心徑係數十~數百μm，在未適當地選擇之情況，測定光會在液中漏洩，而變得難以正確的測定。 However, since the invention described in this document is a technique for measuring turbidity, it is not necessary to receive all the light scattered in the reaction tank. Generally, the core diameter coefficient of the light guiding portion of the optical fiber is ten to several hundreds μm, and when it is not appropriately selected, the measurement light leaks in the liquid, and it becomes difficult to perform accurate measurement.
又，在該文獻所記載之發明中，以光纖在反應構內部突出的方式固定，但一般在工業生產中之無電解銅鍍敷的反應槽係大到數公尺平方，要將光纖間之距離，亦即光路長如上述般控制成100μm以下是有困難的。 Further, in the invention described in this document, the optical fiber is fixed so as to protrude inside the reaction structure, but in general, the electroless copper plating reaction tank in industrial production is as large as several square meters, and the fiber is required to be The distance, that is, the length of the light path is controlled to be 100 μm or less as described above.
又，如[專利文獻4]的[特開2000-304693號公報]所記載之發明可見，在將玻璃竿浸泡於液中進行測定時，在玻璃與藥液的折射率接近之情況，在玻璃竿內導光之光有可能從原本應全反射的玻璃竿側壁漏出，其結果係難以進行正確的測定。 In the invention described in JP-A-2000-304693, when the glass crucible is immersed in a liquid and measured, the refractive index of the glass and the chemical liquid is close to that of the glass. The light guided light in the crucible may leak from the side wall of the glass crucible which should be totally reflected, and as a result, it is difficult to perform accurate measurement.
對此，在[專利文獻5]的[特開2008-116314 號公報]所記載之發明中，揭示一種使光纖近接並固定於V溝之方法。藉此雖可實現100μm以下的光路長，但為了在V溝固定光纖而有必要使用光纖的素線。素線係為不具有保護用被覆之光纖，具有所謂因為彎曲或衝撃而折斷之問題。為使在槽內的藥液濃度均勻，故反應槽內以高速進行攪拌，於浸泡光纖素線的情況，可想會發生折斷、龜裂等，正確的測定變困難。 In this regard, [Patent Document 5] [Specially Open 2008-116314 In the invention described in the Japanese Laid-Open Patent Publication, a method of bringing an optical fiber into proximity to a V-groove is disclosed. Although the optical path length of 100 μm or less can be achieved by this, it is necessary to use a plain fiber of the optical fiber in order to fix the optical fiber in the V-groove. The plain line is an optical fiber that does not have a protective coating, and has a problem of being broken due to bending or punching. In order to make the concentration of the chemical solution in the tank uniform, the reaction tank is stirred at a high speed, and when the optical fiber is immersed, it is thought that fracture or cracking may occur, and accurate measurement becomes difficult.
於是，有鑒於前述之技術上的諸不理想狀況，在要建構一種縮短光路長、使測定部的液流阻礙成為最小限度之不發生光之漏洩等之正確且簡易的線上型濃度測定探針時該如何是好，乃成為技術上的問題點，本發明之目的在於解決此種技術課題。 Therefore, in view of the above-described unsatisfactory state of the art, it is necessary to construct a correct and simple on-line concentration measuring probe that shortens the optical path length and minimizes leakage of the flow in the measuring portion without causing leakage of light. How to be good at the time is a technical problem, and the object of the present invention is to solve such a technical problem.
本發明係為達成前述目的而提案者，請求項1所記載之發明係提供一種用以在反應槽內測定反應液之濃度的探針，係為線上型的吸光度測定探針，在從光源所發出的光經由光纖導引至反應槽並經由光纖將透射反應槽內部的反應液之該光導引至受光元件之探針中，朝受光元件導引透射光用的光纖的核心徑係比導引從光源發出的光用之光纖的核心徑還大，以導引從光源發出的光用之光纖的和光源相反側之端部及朝受光元件導引透射光的和受光元件相反側之端部各自露出的核心面相面對且光纖前端突出之方式固定，相面對之露出的核心面間之距離係以在離線測定反應液濃度之際的光路長除以在離線測定中之稀釋倍率值或其為其以下之方式設定，及 本發明係提供一種如前述之用以在反應槽內測定反應液之濃度的探針，其中關於在導引從上述光源發出的光用的光纖中之含有露出接液部的核心之端部，其端部是被以不受該反應槽內之液所侵害的材質作成之套圈所保護，及本發明係提供一種如前述之用以在反應槽內測定反應液之濃度的探針，其中導引從上述光源發出的光用的光纖之核心徑是62.5μm以下，進一步來說是50μm以下，將透射光導往上述受光元件之光纖的核心徑是100μm以上，進一步來說是200μm以上，及本發明係提供一種如前述之用以在反應槽內測定反應液之濃度的探針，其中導引從上述光源發出的光用之光纖與朝上述受光元件導引透射光用之光纖各自露出之相對向的核心面彼此之距離係1mm以下，進一步來說是200μm以下，及，本發明係提供一種用以在反應槽內測定反應液之濃度測定的濃度測定系統，其特徵為，使用如前述之用以在反應槽內測定反應液之濃度的探針，將測定各種濃度的反應液所作成之檢量線保持在控制用裝置，針對使用上述之濃度測定用的探針以線上方式測定上述反應液之吸光度的測定結果，透過參照該控制用裝置所保持之檢量線而即時換算成濃度。 The present invention provides a probe for measuring the concentration of a reaction liquid in a reaction tank, and is an on-line type absorbance measurement probe. The emitted light is guided to the reaction tank via the optical fiber, and the light of the reaction liquid inside the transmission reaction tank is guided to the probe of the light-receiving element via the optical fiber, and the core diameter ratio of the optical fiber for guiding the transmitted light to the light-receiving element is guided. The core of the optical fiber for emitting light from the light source has a large core diameter to guide the end of the optical fiber for emitting light from the light source opposite to the light source and the end opposite to the light receiving element that guides the transmitted light toward the light receiving element. The exposed core faces of the parts are fixed and the front end of the optical fiber is protruded. The distance between the exposed core faces is the optical path length when the concentration of the reaction solution is measured off-line divided by the dilution ratio value in the off-line measurement. Or set it in the following ways, and The present invention provides a probe for measuring a concentration of a reaction liquid in a reaction tank as described above, wherein an end portion of a core for guiding light receiving light from the light source and a core portion exposing the liquid contact portion is provided The end portion is protected by a ferrule made of a material that is not damaged by the liquid in the reaction tank, and the present invention provides a probe for measuring the concentration of the reaction liquid in the reaction tank as described above, wherein The core diameter of the optical fiber for guiding light emitted from the light source is 62.5 μm or less, further 50 μm or less, and the core diameter of the optical fiber that transmits the transmitted light to the light receiving element is 100 μm or more, further 200 μm or more, and The present invention provides a probe for measuring a concentration of a reaction liquid in a reaction tank as described above, wherein an optical fiber for guiding light emitted from the light source and an optical fiber for guiding transmitted light toward the light receiving element are exposed The distance between the opposing core faces is 1 mm or less, further 200 μm or less, and the present invention provides a concentration measurement for measuring the concentration of the reaction liquid in the reaction tank. The system is characterized in that a probe for measuring a concentration of a reaction liquid in a reaction tank as described above is used to hold a calibration line for measuring a reaction liquid of various concentrations in a control device, and the concentration is determined by using the above concentration. The probe for measuring the absorbance of the reaction solution was measured in an on-line manner, and was immediately converted into a concentration by referring to the calibration curve held by the control device.
依據本發明之構成，在作為使從光源所發出的光及透射的光導光於受光元件之手段方面是使用光 纖，因為朝向反應液中之光漏洩少而可進行正確的濃度測定，在探針的構造變簡單、製造成本、液體流動方面是有利的。又，從以光纖的端部突出的方式固定可知，更有利於液體流動，可即時地反映反應槽整體之濃度。 According to the configuration of the present invention, light is used as means for guiding light emitted from the light source and transmitted light to the light receiving element. Since the fiber is less likely to leak toward the reaction liquid, accurate concentration measurement can be performed, which is advantageous in terms of the structure of the probe being simple, the manufacturing cost, and the liquid flow. Further, it is known from the fact that the end portion of the optical fiber is protruded, and it is more advantageous for the liquid to flow, and the concentration of the entire reaction tank can be immediately reflected.
又，依據本發明之構成，藉由將光纖的接液端部以套圈保護，可防止因液流或衝撃等所致之光纖破損。此時，套圈的材質係以不受反應液侵害之材質較佳，說到無電解銅鍍敷液，藉由使用鋯石或硼矽酸玻璃等而可防止光纖破損。 Further, according to the configuration of the present invention, by protecting the liquid-contacting end portion of the optical fiber with a ferrule, it is possible to prevent breakage of the optical fiber due to liquid flow or punching. At this time, the material of the ferrule is preferably made of a material that is not affected by the reaction liquid. When it is said that the electroless copper plating solution is used, it is possible to prevent breakage of the optical fiber by using zircon or borosilicate glass.
又，依據本發明之構成，藉由將受光側之光纖的核心徑設成比發光側之光纖大而可將朝反應液中之測定光的漏洩抑制在最小限度俾能進行正確的濃度測定。 Further, according to the configuration of the present invention, by setting the core diameter of the optical fiber on the light-receiving side to be larger than the optical fiber on the light-emitting side, it is possible to minimize the leakage of the measurement light in the reaction liquid and to perform accurate concentration measurement.
又，在本發明中，係透過以在離線測定反應槽中之該反應液濃度之際的光路長除以在該離線測定中之稀釋率的值或其以下之方式設定相面對之核心面間距離，而無需對高濃度的反應液進行稀釋，可進行正確的濃度測定。 Further, in the present invention, the facing core surface is set by dividing the optical path length at the time of measuring the concentration of the reaction liquid in the reaction tank offline by the value of the dilution ratio in the off-line measurement or less. The distance can be determined without diluting the high concentration of the reaction solution.
又，依據本發明，係將設定成各種濃度的反應液使用該探針測定而作成檢量線並輸入於控制用機器，該控制用機器等或探針可從線上所測定之吸光度的測定結果輸出正確的濃度。藉此，可即時地監控反應液濃度。 Further, according to the present invention, the reaction liquid set to various concentrations is measured by the probe to be used as a calibration curve, and is input to a control device, and the measurement result of the absorbance measured by the control device or the probe from the line can be measured. Output the correct concentration. Thereby, the concentration of the reaction liquid can be monitored instantaneously.
如以上，總括發明之效果可知，依據本發明，在進行未稀釋通常需稀釋的反應液之濃度測定下，可正確且線上作測定，藉由即時地測定反應液濃度，而可始 終將反應液管理成良好的狀態，其結果，使用該反應液可穩定地製造要製造之製品，可帶來所謂減低該製品之製造成本及依製造成本減低而有助於減低製品成本之很大的有用性。 As described above, according to the effects of the invention, according to the present invention, the measurement can be carried out correctly and on the line under the measurement of the concentration of the undiluted reaction solution which is usually diluted, and the concentration of the reaction solution can be measured immediately. The reaction liquid is finally managed in a good state. As a result, the use of the reaction liquid can stably produce the product to be manufactured, which can bring about a reduction in the manufacturing cost of the product and a reduction in the cost of the product. Great usefulness.
1‧‧‧套圈 1‧‧‧ ferrule
2‧‧‧供設置在板3上的套圈前端貫通之貫通孔 2‧‧‧through holes for the front end of the ferrule provided on the plate 3
3‧‧‧板 3‧‧‧ boards
4a‧‧‧套圈的凸緣 4a‧‧‧Flange flange
4b‧‧‧光纖的本體部(網狀物) 4b‧‧‧ body part of the fiber (mesh)
4a'‧‧‧套圈的凸緣 4a'‧‧‧ ferrule flange
4b'‧‧‧光纖的本體部(網狀物) 4b'‧‧‧ body part of the fiber (mesh)
5‧‧‧光纖支持體 5‧‧‧Fiber support
5'‧‧‧光纖支持體 5'‧‧‧Fiber support
6‧‧‧光纖端部間間隙 6‧‧‧Inter-fiber gap
7‧‧‧橋接構件 7‧‧‧Bridge components
8‧‧‧吸光度測定探針 8‧‧‧Absorbance measuring probe
9‧‧‧反應槽 9‧‧‧Reaction tank
10‧‧‧光源 10‧‧‧Light source
11‧‧‧檢測器 11‧‧‧Detector
12‧‧‧放大器 12‧‧‧Amplifier
13‧‧‧控制用PC 13‧‧‧Control PC
14‧‧‧低通濾波器 14‧‧‧Low-pass filter
〔圖1〕係示意地顯示實施例1中形成光纖支持體的構件之構成的斜視圖。 Fig. 1 is a perspective view schematically showing a configuration of a member for forming a fiber holder in the first embodiment.
〔圖2〕係示意地顯示實施例1中之光纖支持體組立後的態樣之斜視圖。 Fig. 2 is a perspective view schematically showing a state in which the optical fiber support in the embodiment 1 is assembled.
〔圖3〕係示意地顯示實施例1中之對準2個光纖支持體的光軸之態樣的斜視圖。 FIG. 3 is a perspective view schematically showing an aspect in which the optical axes of the two optical fiber supports in the first embodiment are aligned.
〔圖4〕係示意地顯示實施例1中的探針之斜視圖。 Fig. 4 is a perspective view schematically showing the probe in the first embodiment.
〔圖5〕係顯示基於在實施例1組立的探針之測定系統的構成之方塊圖。 Fig. 5 is a block diagram showing the configuration of a measurement system based on the probes assembled in the first embodiment.
本發明係透過提供如下之用以在反應槽內進行反應液的濃度之探針來實現者，即，係為線上型的吸光度測定探針，從光源所發出的光經由光纖導引至反應槽，經由光纖將透射反應槽內部的反應液之該光導引至受光元件，該探針之特徵為，朝受光元件導引透射光用的光纖的核心徑係比導引從光源發出的光用之光纖的核心徑還大，以導引從光源發出的光用之光纖的和光源相反側之端部及朝受光元件導引透射光的和受光元件相反側之端部各自露出的核心面相面對且光纖前端突出之方式固 定，相面對之露出的核心面間之距離係以在離線測定反應液濃度之際的光路長除以在離線測定中之稀釋倍率值或其為其以下之方式設定。此外，以下，雖按照圖面來顯現本發明的實施例，惟本發明不受此所限。 The present invention is achieved by providing a probe for carrying out a concentration of a reaction liquid in a reaction tank, that is, an on-line type absorbance measuring probe, and light emitted from a light source is guided to a reaction tank via an optical fiber. And guiding the light of the reaction liquid inside the reaction cell to the light receiving element via an optical fiber, wherein the probe is characterized in that the core diameter of the optical fiber for guiding the light to the light receiving element is greater than the light emitted from the light source. The core diameter of the optical fiber is also large to guide the end face of the optical fiber emitted from the light source opposite to the light source and the core surface exposed to the end of the light receiving element and the end opposite to the light receiving element. And the way the fiber front end protrudes The distance between the exposed core faces is set by dividing the optical path length when the concentration of the reaction solution is measured off-line by the dilution ratio value in the off-line measurement or the following. Further, the embodiments of the present invention are shown below in the drawings, but the present invention is not limited thereto.
首先，如圖1所示，準備一端為與分光光度計所準備的光連接器相同之連接器且另一端為直徑1.249mm，從前端到凸緣4a的距離是4.95mm的以氧化鋯製套圈加工之帶有被覆的光纖的套圈(光纖)1(NA=0.21、核心徑50μm、被覆徑0.9mm、GI多模光纖)，及可貫通此套圈前端般地設有貫通孔2之厚度1mm、1mm平方的SUS316的板3。同圖中，如前述，4a係前述套圈1的凸緣，4b係形成套圈的主要構成之光纖的本體(網狀物)。 First, as shown in Fig. 1, a connector having the same end as the optical connector prepared by the spectrophotometer is prepared, and the other end is a diameter of 1.249 mm, and the distance from the front end to the flange 4a is 4.95 mm. a ferrule (optical fiber) 1 with a coated optical fiber (NA = 0.21, a core diameter of 50 μm, a coated diameter of 0.9 mm, a GI multimode fiber), and a through hole 2 is provided through the front end of the ferrule. A plate 3 of SUS316 having a thickness of 1 mm and a width of 1 mm. In the same figure, as described above, 4a is the flange of the ferrule 1, and 4b is the body (mesh) of the main fiber of the ferrule.
此外，如圖2所示般，製作使套圈1以套圈的凸緣4a作為止動器在貫穿過SUS316的板3之貫通孔2後並將兩者固定而成之光纖支持體5。此外，在各圖中僅圖示套圈，並未圖示帶有被覆的光纖。 Further, as shown in FIG. 2, the optical fiber support 5 in which the ferrule 1 is a stopper of the ferrule 4a as a stopper through the through hole 2 of the plate 3 of the SUS316, and the both are fixed. Further, only the ferrule is shown in each drawing, and the coated optical fiber is not shown.
與前述光纖支持體5同樣的光纖支持體5'係使用核心徑118μm之帶有被覆的光纖1’與光纖支持用的板3來製作(光纖支持體5'未單獨圖示)。吸光度測定探針的製作係將此等2個支持體5及5'作為1組來使用。 The optical fiber support 5' similar to the above-described optical fiber support 5 is produced by using the coated optical fiber 1' having a core diameter of 118 μm and the optical fiber supporting plate 3 (the optical fiber support 5' is not separately shown). The production of the absorbance measurement probe was performed by using the two support bodies 5 and 5' as one set.
接著，將該光纖支持體5,5'以適切的方法把持於調芯機，如圖3所示般調整2個光纖支持體的光軸。此時，透過使用屬光零件組立機構的調芯機而能高精度進行光軸調整及光纖端部間距離之設定，即，在調芯結束時 光纖端部間的間隙6之距離會成為100μm。藉由將光纖端部間距離設為100μm且使用1cm的單元，使得通常以100倍稀釋進行吸光度測定之反應液可無稀釋進行測定。此外，從基於NA所求的光纖射出之射出角是12°，故而從50μm核心射出之光於位在100μm處的光束徑成為約100μm，但與光纖核心的折射率(1.4~1.6)相比，在無電解銅鍍敷液的折射率低的情況，受光側之光纖的核心徑係100μm以下即可。然而因折射率亦依反應液之濃度而變化，故此處適用核心徑118μm的光纖。此乃相當於液體的折射率2.3以上，通常，水溶液不會成為此種折射率。 Next, the optical fiber supports 5, 5' are held by a aligning machine in an appropriate manner, and the optical axes of the two optical fiber supports are adjusted as shown in FIG. At this time, the optical axis adjustment and the distance between the end portions of the optical fibers can be accurately performed by using the alignment machine of the optical component assembly mechanism, that is, at the end of the alignment The distance between the ends of the fibers 6 will be 100 μm. The reaction liquid which was usually subjected to absorbance measurement at 100-fold dilution was measured without dilution by setting the distance between the end portions of the optical fibers to 100 μm and using a unit of 1 cm. Further, since the exit angle of the fiber exit based on the NA is 12°, the beam diameter of the light emitted from the 50 μm core at 100 μm becomes about 100 μm, but compared with the refractive index of the fiber core (1.4 to 1.6). When the refractive index of the electroless copper plating solution is low, the core diameter of the optical fiber on the light receiving side may be 100 μm or less. However, since the refractive index also varies depending on the concentration of the reaction liquid, an optical fiber having a core diameter of 118 μm is used here. This corresponds to a refractive index of the liquid of 2.3 or more, and usually, the aqueous solution does not become such a refractive index.
調芯結束後，在維持調芯機把持著該光纖支持體5及5’的狀態，如圖4所示般，以橋接兩支持體之方式使用橋接構件7固定。將此等光纖支持體5及5’、橋接構件7湊合而成之構造體係吸光度測定探針8。橋接構件7使用了厚度1mm之SUS316的板。在固定的方法方面可適用接著材或機械固定、溶接等，但此處是以雷射溶接進行固定。在使用接著材時需為不受反應液侵害的材質，在進行機械固定時需考慮在固定時光纖支持體彼此的位置關係不會失常。透過適用雷射溶接而變得不需要此等之考慮。此外，電阻溶接雖亦可適用，但有必要考慮在將溶接探針壓向支持體、橋接構件時支持體彼此的位置關係不會失常。 After the core adjustment is completed, the state in which the fiber holders 5 and 5' are held by the core adjusting machine is maintained, and as shown in Fig. 4, the bridge members 7 are fixed by bridging the two supports. The structural system absorbance measuring probe 8 is obtained by arranging the optical fiber supports 5 and 5' and the bridge member 7. As the bridging member 7, a plate of SUS316 having a thickness of 1 mm was used. In the case of a fixed method, it is possible to apply a backing or mechanical fixing, welding, etc., but here it is fixed by laser welding. When using the backing material, it is necessary to protect the material from the reaction liquid. When mechanically fixing, it is necessary to consider that the positional relationship between the optical fiber supports is not abnormal when fixed. This is not required by the application of laser fusion. Further, although resistance fusion can be applied, it is necessary to consider that the positional relationship between the supports does not become abnormal when the fusion probe is pressed against the support or the bridge member.
在結束固定後，於分光光度計上安裝吸光度測定探針8，進行基於空白之吸光度測定。由於在光纖內會有傳送損失或在光纖端部之菲涅耳反射等，所以在空 白時，並不是所輸入的光全部可受光。 After the fixation was completed, the absorbance measuring probe 8 was attached to a spectrophotometer, and the absorbance measurement based on the blank was performed. In the air, there will be transmission loss or Fresnel reflection at the end of the fiber, etc. When white, not all of the input light can be received.
因為此空白值會受探針之製造誤差的影響，故將探針作個別地測定。 Since this blank value is affected by the manufacturing error of the probe, the probe is individually measured.
使用此等實施例所示之探針來構成用以在反應槽內進行反應液的濃度測定之濃度測定系統。圖5顯示其示意方塊圖。同圖中，9係反應槽，係為了進行線上檢測等而使用探針8而供作濃度檢測之鍍敷浴槽。由發出測定波長的光之雷射光源10與檢測透射反應液的雷射光之檢測器11、放大來自於該檢測器11的信號之放大器12、及雷射光源之控制與接取檢測器的信號之控制用PC13所構成。對PC13預先輸入空白及2種類以上的標準濃度反應液之測定結果，作為檢量線加以保持。此乃係每次探針8改變時進行。由於探針8的光纖間乃自由空間，可想像反應液中的異物會通過光纖間，故設置在從放大器12至PC13的信號路徑***低通濾波器14以將突然的信號變化削除之機構。又，為因應於因異物附著或液體劣化所致吸光度之恆定的變化，故建構成在超過PC13所接收之吸光度的上下限之情況由PC13發出警報。又，藉由測定結果蓄積於PC13，可一邊追蹤反應槽9之反應液的逐次的濃度變化一邊進行濃度檢測。 A concentration measuring system for measuring the concentration of the reaction liquid in the reaction tank was constructed using the probes shown in these examples. Figure 5 shows a schematic block diagram thereof. In the same figure, the 9-series reaction tank is a plating bath for performing concentration detection using the probe 8 for on-line detection or the like. A laser light source 10 that emits light of a measurement wavelength, a detector 11 that detects laser light that transmits the reaction liquid, an amplifier 12 that amplifies a signal from the detector 11, and a signal for controlling and receiving the detector of the laser light source The control is constituted by the PC 13. The measurement results of the blank and two or more standard concentration reaction liquids are input to the PC 13 in advance, and are held as a calibration curve. This is done each time the probe 8 is changed. Since the fibers of the probe 8 are free spaces, it is conceivable that foreign matter in the reaction liquid passes between the optical fibers, so that a signal path from the amplifier 12 to the PC 13 is inserted into the low-pass filter 14 to remove a sudden signal change. Further, in response to a constant change in absorbance due to foreign matter adhesion or liquid deterioration, the PC 13 issues an alarm when the upper and lower limits of the absorbance received by the PC 13 are exceeded. Further, by accumulating the measurement result in the PC 13, it is possible to perform concentration detection while tracking the successive concentration changes of the reaction liquid in the reaction tank 9.
假設在前述之實施例1中反應液的離線測定之稀釋率是100倍，光纖端部間之距離6設為100μm。在離線的稀釋率低，對1cm的測定單元以10倍稀釋進行測定那樣的銅濃度是較稀薄的反應液時，在適用光纖端部 間距離100μm的探針之情況，由於所測定之吸光度變低，故受解析力之降低所影響。 It is assumed that the dilution ratio of the offline measurement of the reaction liquid in the above-described Example 1 is 100 times, and the distance 6 between the ends of the optical fibers is set to 100 μm. When the dilution ratio at the offline is low, when the copper concentration of the measurement unit of 1 cm is measured by 10-fold dilution, the concentration of copper is a relatively thin reaction solution, and the end of the fiber is applied. In the case of a probe having a distance of 100 μm, since the measured absorbance is low, it is affected by a decrease in the resolution.
於是，使探針組立時設定之光纖端部間距離與稀釋率10倍一致設為1mm。在適用前述之核心徑50μm的光纖之情況，在受光端之光束徑成為460μm。因此，受光側之光纖的核心徑亦設成460μm以上，較佳為設成680μm以上(相當於反應液的折射率2以上)。 Then, the distance between the end portions of the optical fibers set at the time of setting the probe assembly was set to 1 mm in accordance with the dilution ratio of 10 times. In the case where the above-mentioned optical fiber having a core diameter of 50 μm is applied, the beam diameter at the light receiving end becomes 460 μm. Therefore, the core diameter of the optical fiber on the light receiving side is also 460 μm or more, and preferably 680 μm or more (corresponding to a refractive index of the reaction liquid of 2 or more).
此外，本發明可在不逸脫本發明基本的精神下作各種改變，且本發明當然可及於該改變者。 In addition, the present invention can be variously modified without departing from the spirit of the invention, and the invention can of course be applied to the changer.
本發明係可期待帶來在反應槽內之濃度測定，特別是可利用於銅鍍敷液中之銅濃度測定、無電解銅鍍敷液槽中之濃度測定等領域中之銅濃度測定上的卓越效用。 The present invention can be expected to bring about concentration measurement in a reaction tank, and in particular, it can be used for measurement of copper concentration in the field of copper concentration in copper plating solution, concentration measurement in electroless copper plating bath, and the like. Excellent utility.
3‧‧‧板 3‧‧‧ boards
4a'‧‧‧套圈的凸緣 4a'‧‧‧ ferrule flange
4b'‧‧‧光纖的本體部(網狀物) 4b'‧‧‧ body part of the fiber (mesh)
5‧‧‧光纖支持體 5‧‧‧Fiber support
5'‧‧‧光纖支持體 5'‧‧‧Fiber support
6‧‧‧光纖端部間間隙 6‧‧‧Inter-fiber gap
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