TWI707383B - Concentration monitoring apparatus for developing solution and developing solution management apparatus - Google Patents

Concentration monitoring apparatus for developing solution and developing solution management apparatus Download PDF

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TWI707383B
TWI707383B TW106141770A TW106141770A TWI707383B TW I707383 B TWI707383 B TW I707383B TW 106141770 A TW106141770 A TW 106141770A TW 106141770 A TW106141770 A TW 106141770A TW I707383 B TWI707383 B TW I707383B
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中川俊元
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日商平間理化硏究所股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3042—Imagewise removal using liquid means from printing plates transported horizontally through the processing stations
    • G03F7/3071—Process control means, e.g. for replenishing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70483—Information management; Active and passive control; Testing; Wafer monitoring, e.g. pattern monitoring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D3/00—Liquid processing apparatus involving immersion; Washing apparatus involving immersion
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/002—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using materials containing microcapsules; Preparing or processing such materials, e.g. by pressure; Devices or apparatus specially designed therefor
    • G03F7/0022—Devices or apparatus
    • G03F7/0025—Devices or apparatus characterised by means for coating the developer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

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Abstract

提供一種由顯影液的特性值高精度地算出呈現鹼性的顯影液的鹼成分、溶解的光阻劑、及所吸收之二氧化碳等的各成分的濃度之濃度監視裝置、及將顯影液的顯影性能維持及管理在最佳的狀態之顯影液管理裝置。 To provide a concentration monitoring device that accurately calculates the concentration of each component such as the alkali component of the alkaline developer, the dissolved photoresist, and the absorbed carbon dioxide from the characteristic value of the developer, and develops the developer A developer management device that maintains and manages performance in the best state.

顯影液的濃度監視裝置A係具備：測定部1，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之顯影液的複數個特性值；運算部2，依據藉測定部1所測定之複數個特性值，藉由多變量分析法算出顯影液的成分濃度；及警報部WD，在藉運算部2所算出之成分濃度中至少一者偏離所設定之管理範圍時發出警報。 The developer concentration monitoring device A is equipped with: a measuring section 1, which measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and a computing section 2, based on the measurement by the measuring section 1. A plurality of characteristic values are calculated by the multivariate analysis method to calculate the component concentration of the developer; and the alarm unit WD, which generates an alarm when at least one of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

Description

顯影液的濃度監視裝置及顯影液管理裝置 Developer concentration monitoring device and developer management device

有關一種在半導體或液晶面板之電路基板的顯影製程等中為了將光阻劑膜(photoresist film)顯影而重複使用之呈現鹼性的顯影液的濃度監視裝置及顯影液管理裝置。 It relates to an alkaline developer concentration monitoring device and developer management device that are repeatedly used in the development process of semiconductor or liquid crystal panel circuit substrates in order to develop photoresist films.

在實現半導體、液晶面板等中之微細配線加工的光微影(photolithography)的顯影製程中，使用呈現鹼性的顯影液(以下稱為「鹼性顯影液」。)作為將成膜於基板上的光阻劑溶解之藥液。 In the development process of photolithography that realizes the processing of fine wiring in semiconductors, liquid crystal panels, etc., an alkaline developer (hereinafter referred to as "alkaline developer") is used as a film on the substrate The photoresist is dissolved in a liquid medicine.

在半導體、液晶面板基板等之製程中，近年來晶圓、玻璃基板等之大型化與配線加工的微細化及高積體化已有長足進展。在這樣的狀況下，為實現大型基板的配線加工的微細化及高積體化，有必要更加高精度地測定鹼性顯影液的主要成分的濃度以維持管理顯影液。 In the manufacturing process of semiconductors, liquid crystal panel substrates, etc., in recent years, great progress has been made in the enlargement of wafers and glass substrates, and the miniaturization and high integration of wiring processing. Under such circumstances, in order to realize the miniaturization and high integration of the wiring processing of large-sized substrates, it is necessary to measure the concentration of the main components of the alkaline developer with higher accuracy to maintain and manage the developer.

如專利文獻1所記載般，習知的鹼性顯影液的成分濃度之測定係利用在鹼性顯影液的鹼成分的濃 度(以下稱為「鹼成分濃度」。)與導電率之間可獲得良好的線性關係、及在已溶解於鹼性顯影液的光阻劑的濃度(以下稱為「溶解光阻劑濃度」。)與吸光度之間可獲得良好的線性關係者。 As described in Patent Document 1, the conventional measurement of the component concentration of an alkaline developer is based on the difference between the concentration of the alkaline component of the alkaline developer (hereinafter referred to as "alkali component concentration") and the electrical conductivity. A good linear relationship and a good linear relationship can be obtained between the concentration of the photoresist dissolved in the alkaline developer (hereinafter referred to as "dissolved photoresist concentration") and the absorbance.

此外，鹼性顯影液會吸收空氣中的二氧化碳，容易產生碳酸鹽而劣化。而且，鹼性顯影液係藉光阻劑的溶解而產生光阻劑鹽，對顯影處理有效的鹼性成分會被消耗。因此，重複使用的鹼性顯影液會成為不僅含有鹼成分，也含有光阻劑、二氧化碳等的多成分系。而且，其等成分各自以不同的貢獻度對顯影性能產生影響。因此為了能高精度地維持管理顯影液的顯影性能，將此等成分對顯影性能的影響一併考量的顯影液管理是必要的。 In addition, the alkaline developer absorbs carbon dioxide in the air, and tends to produce carbonate and deteriorate. In addition, the alkaline developer generates photoresist salt by dissolving the photoresist, and the alkaline components effective for the development process are consumed. Therefore, the repeatedly used alkaline developer becomes a multi-component system containing not only an alkali component but also a photoresist, carbon dioxide, and the like. Moreover, its components have different contributions to the development performance. Therefore, in order to maintain and manage the developing performance of the developer with high accuracy, the management of the developer in consideration of the influence of these components on the developing performance is necessary.

為解決這樣的問題，在專利文獻2中揭示顯影液調製裝置等，係測定顯影液的超音波傳播速度、導電率及吸光度，依據在鹼濃度、碳酸鹽濃度及溶解樹脂濃度下之超音波傳播速度和導電率及吸光度之預先作成的關係(矩陣)來檢測顯影液的鹼濃度、碳酸鹽濃度及溶解樹脂濃度，且根據所測定之顯影液的鹼濃度、碳酸鹽濃度及溶解樹脂濃度，及能發揮CD值(critical dimension value)(線寬)成為固定的值之溶解能力的、鹼濃度與碳酸鹽濃度與溶解樹脂濃度之預先所製作的關係，控制顯影液原液的供給以調節鹼濃度。 In order to solve this problem, Patent Document 2 discloses a developer preparation device, etc., which measure the ultrasonic propagation velocity, conductivity, and absorbance of the developer based on the ultrasonic propagation under the alkali concentration, carbonate concentration, and dissolved resin concentration. The relationship (matrix) between speed, conductivity and absorbance is pre-made to detect the alkali concentration, carbonate concentration and dissolved resin concentration of the developer, and based on the measured alkali concentration, carbonate concentration and dissolved resin concentration of the developer, and The pre-established relationship between alkali concentration and carbonate concentration and dissolved resin concentration can be used to exert the dissolving power of CD value (critical dimension value) (line width) to a fixed value, and control the supply of developer stock solution to adjust alkali concentration.

又，專利文獻3揭示有：測定顯影液的折射率、導電率及吸光度並由此等之測定值來取得顯影液 中的碳酸系鹽類濃度之碳酸系鹽類濃度測定裝置、及具備此碳酸系鹽類濃度測定裝置與控制顯影液中的碳酸系鹽類濃度的控制部之鹼顯影液管理系統等。 In addition, Patent Document 3 discloses: a carbonate-based salt concentration measuring device that measures the refractive index, conductivity, and absorbance of a developer and obtains the concentration of carbonate-based salts in the developer from the measured values, and a device provided with the carbonic acid It is the alkali developer management system of the control unit that controls the concentration of carbonate salts in the developer, etc.

先行技術文獻Advanced technical literature 專利文獻Patent literature

專利文獻1 日本專利第2561578號公報 Patent Document 1 Japanese Patent No. 2561578

專利文獻2 日本特開2008-283162號公報 Patent Document 2 JP 2008-283162 A

專利文獻3 日本特開2011-128455號公報 Patent Document 3 JP 2011-128455 A

但是，鹼性顯影液的超音波傳播速度值、折射率值等係呈現多成分系的鹼性顯影液的液體整體的性質之特性值。呈現這樣的液體整體的性質的特性值，一般不是僅與其液體所含之特定的成分的濃度有關。呈現這樣的液體整體的性質的特性值，通常與其液體所含有的各種成分的濃度分別有關。因此，在從呈現這樣的液體整體的性質之特性值之測定值運算顯影液的成分濃度之情況中，當以某特性值僅和某特定的成分濃度有關(例如處於線性關係)而無視其他成分影響其特性值時，具有無法擁有足夠的精度來算出該特定成分的濃度之問題。 However, the ultrasonic propagation velocity value and the refractive index value of the alkaline developer are characteristic values showing the properties of the entire liquid of the multi-component alkaline developer. The characteristic value showing the properties of such a liquid as a whole is generally not only related to the concentration of a specific component contained in the liquid. The characteristic values showing the properties of the entire liquid are generally related to the concentrations of various components contained in the liquid. Therefore, in the case of calculating the component concentration of the developer from the measured value of the characteristic value showing the properties of the liquid as a whole, when a certain characteristic value is only related to a specific component concentration (for example, in a linear relationship) and other components are ignored When the characteristic value is affected, there is a problem that the concentration of the specific component cannot be calculated with sufficient accuracy.

另一方面，在以顯影液的特性值是顯影液所含之各種成分的濃度的關數而從顯影液的特性值之測定值算出各成分濃度之情況，在測定複數個特性值之 後，有必要採用用以從此等特性值之測定值算出各成分濃度之適切的運算手法。但是，適當地選擇應測定的特性值及找到從特性值之測定值可高精度地算出各成分濃度的適當的運算手法，都非常困難。因此，具有若所測定之特性值與運算手法不適當的話，則無法擁有足夠的精度算出各成分濃度之問題。 On the other hand, in the case of calculating the concentration of each component from the measured value of the characteristic value of the developer by taking the characteristic value of the developer as the correlation of the concentration of the various components contained in the developer, after measuring a plurality of characteristic values, there is It is necessary to adopt an appropriate calculation method to calculate the concentration of each component from the measured values of these characteristic values. However, it is very difficult to appropriately select the characteristic value to be measured and find an appropriate calculation method that can accurately calculate the concentration of each component from the measured value of the characteristic value. Therefore, there is a problem that if the measured characteristic value and calculation method are inappropriate, the concentration of each component cannot be calculated with sufficient accuracy.

而且，在多成分系的液體中，一般而言，某成分的濃度並非和其他成分的濃度相互獨立。在多成分系的液體中，具有所謂當某成分的濃度一變化則其他成分濃度亦同時變化的相互關係。這讓高精度的成分濃度的算出及高精度的顯影液管理更加困難。 Moreover, in a multi-component liquid, generally speaking, the concentration of a certain component is not independent of the concentration of other components. In a multi-component liquid, there is a so-called correlation that when the concentration of a certain component changes, the concentrations of other components also change at the same time. This makes the calculation of high-precision component concentration and high-precision developer management more difficult.

再加上，關於顯影液所吸收的二氧化碳的濃度(以下稱為「吸收二氧化碳濃度」。)，與其呈現良好的相關之顯影液的適當特性值未被知悉，習知係難以高精度地測定吸收二氧化碳濃度。 In addition, with regard to the concentration of carbon dioxide absorbed by the developer (hereinafter referred to as the "absorbed carbon dioxide concentration"), the appropriate characteristic value of the developer, which shows a good correlation with it, is not known, and it is difficult to measure the absorption with high accuracy in the conventional system. Carbon dioxide concentration.

又，專利文獻2中，為檢測顯影液的成分濃度，有必要事先取得顯影液的成分濃度與超音波傳播速度等的特性值之相互關係(矩陣)。然而，在此情況下，當相互關係(矩陣)不細緻時，則無法高精度地算出成分濃度。為了高精度地算出成分濃度，運算所用的顯影液的特性值與成分濃度之相互關係(矩陣)必須夠稠密。因此，越是想將成分濃度的算出精度設高，則越是要預先準備更多的試樣，且必須事先測定其成分濃度與顯影液的特性值之相互關係。預先準備這樣的稠密的相互關係(矩陣)乃係龐大的作業量，成為在實現顯影液的成分濃度之高精度測定上的問題。特別是，監視顯影液的濃度的變化在管理顯影液上是重要的。 In addition, in Patent Document 2, in order to detect the component concentration of the developer, it is necessary to obtain the correlation (matrix) between the component concentration of the developer and the characteristic values such as the ultrasonic wave propagation velocity in advance. However, in this case, when the correlation (matrix) is not detailed, the component concentration cannot be calculated with high accuracy. In order to calculate the component concentration with high accuracy, the correlation (matrix) between the characteristic value of the developer used in the calculation and the component concentration (matrix) must be sufficiently dense. Therefore, the more accurate the calculation of the component concentration is desired, the more samples must be prepared in advance, and the correlation between the component concentration and the characteristic value of the developer must be measured in advance. Preparing such a dense correlation (matrix) in advance is a huge workload, and becomes a problem in achieving high-precision measurement of the component concentration of the developer. In particular, monitoring changes in the concentration of the developer is important in managing the developer.

本發明係為解決上述諸課題而完成者。本發明之目的在於：提供一種可從多成分系的顯影液的特性值高精度地測定顯影液的成分濃度，且可在無需準備龐大數量的試樣且無需預備測定等之下分析顯影液的成分濃度，能監視顯影液的濃度之監視裝置、以及提供能更加精密管理顯影液的成分濃度的顯影液管理裝置。 The present invention was accomplished to solve the above-mentioned problems. The object of the present invention is to provide a method that can measure the component concentration of a developer with high accuracy from the characteristic values of a multi-component developer, and can analyze the developer without preparing a large number of samples and without preliminary measurement, etc. Component concentration, a monitoring device that can monitor the concentration of the developer, and a developer management device that can more precisely manage the component concentration of the developer.

用以達成前述目的之本發明係如下所示。 The present invention for achieving the aforementioned object is as follows.

(1)一種顯影液的濃度監視裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值；運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃度；及警報部，在藉前述運算部所算出之前述成分濃度中至少一者偏離所設定之管理範圍時發出警報。 (1) A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; the computing unit is based on the measurement unit The measured plurality of characteristic values are calculated by multivariate analysis to calculate the component concentration of the developer; and an alarm unit, which generates an alarm when at least one of the component concentrations calculated by the calculation unit deviates from the set management range .

(2)一種顯影液的濃度監視裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值；及運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃度，按前述成分濃度具備在藉前述運算部所算出之前述成分濃度偏離所設定之管理範圍時發出警報的警報部。 (2) A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and a computing unit based on the measuring unit The measured plurality of characteristic values are calculated by multivariate analysis to calculate the component concentration of the developer. According to the component concentration, an alarm is issued when the component concentration calculated by the calculation unit deviates from the set management range. unit.

(3)如(1)或(2)之顯影液的濃度監視裝置，其中作為警報部，至少具備以下任一者：傳送警報信號的外部輸出信號端子、發出警報音的警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子。 (3) The developer concentration monitoring device as in (1) or (2), which serves as an alarm unit at least one of the following: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, and a light spot The warning light that lights up or flashes, the display device that shows the warning, and the relay terminal that switches the contacts on and off.

(4)一種顯影液管理裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值；運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃度；警報部，在藉前述運算部所算出之前述成分濃度中至少一者偏離所設定之管理範圍時發出警報；及控制部，依據從藉前述測定部所測定之前述顯影液的複數個特性值及藉前述運算部所算出之前述顯影液的成分濃度中所選擇之管理對象項目的測定值或算出值，對設在用以輸送要被補給到前述顯影液的補充液之管路上之控制閥發出控制信號。 (4) A developer management device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; an arithmetic unit based on the measurement by the measuring unit The plurality of characteristic values are calculated by the multivariate analysis method to calculate the component concentration of the developer; the alarm unit, when at least one of the component concentrations calculated by the calculation unit deviates from the set management range; and control The part is based on the measured value or calculated value of the management target item selected from the plurality of characteristic values of the developer measured by the measuring part and the component concentration of the developer calculated by the calculating part. The control valve on the pipeline for conveying the replenishing liquid to be replenished to the aforementioned developer sends a control signal.

(5)如(4)之顯影液管理裝置，其中作為警報部，至少具備以下任一者：傳送警報信號的外部輸出信號端子、發出警報音的警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子。 (5) The developer management device as in (4), wherein as an alarm unit, at least one of the following is provided: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, and a warning lamp that lights or flashes light , The display device to display the warning, and the relay terminal to switch the opening and closing of the contact.

(6)一種顯影液管理裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值； 運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃度；及控制部，依據從藉前述測定部所測定之前述顯影液的複數個特性值及藉前述運算部所算出之前述顯影液的成分濃度中所選擇之管理對象項目的測定值或算出值，對設在用以輸送要被補給到前述顯影液的補充液之管路上之控制閥發出控制信號，按濃度而具備在藉前述運算部所算出之前述成分濃度偏離所設定之管理範圍時發出警報的警報部。 (6) A developer management device, comprising: a measuring unit that measures a plurality of characteristic values of the aforementioned developer related to the component concentration of the alkaline developer that is repeatedly used; The arithmetic unit calculates the component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit; and the control unit, based on the plural of the developer measured by the measurement unit The characteristic value and the measured value or calculated value of the management target item selected in the component concentration of the developer calculated by the arithmetic unit are set on the pipeline for conveying the replenishing liquid to be replenished to the developer The control valve emits a control signal, and is equipped with an alarm unit that issues an alarm when the concentration of the component calculated by the calculation unit deviates from the set management range according to the concentration.

(7)如(6)之顯影液管理裝置，其中作為前述警報部，至少具備以下任一者：傳送警報信號的外部輸出、發出警報音的警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子。 (7) The developer management device according to (6), wherein as the aforementioned alarm unit, at least one of the following is provided: an external output that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes light, A display device that displays warnings, and a relay terminal that switches contacts on and off.

(8)如(4)至(7)中任一項所記載之顯影液管理裝置，其中前述成分濃度是前述顯影液的鹼成分的濃度及光阻劑的濃度，前述測定部具備：第一測定構件，測定與前述顯影液的成分中至少鹼成分的濃度有關之前述顯影液的特性值；及第二測定構件，測定與前述顯影液的成分中至少溶解於前述顯影液的光阻劑的濃度有關之前述顯影液的特性值，前述運算部具備算出前述顯影液的鹼成分的濃度及光阻劑的濃度之運算塊。 (8) The developer management device according to any one of (4) to (7), wherein the component concentration is the concentration of the alkali component of the developer and the concentration of the photoresist, and the measurement unit includes: A measuring means for measuring the characteristic value of the developer related to the concentration of at least the alkali component in the components of the developer; and a second measuring means for measuring the photoresist at least dissolved in the developer in the components of the developer Regarding the characteristic value of the developer with respect to the concentration, the arithmetic unit includes an arithmetic block for calculating the concentration of the alkali component of the developer and the concentration of the photoresist.

(9)如(4)至(7)中任一項之顯影液管理裝置，其中前述成分濃度為前述顯影液的鹼成分的濃度、光阻劑的濃度及二氧化碳的濃度，前述測定部具備：第一測定構件，測定與前述顯影液的成分中至少鹼成分的濃度有關之前述顯影液的特性值；第二測定構件，測定與前述顯影液的成分中至少溶解於前述顯影液的光阻劑的濃度有關之前述顯影液的特性值；及第三測定構件，測定與前述顯影液的成分中至少前述顯影液所吸收的二氧化碳的濃度有關之前述顯影液的特性值，前述運算部具備算出前述顯影液的鹼成分的濃度、光阻劑的濃度及二氧化碳的濃度之運算塊。 (9) The developer management device according to any one of (4) to (7), wherein the component concentration is the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide, and the measurement unit includes: The first measuring means measures the characteristic value of the developer with respect to the concentration of at least the alkali component in the components of the developer; the second measuring means measures the photoresist dissolved in the developer at least among the components of the developer The characteristic value of the developer related to the concentration of the developer; and a third measuring means for measuring the characteristic value of the developer related to the concentration of at least the carbon dioxide absorbed by the developer in the components of the developer, and the arithmetic unit is equipped to calculate the A calculation block for the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide.

依據本發明，由於藉由使用了多變量分析法(例如，多元回歸分析法)的運算構件算出多成分系的鹼性顯影液的成分濃度，故與所測定的特性值和特定的成分濃度是處於既定的相關關係(例如，線性關係)算出成分濃度的習知手法相比，從受到複數個顯影液成分的影響之特性值亦可高精度地算出顯影液的成分濃度。特別是，依據本發明，可測定在習知難以測定的顯影液的吸收二氧化碳濃度。又，與事前準備複數個測定特性值和複數個成分濃度之相關關係(矩陣)而用在成分濃度的算出之手法相比，本發明中亦無需準備龐大數量的試樣並實施預備測定。且可容易地監視顯影液的濃度。 According to the present invention, since the component concentration of the multi-component alkaline developer is calculated by the arithmetic means using the multivariate analysis method (for example, the multiple regression analysis method), it is the same as the measured characteristic value and the specific component concentration. Compared with the conventional method of calculating the component concentration in a predetermined correlation (for example, a linear relationship), the component concentration of the developer can be calculated with high accuracy from the characteristic value affected by a plurality of developer components. In particular, according to the present invention, it is possible to measure the absorbed carbon dioxide concentration of a developer which is difficult to measure in the prior art. In addition, compared with the method of preparing correlations (matrices) between a plurality of measured characteristic values and a plurality of component concentrations in advance and using them for calculating component concentrations, there is no need to prepare a huge number of samples and perform preliminary measurements in the present invention. And can easily monitor the concentration of the developer.

依據本發明，由於能比習知更高精度地測定多成分系的鹼性顯影液的各成分濃度，故可比習知者還更能精確控制鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度。又，依據本發明，亦可選擇將顯影液的導電率值控制成固定的管理、將顯影液的吸光度值控制在固定的吸光度值以下的管理。 According to the present invention, since the concentration of each component of the multi-component alkaline developer can be measured with higher accuracy than the conventional one, the concentration of the alkali component, the concentration of the dissolved photoresist and the concentration of carbon dioxide absorption can be controlled more accurately than the conventional one. . Furthermore, according to the present invention, it is also possible to select management to control the conductivity value of the developer to a fixed value, and management to control the absorbance value of the developer to be below a fixed absorbance value.

A:濃度監視裝置 A: Concentration monitoring device

B:顯影製程設備 B: Development process equipment

C:補充液貯留部 C: Replenishment liquid storage part

D:循環攪拌機構 D: Circulating stirring mechanism

E:顯影液管理裝置 E: Developer management device

1:測定部 1: Measurement department

11:第一測定構件 11: The first measurement component

12:第二測定構件 12: The second measuring component

13:第三測定構件 13: The third measuring component

11a、12a、13a:測定裝置本體 11a, 12a, 13a: measuring device body

11b、12b、13b:測定探針 11b, 12b, 13b: measuring probe

14、14a、14b、14c:取樣泵 14, 14a, 14b, 14c: sampling pump

15、15a、15b、15c:取樣配管 15, 15a, 15b, 15c: sampling piping

16、16a、16b、16c:回流配管 16, 16a, 16b, 16c: return piping

17:送液泵 17: Liquid delivery pump

18:送液配管 18: Liquid delivery piping

19:廢液配管 19: Waste liquid piping

2:運算部 2: Computing Department

21:利用多變量分析法的運算塊 21: Operation block using multivariate analysis

22:利用校準曲線法的運算塊 22: Operation block using calibration curve method

23:運算控制部(例如電腦) 23: Operation control unit (e.g. computer)

3:控制部 3: Control Department

31、32、33:控制塊31, 32, 33: control block

4‧‧‧閥 4‧‧‧Valve

41~43‧‧‧控制閥 41~43‧‧‧Control valve

44、45‧‧‧閥 44、45‧‧‧valve

46、47‧‧‧加壓氣體用閥 46、47‧‧‧Valve for pressurized gas

5‧‧‧信號線 5‧‧‧Signal line

51~53‧‧‧測定數據用信號線 51~53‧‧‧Signal line for measurement data

54‧‧‧運算數據用信號線 54‧‧‧Operation data signal line

55~57‧‧‧控制信號用信號線 55~57‧‧‧Signal line for control signal

61‧‧‧顯影液貯留槽 61‧‧‧Developer storage tank

62‧‧‧溢流槽 62‧‧‧Overflow trough

63‧‧‧液面計 63‧‧‧Level Gauge

64‧‧‧顯影室罩 64‧‧‧Development chamber cover

65‧‧‧滾輪式輸送機 65‧‧‧Roller Conveyor

66‧‧‧基板 66‧‧‧Substrate

67‧‧‧顯影液噴灑頭 67‧‧‧Developer spray head

71‧‧‧廢液泵 71‧‧‧Waste pump

72、74‧‧‧循環泵 72、74‧‧‧Circulating pump

73、75‧‧‧過濾器 73、75‧‧‧Filter

8‧‧‧流體管路 8‧‧‧Fluid pipeline

80‧‧‧顯影液管路 80‧‧‧Developing solution pipeline

81、82‧‧‧補充液(顯影原液及/或新液) 用管路 81、82‧‧‧Supply solution (developing stock solution and/or new solution) pipeline

83‧‧‧純水用管路 83‧‧‧Pure water pipeline

84‧‧‧合流管路 84‧‧‧Combined pipeline

85‧‧‧循環管路 85‧‧‧Circulation pipeline

86:氮氣用管路 86: Nitrogen pipeline

9:補充液貯留槽、其他 9: Replenishment liquid storage tank, others

91、92:補充液(顯影原液及/或新液)貯留槽 91, 92: Replenisher (developing stock solution and/or new solution) storage tank

93:添加試藥 93: Add reagent

WD:警報部 WD: Alarm Department

圖1係顯示在由二個特性值測定二個成分的成分濃度之情況下的信號流動之成分濃度測定方法的流程圖。 Fig. 1 is a flowchart showing a method of measuring the component concentration of a signal flow when the component concentration of two components is measured from two characteristic values.

圖2係顯示在由三個以上的特性值測定三個成分以上的成分濃度之情況下的信號流動之成分濃度測定方法的流程圖。 Fig. 2 is a flowchart showing a component concentration measurement method of signal flow when the component concentration of three or more components is measured from three or more characteristic values.

圖3係顯示在含有與多變量分析法相異的運算手法的情況下的信號流動之成分濃度測定方法的流程圖。 Fig. 3 is a flowchart showing a method of measuring the component concentration of the signal flow when an operation method different from the multivariate analysis method is included.

圖4係測定顯影液的二個成分之濃度監視裝置的示意圖。 Figure 4 is a schematic diagram of a monitoring device for measuring the concentration of two components of a developer.

圖5係測定顯影液的三個成分之濃度監視裝置的示意圖。 Figure 5 is a schematic diagram of a monitoring device for measuring the concentration of three components of a developer.

圖6係在運算部具有利用與多變量分析法相異的運算手法的運算塊之濃度監視裝置的示意圖。 Fig. 6 is a schematic diagram of a concentration monitoring device having an arithmetic block using an arithmetic method different from the multivariate analysis method in the arithmetic section.

圖7係測定部與運算部為分開且進行線內(inline)測定的情況之濃度監視裝置的示意圖。 Fig. 7 is a schematic diagram of a concentration monitoring device when the measurement unit and the calculation unit are separated and inline measurement is performed.

圖8係測定構件為由本體與探針部構成的情況之濃度監視裝置的示意圖。 Fig. 8 is a schematic diagram of a concentration monitoring device when the measuring member is composed of a main body and a probe part.

圖9係並列地具備測定構件之濃度監視裝置的示意圖。 Fig. 9 is a schematic diagram of a concentration monitoring device provided with measuring means in parallel.

圖10係具備需要添加藥劑的測定裝置的情況之濃度監視裝置的示意圖。 Fig. 10 is a schematic diagram of a concentration monitoring device in a case where a measurement device that requires drug addition is provided.

圖11係將濃度監視裝置應用於顯影液管理裝置之示意圖。 Figure 11 is a schematic diagram of applying a concentration monitoring device to a developer management device.

圖12係用以呈現濃度監視裝置的應用事例之示意圖。 Fig. 12 is a schematic diagram showing an application example of the concentration monitoring device.

圖13係藉由成分濃度管理顯影液的二個成分之顯影液管理方法的流程圖。 FIG. 13 is a flowchart of a developer management method for managing two components of a developer by component concentration.

圖14係顯影液的二個成分中的一者藉由成分濃度而另一者藉由特性值作管理之顯影液管理方法的流程圖。 14 is a flowchart of a developer management method in which one of the two components of the developer is managed by the component concentration and the other is managed by the characteristic value.

圖15係顯影液的三個成分藉由成分濃度作管理之顯影液管理方法的流程圖。 FIG. 15 is a flowchart of a developer management method in which the three components of the developer are managed by the component concentration.

圖16係顯影液的三個成分中的一個藉由特性值而其他二個藉由成分濃度作管理之顯影液管理方法的流程圖。 FIG. 16 is a flowchart of a developer management method in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration.

圖17係顯影液的三個成分中的二個藉由特性值而另一個藉由成分濃度作管理之顯影液管理方法的流程圖。 FIG. 17 is a flowchart of a developer management method in which two of the three components of the developer are managed by characteristic values and the other is managed by the component concentration.

圖18係用以說明本發明的顯影液管理裝置之顯影製程的示意圖。 FIG. 18 is a schematic diagram for explaining the development process of the developer management device of the present invention.

圖19係對裝置外的控制閥進行控制之顯影液管理裝置的示意圖。Figure 19 is a schematic diagram of a developer management device that controls a control valve outside the device.

圖20係具備一併擁有運算功能和控制功能的運算控制部之顯影液管理裝置的示意圖。 Fig. 20 is a schematic diagram of a developer management device provided with an arithmetic control unit having arithmetic and control functions.

圖21係管理顯影液的二個成分之顯影液管理裝置的示意圖。 Figure 21 is a schematic diagram of a developer management device that manages two components of a developer.

圖22係顯影液的二個成分藉由成分濃度作管理之顯影液管理裝置的示意圖。 Fig. 22 is a schematic diagram of a developer management device in which two components of a developer are managed by component concentrations.

圖23係顯影液的三個成分中的二個藉由特性值而另一個藉由成分濃度作管理之顯影液管理裝置的示意圖。 FIG. 23 is a schematic diagram of a developer management device in which two of the three components of the developer are managed by characteristic values and the other by the component concentration.

圖24係顯影液的三個成分中的一個藉由特性值而另二個藉由成分濃度作管理之顯影液管理裝置的示意圖。 FIG. 24 is a schematic diagram of a developer management device in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration.

圖25係顯影液的三個成分藉由成分濃度作管理之顯影液管理裝置的示意圖。 FIG. 25 is a schematic diagram of a developer management device in which three components of a developer are managed by component concentrations.

以下，一邊參照適當圖式一邊就本發明的較佳實施形態詳細說明。但，此等實施形態中所記載的裝置等之形狀、大小、尺寸比、其相對配置等，只要未有特定的記載，即不應僅限定於圖示在本發明範圍中的內容，只不過是作為單純說明例作示意性圖示而已。 Hereinafter, the preferred embodiments of the present invention will be described in detail while referring to appropriate drawings. However, the shapes, sizes, size ratios, relative arrangements, etc. of the devices and the like described in these embodiments should not be limited to the content shown in the scope of the present invention as long as there is no specific description. It is a schematic illustration as a purely illustrative example.

又，在以下的說明中，作為顯影液的具體例，適當地使用在半導體、液晶面板基板等之製造製程中主要使用的2.38%氫氧化四甲銨(tetramethyl ammonium hydroxide)水溶液(以下，將氫氧化四甲銨稱為TMAH。)來作說明。但是，適用本發明的顯影液並非受 此所限定者。作為可適用本發明的顯影液的濃度監視裝置、顯影液管理裝置等之其他的顯影液之例子，可舉出氫氧化鉀、氫氧化鈉、磷酸鈉、矽酸鈉等的無機化合物之水溶液和氫氧化三甲基單乙醇胺(trimethyl monoethanol ammonium hydroxide)(choline：膽鹼)等的有機化合物水溶液。 In addition, in the following description, as a specific example of the developer, a 2.38% tetramethyl ammonium hydroxide aqueous solution (hereinafter referred to as hydrogen), which is mainly used in the manufacturing process of semiconductors and liquid crystal panel substrates, is suitably used. Tetramethylammonium oxide is called TMAH.) for illustration. However, the developer to which the present invention is applied is not limited by this. Examples of other developer solutions that can be applied to the developer concentration monitoring device and developer management device of the present invention include aqueous solutions of inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, and sodium silicate. An aqueous solution of an organic compound such as trimethyl monoethanol ammonium hydroxide (choline).

又，多變量分析法(例如多元回歸分析法)在成分濃度的算出之際，成分濃度未取決於是哪種單位的濃度，但在以下的說明中，鹼成分濃度、溶解光阻劑濃度、吸收二氧化碳濃度等的成分濃度係採用重量百分率濃度(wt%)的濃度。「溶解光阻劑濃度」意指將溶解的光阻劑作為光阻劑的量換算之情況的濃度，「吸收二氧化碳濃度」意指將所吸收的二氧化碳作為二氧化碳的量換算之情況的濃度。 In addition, the multivariate analysis method (such as the multiple regression analysis method) does not depend on the concentration of the component when calculating the component concentration. However, in the following description, the alkali component concentration, dissolved photoresist concentration, absorption The concentration of the components such as carbon dioxide concentration is the concentration by weight percentage concentration (wt%). The "dissolved photoresist concentration" means the concentration when the dissolved photoresist is converted into the amount of the photoresist, and the "absorbed carbon dioxide concentration" means the concentration when the absorbed carbon dioxide is converted into the amount of carbon dioxide.

在顯影處理製程中，透過顯影液溶解曝光處理後的光阻劑膜之不要部分而進行顯影。溶解於顯影液的光阻劑會在與顯影液的鹼成分之間產生光阻劑鹽。因此，若未將顯影液適當地管理，則伴隨著顯影處理進行，顯影液就會因具有顯影活性的鹼成分被消耗而劣化，使得顯影性能持續惡化。同時，溶解於顯影液的光阻劑係以與鹼成分生成光阻劑鹽的形式而逐漸累積。 In the development process, the unnecessary part of the photoresist film after the exposure treatment is dissolved through the developer solution for development. The photoresist dissolved in the developer solution generates a photoresist salt with the alkali component of the developer solution. Therefore, if the developer is not properly managed, as the development process progresses, the developer will be degraded due to the consumption of alkali components having development activity, and the development performance will continue to deteriorate. At the same time, the photoresist dissolved in the developer is gradually accumulated in the form of a photoresist salt with the alkali component.

溶解於顯影液的光阻劑係在顯影液中呈現界面活性作用。因此，溶解於顯影液的光阻劑係提高對於供作顯影處理的光阻劑膜的顯影液之浸潤性(wettability)，並改善顯影液與光阻劑膜之親和性。因 此，在適度地含有光阻劑的顯影液中，顯影液亦遍佈在光阻劑膜之微細的凹部內，可對具有微細的凹凸之光阻劑膜良好地實施顯影處理。 The photoresist dissolved in the developing solution exhibits interfacial activity in the developing solution. Therefore, the photoresist dissolved in the developing solution improves the wettability of the developing solution to the photoresist film used for development, and improves the affinity between the developing solution and the photoresist film. Therefore, in the developer containing a moderate amount of photoresist, the developer also spreads in the fine recesses of the photoresist film, and the photoresist film with fine irregularities can be well developed.

又，在近年來的顯影處理中，伴隨著基板大型化，由於大量的顯影液成為被重複使用，故顯影液暴露在空氣的機會增加。然而，當鹼性顯影液暴露於空氣時會吸收空氣中的二氧化碳。所吸收的二氧化碳會與顯影液的鹼成分之間生成碳酸鹽。因此，若未將顯影液適當地管理，則顯影液中具有顯影活性的鹼成分便會被所吸收之二氧化碳消耗並減少。同時，顯影液中所吸收的二氧化碳是以與鹼成分生成的碳酸鹽之形式而逐漸累積。 In addition, in recent development processes, along with the enlargement of the substrate, a large amount of the developer has been reused, so the chance of the developer being exposed to the air has increased. However, when the alkaline developer is exposed to the air, it absorbs carbon dioxide in the air. Carbonate is formed between the absorbed carbon dioxide and the alkali component of the developer. Therefore, if the developer is not properly managed, the alkali components with development activity in the developer will be consumed and reduced by the absorbed carbon dioxide. At the same time, the carbon dioxide absorbed in the developer is gradually accumulated in the form of carbonate formed with alkali components.

顯影液中的碳酸鹽由於在顯影液中呈現鹼性，故具有顯影作用。在例如2.38%TMAH水溶液的情況，若二氧化碳在顯影液中大約為0.4wt%程度以下，則可顯影。 The carbonate in the developer has a developing effect because it is alkaline in the developer. For example, in the case of a 2.38% TMAH aqueous solution, if the carbon dioxide in the developer is about 0.4 wt% or less, the development can be performed.

如上述，不同於會使顯影處理的顯影活性失去活性的過往認知，顯影液中所溶解的光阻劑和所吸收的二氧化碳實際上是有助於顯影液的顯影性能的。因此，所必須進行的乃係在容許顯影液中溶解並存在有溶解光阻劑和吸收二氧化碳下，將溶解光阻劑和吸收二氧化碳維持管理在最佳濃度的顯影液管理，而非將溶解光阻劑和吸收二氧化碳完全移除的顯影液管理。 As mentioned above, unlike the previous recognition that the development activity of the development process will be inactivated, the photoresist dissolved in the developer and the carbon dioxide absorbed actually contribute to the development performance of the developer. Therefore, what must be done is the developer management that allows the dissolved photoresist and carbon dioxide to be dissolved in the developer solution and the presence of dissolved photoresist and absorbs carbon dioxide, and maintains management of the dissolved photoresist and carbon dioxide absorption at the optimal concentration, rather than the management of the dissolved light. Developer management for complete removal of resist and carbon dioxide absorption.

再者，產生於顯影液中的光阻劑鹽、碳酸鹽等其一部分會解離而生成光阻劑離子、碳酸離子、碳 酸氫離子等各種游離離子。而且，此等游離離子會以各種貢獻率(contributing rate)影響顯影液的導電率。 Furthermore, part of the photoresist salt, carbonate, etc. generated in the developer is dissociated to generate various free ions such as photoresist ions, carbonate ions, and hydrogen carbonate ions. Moreover, these free ions will affect the conductivity of the developer with various contribution rates.

習知的鹼性顯影液的成分濃度分析為，利用顯影液的鹼成分濃度和顯影液的導電率值具有良好的線性關係，及顯影液的溶解光阻劑濃度具有和顯影液的吸光度值良好的線性關係者(以下將其稱為「習知方法」。)。在習知的顯影製程中所要求的顯影液管理精度亦有二氧化碳的吸收量還不多的情況，利用此分析手法已可充分實現。 The analysis of the component concentration of the conventional alkaline developer is that the alkali component concentration of the developer and the conductivity value of the developer have a good linear relationship, and the dissolved photoresist concentration of the developer has a good absorbance value. (Hereinafter referred to as "the conventional method"). The developer management precision required in the conventional development process may also have a low carbon dioxide absorption, which can be fully realized by this analysis method.

顯影液的導電率值為取決於顯影液中所含的離子等帶電粒子數及其電荷量的物性值。如上所述，顯影液中不僅存在有鹼成分，也存在有溶解於顯影液的光阻劑或來自顯影液所吸收的二氧化碳的各種游離離子。因而，為了提高成分濃度的分析精度，有必要使用亦加入有此等游離離子對顯影液之導電率值的影響在內的運算手法。 The electrical conductivity value of the developer is a physical property value that depends on the number of charged particles such as ions contained in the developer and the amount of charge. As described above, there are not only alkali components in the developer, but also photoresist dissolved in the developer or various free ions derived from carbon dioxide absorbed by the developer. Therefore, in order to improve the analysis accuracy of the component concentration, it is necessary to use an algorithm that also includes the influence of such free ions on the conductivity value of the developer.

顯影液的吸光度值係為和選擇性吸收其測定波長之光的特定成分的濃度具有線性關係的物性值(Lambert-Beer law，朗伯-比爾定律)。但是，多成分系中，雖因測定波長而有其程度不同，但通常其他成分的吸光光譜會和對象成分的吸光光譜重疊。因此，為了提高成分濃度的分析精度，有必要使用不僅是溶解於顯影液的光阻劑，且亦加入有其他成分對顯影液之吸光度值的影響在內的運算手法。 The absorbance value of the developer is a physical property value (Lambert-Beer law, Lambert-Beer law) that has a linear relationship with the concentration of a specific component that selectively absorbs the light of its measurement wavelength. However, in a multi-component system, although the degree of difference varies depending on the measurement wavelength, the absorption spectrum of other components generally overlaps the absorption spectrum of the target component. Therefore, in order to improve the analysis accuracy of the component concentration, it is necessary to use not only the photoresist dissolved in the developer, but also the influence of other components on the absorbance value of the developer.

發明人針對此等各點，持續精心研究的結果，發現若於運算手法上使用多變量分析法(例如，多元回歸分析法)，則從使用習知方法的情況，可高精度地算出顯影液的各成分的濃度、及可進行習知難以測定的吸收二氧化碳濃度。又，發明人發現若使藉多變量分析法(例如，多元回歸分析法)所算出之顯影液的成分濃度，則能將顯影液的溶解光阻劑濃度、吸收二氧化碳濃度等維持管理在良好的狀態。 The inventors have continued to carefully study these points and found that if a multivariate analysis method (for example, multiple regression analysis) is used in the calculation method, the developer can be calculated with high accuracy based on the conventional method. The concentration of each component, and the concentration of carbon dioxide absorbed can be measured, which is difficult to measure conventionally. In addition, the inventor found that if the component concentration of the developer calculated by a multivariate analysis method (for example, a multiple regression analysis method) is used, the dissolved photoresist concentration and the absorbed carbon dioxide concentration of the developer can be maintained and managed in a good status.

發明人係假設進行2.38%TMAH水溶液的管理之情況，調製了使鹼成分濃度、溶解光阻劑濃度、吸收二氧化碳濃度有多種變化而得的TMAH水溶液作為模擬顯影液試樣。發明人由針對此等模擬顯影液試樣所測定之各種特性值，藉由多元回歸分析法進行了求得其成分濃度之實驗。以下，說明利用多元回歸分析法之一般的運算手法，之後，依據發明人所進行的實驗，針對使用多元回歸分析法之顯影液的成分濃度的運算手法作說明。 The inventor assumed the management of a 2.38% TMAH aqueous solution, and prepared a TMAH aqueous solution obtained by varying the alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration as a simulated developer sample. The inventors conducted experiments to obtain the component concentrations of the various characteristic values measured for these simulated developer samples by multiple regression analysis. Hereinafter, the general calculation method using the multiple regression analysis method will be explained, and then, based on the experiment conducted by the inventor, the calculation method of the component concentration of the developer using the multiple regression analysis method will be explained.

多元回歸分析係由校正與預測的二階段組成。n成分系的多元回歸分析中，係假設準備m個校正標準溶液。將存在於第i個溶液中的第j個成分的濃度以Cij表示。此處，i=1至m、j=1至n。針對m個標準溶液，分別測定p個特性值(例如，某波長的吸光度或者導電率等之物性值)Aik(k=1至p)。濃度數據與特性數據可分別彙整顯示成矩陣的形式(C,A)。 The multiple regression analysis system consists of two stages of correction and prediction. In the multiple regression analysis of the n-component system, it is assumed that m calibration standard solutions are prepared. The concentration of the j-th component present in the i-th solution is represented by C ij . Here, i=1 to m, j=1 to n. For m standard solutions, respectively measure p characteristic values (for example, physical property values such as absorbance or conductivity at a certain wavelength) A ik (k=1 to p). Concentration data and characteristic data can be aggregated and displayed in matrix form (C, A).

Figure 106141770-A0202-12-0016-1
Figure 106141770-A0202-12-0016-1

使此等矩陣賦予關係的矩陣稱為校正矩陣，在此係以記號S(Skj；k=1至p、j=1至n)表示。 The matrix that gives these matrices a relationship is called a correction matrix, and is represented by the notation S (S kj ; k=1 to p, j=1 to n) here.

數學式2 C=A．S Mathematical formula 2 C=A. S

藉矩陣運算從已知的C與A(A的內容係即使非為同質的測定值而混入有異質的測定值亦無妨。例如，導電率、吸光度及密度。)運算算出S的情況係為校正階段。此時，必須為p≧n，且m≧np。因S的各要素皆為未知數，故以m>np為佳。在此情況中，係以下列方式進行最小平方運算。 Matrix calculations are used to calculate S from the known C and A (even if the content of A is not a homogeneous measurement value but mixed with a heterogeneous measurement value. For example, conductivity, absorbance, and density.) The calculation of S is a correction stage. At this time, it must be p≧n and m≧np. Since each element of S is unknown, m>np is better. In this case, the least square operation is performed in the following manner.

Figure 106141770-A0202-12-0016-2
Figure 106141770-A0202-12-0016-2

此處，上標的T意指轉置矩陣，上標的-1則為逆矩陣。 Here, the superscript T means the transposed matrix, and the superscript -1 means the inverse matrix.

針對未知濃度的試料液測定p個特性值，若設此等特性值為Au(Auk；k=1至p)，則對此等特性值乘以S即可獲得應求取的濃度Cu(Cuj；j=1至n)。 Measure p characteristic values for a sample solution of unknown concentration. If these characteristic values are set to Au(Au k ; k=1 to p), then these characteristic values can be multiplied by S to obtain the desired concentration Cu( Cu j ; j=1 to n).

數學式4 Cu=Au．S Mathematical formula 4 Cu=Au. S

此乃預測階段。 This is the forecast stage.

發明人係將使用過的鹼性顯影液(2.38%TMAH水溶液)視為由鹼成分、溶解光阻劑及吸收二氧化碳等3個成分所組成之多成分系(n=3)，從作為該顯影液的特性值之3個物性值(p=3)、亦即從顯影液的導電率值、特定波長中的吸光度值及密度值，藉由上述多元回歸分析法進行了算出各成分濃度之實驗。發明人係以2.38%TMAH水溶液作為顯影液的基本組成，調製了使鹼成分濃度(TMAH濃度)、溶解光阻劑濃度及吸收二氧化碳濃度有多種變化的11個校正標準溶液(m=11，滿足p≧n且m>np)。 The inventor considers the used alkaline developer (2.38% TMAH aqueous solution) as a multi-component system (n=3) composed of three components: alkali component, dissolved photoresist, and carbon dioxide absorption. Three physical property values (p=3) of the characteristic value of the liquid, that is, from the conductivity value of the developer, the absorbance value at a specific wavelength, and the density value, the experiment was performed to calculate the concentration of each component by the above-mentioned multiple regression analysis method . The inventors used 2.38% TMAH aqueous solution as the basic composition of the developer, and prepared 11 calibration standard solutions (m=11, satisfying various changes in alkali component concentration (TMAH concentration), dissolved photoresist concentration, and absorbed carbon dioxide concentration) p≧n and m>np).

實驗係針對11個校正標準溶液，測定導電率值、波長λ=560nm中的吸光度值及密度值作為顯影液的特性值，藉由線形多元回歸分析(Multiple Linear Regression-Inverse Least Squares；MLR-ILS)運算各成分濃度。 In the experiment, the conductivity value, absorbance value and density value in the wavelength λ=560nm were measured for 11 calibration standard solutions as the characteristic value of the developer. By linear multiple regression analysis (Multiple Linear Regression-Inverse Least Squares; MLR-ILS ) Calculate the concentration of each component.

關於測定的方式，係將校正標準溶液的溫度調整至25.0℃，再進行。溫度調整係為將裝有校正標準溶液的瓶子(bottle)長時間浸漬在溫度被管理在25℃附近的恆溫水槽，由此進行取樣，然後於即將進行測定之前利用溫度控制器再度設為25.0℃。導電率計係採用本公司製造的導電率計。使用經施行鉑黑處理之本公司製造的導電率流通槽作了測定。導電率計被輸入另外藉校正作業所確認之導電率流通槽的槽常數(cell constant)。吸光光度計亦採用了本公司製品。吸光光度計係具備有波長λ=560nm的光源部和測光部及玻璃流通 槽。密度測定係使用密度計，該密度計係採用從將U字管流通槽激勵而測定之固有振動頻率求取密度之固有振動法的密度計。所測得之導電率值、吸光度值及密度值的單位分別為mS/cm、Abs.(Absorbance)及g/cm3。 Regarding the method of measurement, adjust the temperature of the calibration standard solution to 25.0°C before proceeding. The temperature adjustment system is to immerse a bottle containing a calibration standard solution for a long time in a constant temperature water tank whose temperature is controlled to be around 25°C, to sample, and then set it to 25.0°C with a temperature controller immediately before the measurement. . The conductivity meter is made by our company. The measurement was performed using a conductivity flow cell manufactured by our company that has been subjected to platinum black treatment. The conductivity meter is inputted with the cell constant of the conductivity flow cell that is additionally confirmed by calibration. The company's products are also used in the absorbance photometer. The absorbance photometer is equipped with a light source unit with a wavelength of λ=560nm, a photometric unit, and a glass flow cell. Density measurement uses a densitometer that uses the natural vibration method to obtain density from the natural vibration frequency measured by exciting the U-tube flow groove. The units of the measured conductivity value, absorbance value and density value are mS/cm, Abs. (Absorbance) and g/cm 3 respectively .

關於運算所採用的手法，係利用將11個校正標準溶液中的一個作為未知試料，再以剩餘的10個標準求取校正矩陣，算出所假設的未知試料的濃度，再與已知的值(藉由其他正確的分析手法所測定之濃度值、重量調製值)作比較的手法(留一交叉驗證法；Leave-One-Out法)。 Regarding the calculation method, one of the 11 calibration standard solutions is used as an unknown sample, and the remaining 10 standards are used to obtain the calibration matrix to calculate the assumed concentration of the unknown sample, and then compare it with the known value ( The method of comparison (Leave-One-Out method; Leave-One-Out method) is used to compare the concentration value and weight modulation value measured by other correct analysis methods.

將進行了MLR-ILS計算之結果顯示於表1。 The results of MLR-ILS calculations are shown in Table 1.

Figure 106141770-A0202-12-0018-28
Figure 106141770-A0202-12-0018-28

在進行MLR-ILS計算時，有鑒於TMAH水溶液是強鹼性且容易因吸收二氧化碳劣化，關於運算所用的濃度矩陣，係使用另以可正確地分析鹼成分濃度、吸收二氧化碳濃度等之滴定分析法將校正標準溶液作測定而得的值。惟，關於溶解光阻劑濃度，係使用重量調製值。 When calculating MLR-ILS, considering that the TMAH aqueous solution is strongly alkaline and easily degraded by carbon dioxide absorption, the concentration matrix used in the calculation is based on another titration analysis method that can accurately analyze the concentration of alkali components and the concentration of carbon dioxide absorbed. The value obtained by measuring the calibration standard solution. However, regarding the dissolved photoresist concentration, the weight modulation value is used.

關於滴定方式，係將鹽酸設為滴定試藥的中和滴定。作為滴定裝置，使用了三菱化學Analytech公司製造的自動滴定裝置GT-200。 Regarding the titration method, the neutralization titration using hydrochloric acid as the titration reagent. As the titration device, an automatic titration device GT-200 manufactured by Mitsubishi Chemical Analytech was used.

以下，將濃度矩陣顯示於表2。 Below, the concentration matrix is shown in Table 2.

Figure 106141770-A0202-12-0019-29
Figure 106141770-A0202-12-0019-29

將此時之校正標準溶液的物性值之測定結果顯示於表3。吸光度的欄位為波長λ=560nm中之吸光度值(光路長d=10mm)。 The measurement results of the physical properties of the calibration standard solution at this time are shown in Table 3. The absorbance column is the absorbance value in the wavelength λ=560nm (optical path length d=10mm).

Figure 106141770-A0202-12-0019-30
Figure 106141770-A0202-12-0019-30

將校正矩陣顯示於表4。 The correction matrix is shown in Table 4.

Figure 106141770-A0202-12-0020-31
Figure 106141770-A0202-12-0020-31

表5呈現表2的濃度測定值與表1的MLR-ILS計算值之比較。 Table 5 presents the comparison between the measured concentration values in Table 2 and the calculated values of MLR-ILS in Table 1.

Figure 106141770-A0202-12-0020-32
Figure 106141770-A0202-12-0020-32

如表5所示，藉由多元回歸分析法所求得之TMAH濃度、溶解光阻劑濃度及吸收二氧化碳濃度，均成為與藉由滴定分析所測定之TMAH濃度、吸收二氧化碳濃度及從調整重量等所求得之溶解光阻劑濃度相當近似的值。 As shown in Table 5, the TMAH concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration obtained by the multiple regression analysis method are all compared with the TMAH concentration, absorbed carbon dioxide concentration and adjusted weight determined by titration analysis. The obtained dissolved photoresist concentration is quite approximate.

如此，理解到透過測定鹼性顯影液的導電率、特定波長中之吸光度、及密度，使用多變量分析法(例如，多元回歸分析法)，便可測定顯影液的鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度。 In this way, it is understood that by measuring the conductivity of the alkaline developer, the absorbance at a specific wavelength, and the density, the use of multivariate analysis methods (for example, multiple regression analysis) can determine the alkali component concentration of the developer and the dissolved photoresist Concentration and absorption of carbon dioxide.

多變量分析法(例如，多元回歸分析法)在運算並求取複數個成分的濃度有很好的效果。測定顯影液的複數個特性值a、b、c、…，再從此等測定值可藉由多變量分析法(例如，多元回歸分析法)求取成分濃度A、B、C、…。此時，針對所要求取的成分濃度，至少與此成分濃度有關之特性值是必須有至少一個經測定並被用在運算上。 Multivariate analysis (for example, multiple regression analysis) has a good effect in calculating and calculating the concentration of multiple components. A plurality of characteristic values a, b, c, ... of the developer are measured, and from these measured values, the component concentrations A, B, C, ... can be obtained by a multivariate analysis method (for example, a multiple regression analysis method). At this time, for the required component concentration, at least one characteristic value related to the component concentration must be measured and used in the calculation.

此處，所謂與成分濃度「有關」的顯影液特性值，係指其特性值和其成分濃度有關係，特性值會隨著該成分濃度的變化而改變的關係。例如，顯影液之成分濃度中，所謂至少和成分濃度A有關的顯影液特性值a，係指欲利用以成分濃度為變數的函數求取特性值a時，其中一變數至少要包含成分濃度A。特性值a可僅為成分濃度A的函數，但通常除了成分濃度A之外，還形成為以成分濃度B或C等為變數的多變數函數時，使用多變量分析法(例如，多元回歸分析法)的意義較大。 Here, the so-called developer characteristic value "related" to the component concentration means that the characteristic value is related to the component concentration, and the characteristic value changes with the change of the component concentration. For example, in the component concentration of the developer, the so-called developer characteristic value a that is at least related to the component concentration A means that when the characteristic value a is to be obtained using a function with the component concentration as a variable, one of the variables must include at least the component concentration A . The characteristic value a can only be a function of the component concentration A, but usually in addition to the component concentration A, when it is also formed as a multivariate function with component concentration B or C as a variable, a multivariate analysis method (for example, multiple regression analysis Law) is of greater significance.

再者，成分濃度係為表示其成分相對於整體之相對量的程度。像重複使用的顯影液之類的成分會隨時間而增減的混合液的成分濃度，無法以其成分單獨決定，通常是成為其他成分之濃度的函數。因此，顯影液之特性值和成分濃度的關係，有很多難以用平面圖表(graph)顯示的情況。在這樣的情況下，使用校準曲線的運算法等並無法從顯影液的特性值算出成分濃度。 In addition, the component concentration means the degree of the relative amount of the component to the whole. The component concentration of the mixed solution whose components such as the repeatedly used developer increase or decrease over time cannot be determined by its components alone, and is usually a function of the concentration of other components. Therefore, the relationship between the characteristic value of the developer and the component concentration is difficult to display with a graph. In such a case, it is impossible to calculate the component concentration from the characteristic value of the developer using the calculation method of the calibration curve.

然而，若依據多變量分析法(例如，多元回歸分析法)，則只要收集到一組和想要算出的成分濃度有 關的複數個特性值的測定值，將該些測定值使用於運算，即可算出一組成分濃度。即使是在習知的見解下看來是難以測定的成分濃度，以利用多變量分析法(例如，多元回歸分析法)的成分濃度測定，亦可獲得透過測定特性值能測定成分濃度之顯著效果。 However, if it is based on a multivariate analysis method (for example, multiple regression analysis), you only need to collect a set of measured values of a plurality of characteristic values related to the component concentration you want to calculate, and use these measured values in the calculation, that is Can calculate the concentration of a group of ingredients. Even if the concentration of the component is difficult to be measured under the conventional knowledge, the measurement of the component concentration using a multivariate analysis method (for example, multiple regression analysis) can obtain a significant effect of measuring the component concentration by measuring the characteristic value. .

如同上述，依據本發明的運算手法，可依據顯影液的特性值(例如，導電率、特定波長中之吸光度、及密度)之測定值算出顯影液的鹼成分濃度、溶解光阻劑濃度、及吸收二氧化碳濃度。依據本發明的運算手法，相較於習知方法，可以更高精度算出各成分濃度。 As mentioned above, according to the algorithm of the present invention, the alkali component concentration of the developer, the dissolved photoresist concentration, and the measured values of the characteristic values of the developer (for example, conductivity, absorbance at a specific wavelength, and density) can be calculated Absorb the concentration of carbon dioxide. According to the calculation method of the present invention, the concentration of each component can be calculated with higher accuracy than the conventional method.

又，本發明中由於使用多變量分析法(例如，多元回歸分析法)，故在算出顯影液的成分濃度的運算上亦能採用和顯影液的特定的成分濃度無線性關係的顯影液的特性值。 In addition, in the present invention, since a multivariate analysis method (for example, a multiple regression analysis method) is used, it is also possible to use the characteristics of the developer that are wirelessly related to the specific component concentration of the developer in the calculation to calculate the component concentration of the developer. value.

又，依據本發明，並不需要專利文獻2的發明中為必要之可進行高精度測定用的非常多數的試樣之準備和預備測定。(如前述的實驗例，若為成分數n=3的顯影液，則令進行測定之特性值的個數p=3，滿足m≧np的試樣數p(例如p=11個試樣)來進行測定即足夠。若為成分數n=2，則試樣數亦可更少。) In addition, according to the present invention, the preparation and preliminary measurement of a very large number of samples for high-precision measurement are not required in the invention of Patent Document 2. (As in the previous experimental example, if it is a developer with the number of components n=3, let the number of characteristic values to be measured p=3, and the number of samples p satisfying m≧np (for example, p=11 samples) It is sufficient to perform the measurement. If the number of components is n=2, the number of samples may be smaller.)

再者，本發明由於使用多變量分析法(例如，多元回歸分析法)，故可高精度地算出在習知難以測定之顯影液的吸收二氧化碳濃度。 Furthermore, since the present invention uses a multivariate analysis method (for example, a multiple regression analysis method), it is possible to accurately calculate the absorbed carbon dioxide concentration of the developer, which is difficult to measure in the prior art.

其次，針對具體的實施例，一邊參照圖面一邊作說明。在以下的實施例中，特性值a、b、c、…、 成分濃度A、B、C、…等，適當地使用字母作說明。為了能更具體的理解，特性值a、b、c、…係分別重新理解成導電率、特定波長(例如λ=560nm)中的吸光度、密度、…等，且成分濃度A、B、C、…係分別重新理解成鹼成分濃度、溶解光阻劑濃度、吸收二氧化碳濃度、…等即可。 Next, specific embodiments will be described with reference to the drawings. In the following examples, the characteristic values a, b, c,..., and the component concentrations A, B, C,..., etc., are described using letters as appropriate. In order to be more specific, the characteristic values a, b, c, ... are re-understood as conductivity, absorbance at a specific wavelength (for example, λ=560nm), density, ..., etc., and component concentrations A, B, C, …Are re-understood as alkali component concentration, dissolved photoresist concentration, carbon dioxide absorption concentration, etc.

其中，將特性值a、b、c設為導電率、特定波長(例如λ=560nm)中的吸光度及密度等，終究不過是依本發明算出顯影液的鹼成分濃度、溶解光阻劑濃度、吸收二氧化碳濃度等之情況下的最佳特性值之組合的例示而已，但不受此所限。特性值a、b、c、…係可因應成分濃度A、B、C、…選擇各種組合。作為可採用的特性值，例如，可舉出顯影液的導電率、吸光度、超音波傳播速度、折射率、密度、滴定終點、pH等。由於亦有在顯影液含有各種添加材之情況，所以在成分濃度中除了上述三個成分以外亦可含有添加劑濃度等。 Among them, setting the characteristic values a, b, and c as electrical conductivity, absorbance and density at a specific wavelength (for example, λ=560nm), etc., is nothing more than calculating the alkali component concentration of the developer, the dissolved photoresist concentration, etc. according to the present invention. The combination of optimal characteristic values in the case of absorbing carbon dioxide concentration etc. is only an example, but it is not limited to this. The characteristic values a, b, c,... can be selected in various combinations according to the component concentrations A, B, C,... Usable characteristic values include, for example, the conductivity, absorbance, ultrasonic propagation velocity, refractive index, density, titration end point, pH, etc. of the developer. Since there are cases where various additives are contained in the developer, the concentration of additives may be contained in addition to the above three components in the component concentration.

在測定顯影液的鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度以管理顯影液之情況，適合以導電率、特定波長中之吸光度、密度的組合作為特性值。測定吸光度之特定波長係以採用可視區域為宜，較佳為360~600nm的波長區域之特定波長，更佳為波長λ=480nm或560nm。此乃係在顯影液的吸收二氧化碳濃度較少且其經時變化和緩時，顯影液的導電率係和鹼成分濃度處於較良好的線性關係，顯影液的特定波長(例如λ=560nm)中之吸光度和溶解光阻劑濃度處於較良好的線性關係之緣故。此外，較佳為亦能採用導電率、特定波 長中之吸光度及超音波傳播速度的組合、導電率、特定波長中之吸光度及折射率的組合等。 When measuring the alkali component concentration, dissolved photoresist concentration, and carbon dioxide absorption concentration of the developer to manage the developer, it is suitable to use the combination of conductivity, absorbance at a specific wavelength, and density as characteristic values. The specific wavelength for measuring absorbance is preferably in the visible region, preferably the specific wavelength in the wavelength region of 360 to 600 nm, and more preferably the wavelength λ=480 nm or 560 nm. This is when the concentration of carbon dioxide absorbed by the developer is small and its change over time is gentle, the conductivity of the developer and the concentration of the alkali component are in a good linear relationship, and the developer’s specific wavelength (for example, λ=560nm) The absorbance and the dissolved photoresist concentration are in a relatively good linear relationship. In addition, it is preferable that the combination of conductivity, absorbance at a specific wavelength and ultrasonic propagation velocity, conductivity, combination of absorbance at a specific wavelength and refractive index, etc. can also be used.

以下要說明的第一到第三實施形態係有關本發明的顯影液的成分濃度測定方法。 The first to third embodiments described below relate to the method of measuring the component concentration of the developer of the present invention.

圖1係顯示在從顯影液的二個特性值測定顯影液的二個成分之成分濃度的情況的信號之流動的本實施形態的成分濃度測定方法的流程圖。 FIG. 1 is a flowchart showing the flow of a signal when the component concentration of two components of the developer is measured from two characteristic values of the developer.

在本實施形態的成分濃度運算方法中，首先，於測定顯影液的特性值a、b的步驟中，取得各個測定值am與bm。所取得之測定值am與bm被送到運算步驟。其次，運算步驟係接收測定值am與bm，使用此等，藉由多變量分析法(例如，多元回歸分析法)算出成分濃度A、B。如此，測定成分濃度A、B。又，若重複此流程，則可連續測定顯影液的成分濃度A、B。 In the component concentration calculation method of this embodiment, first, in the step of measuring the characteristic values a and b of the developer, the respective measured values a m and b m are obtained . The obtained measured values a m and b m are sent to the calculation step. Next, the calculation step is to receive the measured values a m and b m , and use these to calculate the component concentrations A and B by a multivariate analysis method (for example, a multiple regression analysis method). In this way, the component concentrations A and B are measured. Moreover, if this process is repeated, the component concentrations A and B of the developer can be continuously measured.

圖2係顯示從顯影液的三個或三個以上的特性值測定顯影液的三個或三個以上的成分之成分濃度的情況的信號之流動的本實施形態的成分濃度測定方法之流程圖。 Figure 2 is a flow chart of the component concentration measurement method of the present embodiment showing the flow of signals when the component concentration of three or more components of the developer is measured from three or more characteristic values of the developer .

在本實施形態的成分濃度運算方法中，首先，於測定顯影液的特性值a、b、c、…的步驟中，取得各個測定值am、bm、cm、…。所取得之測定值am、bm、cm、…係被送到運算步驟。其次，運算步驟係接收測定值am、bm、cm、…，使用此等藉由多變量分析法(例如，多元回歸分析法)算出成分濃度A、B、C、…。如此，測定成分濃度A、B、C、…。又，若重複此流程，則可連續測定顯影液的成分濃度A、B、C、…。 The method of calculating the concentration step according to the present embodiment, first, the characteristics of the developer measured values a, b, c, ..., the respective measurement values to obtain a m, b m, c m , .... The measurement value obtained a m, b m, c m , ... is sent to the system operation step. Next, the step of calculating the measured value based receiving a m, b m, c m , ..., by use of such a multivariate analysis (e.g., multiple regression analysis) was calculated concentration of the component A, B, C, .... In this way, the component concentrations A, B, C, ... are measured. In addition, if this process is repeated, the component concentrations A, B, C,... of the developer can be continuously measured.

圖3係表示在從複數個顯影液的特性值測定複數個成分濃度之情況，運算步驟亦含有利用與多變量分析法相異的運算手法之步驟的情況的信號流動之本實施形態的成分濃度測定方法的流程圖。 Figure 3 shows the measurement of the component concentration in the present embodiment of the signal flow when the concentration of a plurality of components is measured from the characteristic values of a plurality of developers, and the calculation step also includes a step using a calculation method different from the multivariate analysis method Flow chart of the method.

此實施形態係於採用僅與顯影液的某成分的濃度P有關係的顯影液的特性值p作為測定對象之情況等可適當被選擇使用。更具體言之，可例舉藉由多變量分析法而由顯影液的導電率值和密度值算出顯影液的鹼成分濃度和吸收二氧化碳濃度，將顯影液的溶解光阻劑濃度以使用和特定波長(例如λ=560nm)中的吸光度之線性關係作為校準曲線算出並作測定的情況等。 This embodiment can be appropriately selected and used when the characteristic value p of the developer only related to the concentration P of a certain component of the developer is used as the measurement target. More specifically, a multivariate analysis method can be used to calculate the alkali component concentration and carbon dioxide absorption concentration of the developer from the conductivity value and density value of the developer, and the dissolved photoresist concentration of the developer can be used and specified. The linear relationship of absorbance in wavelength (for example, λ=560nm) is calculated and measured as a calibration curve.

在本實施態樣的顯影液的成分濃度測定方法中，於測定步驟，測定將複數個成分濃度作為變數的顯影液的特性值a、b、…、及僅將成分濃度P作為變數的顯影液的特性值p、…，且將其測定值am、bm、…、及pm、…送到運算步驟。 In the method for measuring the component concentration of the developer of this embodiment, in the measuring step, the characteristic values a, b, ... of the developer with a plurality of component concentrations as variables are measured, and the developer with only the component concentration P as the variable is measured The characteristic values p,..., and the measured values a m , b m ,..., and p m ,... are sent to the calculation step.

運算步驟包含：藉多變量分析法(例如，多元回歸分析法)算出成分濃度的步驟；及藉與多變量分析法相異的運算方法(例如，校準曲線法等)算出成分濃度的步驟。此等步驟的運算之先後不限。亦可同時。 The calculation step includes a step of calculating the component concentration by a multivariate analysis method (for example, multiple regression analysis method); and a step of calculating the component concentration by a calculation method different from the multivariate analysis method (for example, a calibration curve method, etc.). The order of these steps is not limited. Can also be at the same time.

藉由多變量分析法(例如，多元回歸分析法)算出成分濃度的步驟，係由在測定步驟所測定之顯影液的特性值a、b、…之測定值，藉由多變量分析法(例如，多元回歸分析法)算出成分濃度A、B、…。 The step of calculating the component concentration by a multivariate analysis method (for example, multiple regression analysis) is based on the measured values of the characteristic values a, b, ... of the developer measured in the measuring step, and by a multivariate analysis method (for example, , Multiple regression analysis method) Calculate the component concentrations A, B, ....

藉由與多變量分析法相異的運算方法(例如，校準曲線法)算出成分濃度之步驟，係將已預先取得之特性值p和成分濃度P之線性關係作為校準曲線使用等，由在測定步驟所測定之顯影液的特性值p、…之測定值算出成分濃度P、…。 The step of calculating the component concentration by a calculation method different from the multivariate analysis method (for example, the calibration curve method) is to use the linear relationship between the characteristic value p and the component concentration P obtained in advance as a calibration curve, etc., by the measurement step Calculate the component concentration P,... from the measured value of the measured characteristic value p of the developer.

以上，顯影液的成分濃度測定方法包含：測定步驟，測定與顯影液的成分濃度有關之顯影液的複數個特性值；及運算步驟，依據所測定之複數個特性值，藉由多變量分析法算出顯影液的成分濃度。 Above, the method for measuring the component concentration of the developer includes: a measuring step, measuring multiple characteristic values of the developer related to the component concentration of the developer; and an arithmetic step, based on the measured plural characteristic values, by a multivariate analysis method Calculate the component concentration of the developer.

測定步驟更包含：測定特性值a之測定步驟；測定特性值b之測定步驟；測定特性值c之測定步驟、…等。但是，此等步驟之順序不限。也可同時測定。又，溫度調整步驟、試藥添加步驟、廢液步驟等，亦可含有因應測定手法而適當地需要的步驟。 The measuring step further includes: the measuring step of measuring the characteristic value a; the measuring step of measuring the characteristic value b; the measuring step of measuring the characteristic value c, etc. However, the order of these steps is not limited. It can also be measured at the same time. In addition, the temperature adjustment step, the reagent addition step, the waste solution step, and the like may include steps appropriately required in accordance with the measurement method.

運算步驟只要包含藉多變量分析法算出成分濃度的運算步驟即可。亦可包含藉與多變量分析法相異的運算方法(例如校準曲線法)算出成分濃度的步驟等。 The calculation step only needs to include the calculation step of calculating the component concentration by the multivariate analysis method. It may also include a step of calculating the component concentration by a calculation method different from the multivariate analysis method (for example, a calibration curve method).

以下，第一到第七實施形態係有關本發明的顯影液的濃度監視裝置。 Hereinafter, the first to seventh embodiments relate to the developer concentration monitoring device of the present invention.

[第一實施形態] [First Embodiment]

圖4係測定顯影液的二個成分之濃度監視裝置的示意圖。為方便說明，顯影液的濃度監視裝置A係以連接於顯影製程設備B的態樣下連同顯影製程設備B一起圖示。 Figure 4 is a schematic diagram of a monitoring device for measuring the concentration of two components of a developer. For the convenience of description, the developer concentration monitoring device A is shown together with the development process equipment B in a state of being connected to the development process equipment B.

首先，針對顯影製程設備B作簡單說明。 First, a brief description of the development process equipment B will be given.

顯影製程設備B主要由顯影液貯留槽61、溢流槽62、顯影室罩(hood)64、滾輪式輸送機(roller conveyor)65、顯影液噴灑頭(shower nozzle)67等所構成。在顯影液貯留槽61貯留有顯影液。顯影液係被補充補充液而作組成管理，但在圖4中被省略了。顯影液貯留槽61係具備液面計63和溢流槽62，藉以管理因補給補充液所致之液量的增加。顯影液貯留槽61與顯影液噴灑頭67係藉由顯影液管路80連接，顯影液貯留槽61內所貯留的顯影液藉由設於顯影液管路80的循環泵72經由過濾器73被輸送到顯影液噴灑頭67。滾輪式輸送機65係設於顯影液貯留槽61上方以搬送成膜有光阻劑膜的基板66。顯影液從顯影液噴灑頭67滴下，藉滾輪式輸送機65搬送的基板66係通過滴下的顯影液之中而浸漬於顯影液。之後，顯影液被顯影液貯留槽61回收並再貯留。如此，顯影液係在顯影製程循環地被重複使用。此外，小型玻璃基板中之顯影室內亦有藉由充滿氮氣等而施以不會吸收空氣中的二氧化碳之處理的情況。此外，劣化的顯影液係透過作動廢液泵71而被廢液(排放：(drain))。 The developing process equipment B is mainly composed of a developer storage tank 61, an overflow tank 62, a developing room hood 64, a roller conveyor 65, a developer nozzle 67 and the like. The developer liquid is stored in the developer liquid storage tank 61. The developer system is replenished with replenisher for composition management, but this is omitted in FIG. 4. The developer storage tank 61 is equipped with a level gauge 63 and an overflow tank 62 to manage the increase in the liquid volume caused by the replenishment of the replenishing liquid. The developer storage tank 61 and the developer spray head 67 are connected by the developer pipeline 80, and the developer stored in the developer storage tank 61 is passed through the filter 73 by the circulating pump 72 provided in the developer pipeline 80. Transported to the developer spray head 67. The roller conveyor 65 is installed above the developer storage tank 61 to transport the substrate 66 on which the photoresist film is formed. The developer is dropped from the developer spray head 67, and the substrate 66 conveyed by the roller conveyor 65 is immersed in the developer through the dropped developer. After that, the developer is recovered by the developer storage tank 61 and stored again. In this way, the developer is repeatedly used in the development process. In addition, the developing chamber in the small glass substrate may be filled with nitrogen gas to prevent the carbon dioxide in the air from being absorbed. In addition, the deteriorated developer is drained (drain) by operating the waste pump 71.

其次，針對本實施形態的顯影液的濃度監視裝置A作說明。本實施形態的濃度監視裝置係取樣顯影液以測定特性值之方式的濃度監視裝置。 Next, the developer concentration monitoring device A of this embodiment will be described. The concentration monitoring device of this embodiment is a concentration monitoring device that samples the developer to measure the characteristic value.

顯影液的濃度監視裝置A具備測定部1和運算部2，藉由取樣配管15及回流配管16連接到顯影液貯留槽61。測定部1與運算部2係藉由測定數據用信號線51、52連接。 The developer concentration monitoring device A includes a measurement unit 1 and a calculation unit 2, and is connected to a developer storage tank 61 via a sampling pipe 15 and a return pipe 16. The measurement unit 1 and the calculation unit 2 are connected by signal lines 51 and 52 for measurement data.

測定部1具備取樣泵14、第一測定構件11及第二測定構件12(有將第一測定構件11及第二測定構件12稱為測定構件的情況)。測定構件11、12係串列地連接於取樣泵14的後段。測定部1更具備為了提高測定精度而使所取樣的顯影液穩定為既定的溫度之溫度調節構件(未圖示)者較理想。此際，溫度調節構件係以設於測定構件的前方較佳。取樣配管15連接於測定部1的取樣泵14，回流配管16係和測定構件末端的配管連接。 The measurement unit 1 includes a sampling pump 14, a first measurement member 11, and a second measurement member 12 (the first measurement member 11 and the second measurement member 12 may be referred to as measurement members). The measuring members 11 and 12 are connected in series to the rear stage of the sampling pump 14. It is more preferable that the measurement unit 1 is provided with a temperature adjustment member (not shown) that stabilizes the sampled developer to a predetermined temperature in order to improve the measurement accuracy. In this case, the temperature adjusting member is preferably provided in front of the measuring member. The sampling pipe 15 is connected to the sampling pump 14 of the measurement unit 1, and the return pipe 16 is connected to the pipe at the end of the measurement member.

運算部2包含利用多變量分析法的運算塊21。利用多變量分析法的運算塊21，係連接於藉測定數據用信號線51而設置於測定部1的第一測定構件11、及藉測定數據用信號線52而設置於測定部1的第二測定構件12。 The calculation unit 2 includes a calculation block 21 using a multivariate analysis method. The arithmetic block 21 using the multivariate analysis method is connected to the first measurement member 11 provided in the measurement section 1 via the measurement data signal line 51 and the second measurement member 11 provided in the measurement section 1 via the measurement data signal line 52. Measuring member 12.

其次，針對濃度監視裝置A之測定動作及運算動作進行說明。 Next, the measurement operation and calculation operation of the concentration monitoring device A will be described.

藉取樣泵14從顯影液貯留槽61所採液之顯影液，係通過取樣配管15被導入濃度監視裝置A之測定部1內。之後，於具備溫度調節構件的情況，所取樣之顯影液係被輸送到溫度調節構件以維持在既定的測定溫度(例如25℃)，且輸送到測定構件11、12。以第一測定構件測定顯影液的特性值a，以第二測定構件測定顯影液的特性值b。測定後的顯影液係通過回流配管16返回顯影液貯留槽61。 The developer collected from the developer storage tank 61 by the sampling pump 14 is introduced into the measuring section 1 of the concentration monitoring device A through the sampling pipe 15. After that, in the case where the temperature adjustment member is provided, the sampled developer is sent to the temperature adjustment member to maintain a predetermined measurement temperature (for example, 25° C.), and is then sent to the measurement members 11 and 12. The characteristic value a of the developer is measured by the first measuring member, and the characteristic value b of the developer is measured by the second measuring member. The developer after the measurement is returned to the developer storage tank 61 through the return pipe 16.

藉由第一測定構件11所測定之顯影液的特性值a之測定值am，及藉由第二測定構件12所測定之顯影液的特性值b之測定值bm，係分別經由測定數據用信號線51、52被送至利用多變量分析法的運算塊21。接收到測定值am、bm的運算塊21係藉由多變量分析法運算其等之測定值而算出顯影液的成分濃度A及B。如此，藉由濃度監視裝置A而測定顯影液的成分濃度A、B。 The measured value a m of the characteristic value a of the developer measured by the first measuring member 11 and the measured value b m of the characteristic value b of the developer measured by the second measuring member 12 are respectively measured through the measurement data The signal lines 51 and 52 are sent to the arithmetic block 21 using the multivariate analysis method. The arithmetic block 21 that has received the measured values a m and b m calculates the component concentrations A and B of the developer by calculating the measured values thereof by a multivariate analysis method. In this way, the concentration monitoring device A measures the component concentrations A and B of the developer.

實施形態的濃度監視裝置A具備警報部WD。警報部WD係可在藉運算部2所算出之成分濃度(例如，A或B)中至少任一者偏離所設定之管理範圍時，發出警報。 The concentration monitoring device A of the embodiment includes an alarm unit WD. The alarm unit WD can issue an alarm when at least any one of the component concentrations (for example, A or B) calculated by the calculation unit 2 deviates from the set management range.

例如，可在運算部2預先記憶管理範圍，藉運算部2判斷成分濃度是否為管理範圍外。將其資訊從運算部2傳送到警報部，依據資訊可讓警報部WD發出警報。 For example, the management range can be stored in the calculation unit 2 in advance, and the calculation unit 2 can determine whether the component concentration is outside the management range. The information is sent from the computing unit 2 to the alarm unit, and the alarm unit WD can issue an alarm based on the information.

又，在警報部WD預先記憶管理範圍，從運算部2接收成分濃度的資訊，藉警報部WD判斷成分濃度是否為管理範圍內。依據此判斷，可讓警報部WD發出警報。 In addition, the management range is stored in the alarm unit WD in advance, and information on the component concentration is received from the computing unit 2, and the alarm unit WD determines whether the component concentration is within the management range. Based on this judgment, the alarm unit WD can issue an alarm.

只要警報部WD可發出警報，則管理範圍的記憶構件、及判斷構件未特別作限定。 As long as the alarm unit WD can issue an alarm, the memory means and judgment means in the management range are not particularly limited.

就警報部WD而言，較佳為，具備傳送警報信號之外部輸出信號端子、發出警報音之警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子當中至少任一者。 As for the alarm unit WD, it is preferable to include an external output signal terminal for transmitting an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, a display device that displays a warning, and a switch contact opening and closing At least any one of the relay terminals.

在警報部WD是傳送警報信號之外部輸出信號端子之情況，外部輸出信號端子連接到未圖示的裝置。當裝置從外部輸出信號端子接到警報信號時、可進行既定的動作。例如，若為含有濃度監視裝置的系統的話，則可使系統停止。 When the alarm part WD is an external output signal terminal that transmits an alarm signal, the external output signal terminal is connected to a device not shown. When the device receives an alarm signal from an external output signal terminal, it can perform a predetermined action. For example, if it is a system containing a concentration monitoring device, the system can be stopped.

在警報部WD是發出警報音的警報裝置、或使光點亮或閃爍的警告燈之情況，可引起在濃度監視裝置附近之作業者的注意。作業者可確認濃度監視裝置的狀態，進行適當的應對。 In the case where the alarm unit WD is an alarm device that emits an alarm sound, or a warning lamp that lights or flashes the light, it can attract the attention of the operator near the concentration monitoring device. The operator can confirm the state of the concentration monitoring device and take appropriate measures.

在警報部WD是顯示警告的顯示裝置之情況，同様可引起作業者的注意。又，在顯示裝置是與運算部2以電氣方式有線、或無線連接的情況，對於離開濃度監視裝置的作業者亦可引起注意。 In the case where the alarm part WD is a display device that displays warnings, the same can attract the attention of the operator. In addition, when the display device is electrically wired or wirelessly connected to the computing unit 2, the operator who is away from the concentration monitoring device can also draw attention.

在警報部WD是切換接點之開閉的繼電器端子之情況，可切換被連接到繼電器端子之裝置的ON與OFF、能使裝置進行既定的動作。 When the alarm part WD is a relay terminal that switches the opening and closing of the contact, the device connected to the relay terminal can be switched on and off, enabling the device to perform a predetermined action.

又，亦可按各成分濃度而具備警報部WD。透過按各成分濃度而具備警報部WD，可由警報部WD所傳送的警報知悉是針對哪個成分濃度之警報。 In addition, the alarm unit WD may be provided for each component concentration. By providing the alarm unit WD for each component concentration, the alarm sent by the alarm unit WD can know which component concentration the alarm is for.

[第二實施形態] [Second Embodiment]

圖5係測定顯影液的三個成分之濃度監視裝置的示意圖。顯影液的濃度監視裝置A具備測定部1和運算部2，藉取樣配管15及回流配管16連接到顯影製程設備B(顯影液貯留槽61)。測定部1具備第一測定 構件11、第二測定構件12及第三測定構件13，藉由此等來測定顯影液的三個特性值。所測定之三個特性值之測定值經由測定數據用信號線51、52、53送到運算部2，藉由多變量分析法算出顯影液的三個成分之成分濃度。測定動作、運算動作係和圖4重複的構件之說明係和第一實施形態相同，故予以省略。 Figure 5 is a schematic diagram of a monitoring device for measuring the concentration of three components of a developer. The developer concentration monitoring device A includes a measurement unit 1 and a calculation unit 2, and is connected to a development process equipment B (developer storage tank 61) via a sampling pipe 15 and a return pipe 16. The measurement unit 1 has the first measurement The member 11, the second measuring member 12, and the third measuring member 13 are used to measure three characteristic values of the developer. The measured values of the measured three characteristic values are sent to the calculation section 2 via the signal lines 51, 52, and 53 for measurement data, and the component concentrations of the three components of the developer are calculated by the multivariate analysis method. The description of the measurement operation, the calculation operation system and the components that are repeated in FIG. 4 is the same as in the first embodiment, so it is omitted.

實施形態的濃度監視裝置A具備警報部WD。警報部WD係可在藉運算部2所算出之成分濃度(例如，A、B或C)中至少任一者偏離所設定之管理範圍時發出警報。 The concentration monitoring device A of the embodiment includes an alarm unit WD. The alarm unit WD can issue an alarm when at least one of the component concentrations (for example, A, B, or C) calculated by the calculation unit 2 deviates from the set management range.

[第三實施形態] [Third Embodiment]

圖6係在運算部2具有利用與多變量分析法相異的運算手法之運算塊的濃度監視裝置的示意圖。適用於例如藉由校準曲線法等從所測定之顯影液的物性值可測定顯影液的成分濃度之顯影液的特性值與成分濃度有成組之情況。 FIG. 6 is a schematic diagram of a concentration monitoring device having an arithmetic block using an arithmetic method different from the multivariate analysis method in the arithmetic section 2. It is suitable for the case where the characteristic value of the developer and the component concentration can be determined from the measured physical property value of the developer by the calibration curve method.

本實施形態的濃度監視裝置A具備測定顯影液的複數個特性值之測定部1、由其測定值算出顯影液的成分濃度之運算部2。運算部2包含利用多變量分析法的運算塊21、利用多變量分析法以外的運算手法(例如校準曲線法)之運算塊22。 The concentration monitoring device A of this embodiment includes a measuring unit 1 that measures a plurality of characteristic values of the developer, and a computing unit 2 that calculates the component concentration of the developer from the measured values. The calculation unit 2 includes a calculation block 21 that uses a multivariate analysis method, and a calculation block 22 that uses a calculation method other than the multivariate analysis method (for example, a calibration curve method).

在多變量分析法中用於運算的顯影液的特性值之測定值，係在被測定部1測定後送到運算部2之利用多變量分析法的運算塊21。用在多變量分析法以外 的運算手法(例如校準曲線法)之顯影液的特性值之測定值係被送到運算塊22。透過在運算塊21、22進行運算，算出顯影液的成分濃度。 The measured value of the characteristic value of the developer used for calculation in the multivariate analysis method is measured by the measurement section 1 and sent to the calculation block 21 using the multivariate analysis method in the calculation section 2. Used outside of multivariate analysis The measured value of the characteristic value of the developer in the calculation method (for example, the calibration curve method) is sent to the calculation block 22. By performing calculations in the calculation blocks 21 and 22, the component concentration of the developer is calculated.

此外，利用多變量分析法以外之運算手法(例如校準曲線法)的運算塊22可為複數。針對利用多變量分析法之運算與利用其以外的手法(例如校準曲線法)之運算，其運算之順序不限。其他與第一、第二實施形態重複之構件等之說明係省略。 In addition, the arithmetic block 22 using an arithmetic method other than the multivariate analysis method (for example, the calibration curve method) may be a complex number. Regarding the calculation using the multivariate analysis method and the calculation using other methods (such as the calibration curve method), the order of the calculation is not limited. The description of other components that overlap with the first and second embodiments is omitted.

實施形態的濃度監視裝置A具備警報部WD。警報部WD係可在利用多變量分析法的運算塊21所算出之成分濃度、或利用除了多變量分析法以外的運算手法(例如校準曲線法)的運算塊22所算出的成分濃度之中至少任一者偏離所設定之管理範圍時，發出警報。 The concentration monitoring device A of the embodiment includes an alarm unit WD. The alarm unit WD can be at least among the component concentration calculated by the calculation block 21 of the multivariate analysis method or the component concentration calculated by the calculation block 22 of the calculation method (for example, the calibration curve method) other than the multivariate analysis method. When any one of them deviates from the set management range, an alarm is issued.

[第四實施形態]〕 [Fourth Embodiment]]

圖7係測定部1和運算部2分開構成的濃度監視裝置的示意圖。濃度監視裝置具備警報部WD，可在藉運算部2所算出之成分濃度中至少任一者偏離所設定之管理範圍時發出警報。 FIG. 7 is a schematic diagram of a concentration monitoring device in which the measuring unit 1 and the computing unit 2 are separately constructed. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

在本實施形態的濃度監視裝置A中，測定部1設置於從顯影製程設備B的顯影液管路80旁通(bypass)的管路上，以測定數據用信號線51~53和運算部2連接。亦可直接連接於顯影液管路80、其他的管路等。亦可將流量調節閥(未圖示)等組合使用，以取代取樣泵14。 In the concentration monitoring device A of the present embodiment, the measuring section 1 is provided on a pipeline bypassed from the developer pipeline 80 of the developing process equipment B, and the measurement data signal lines 51 to 53 are connected to the computing section 2 . It can also be directly connected to the developer pipeline 80 or other pipelines. It is also possible to use a flow regulating valve (not shown) in combination to replace the sampling pump 14.

[第五實施形態] [Fifth Embodiment]

圖8係在測定顯影液的特性值之測定構件11~13是由各個測定裝置本體11a、12a、13a與測定探針11b、12b、13b所構成之情況的濃度監視裝置的示意圖。濃度監視裝置具備警報部WD，可在藉運算部2所算出之成分濃度中至少任一者偏離所設定之管理範圍時發出警報。 FIG. 8 is a schematic diagram of the concentration monitoring device in the case where the measuring members 11 to 13 for measuring the characteristic value of the developer are composed of the respective measuring device main bodies 11a, 12a, 13a and the measuring probes 11b, 12b, 13b. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

本實施形態中，測定構件11~13之測定探針11b~13b是透過浸漬於貯留在顯影液貯留槽61的顯影液而測定顯影液的特性值。所測定之顯影液的特性值經由測定數據用信號線51~53送到運算部2。透過利用多變量分析法在運算部2算出成分濃度，藉以測定顯影液的成分濃度。 In the present embodiment, the measuring probes 11b to 13b of the measuring members 11 to 13 measure the characteristic value of the developer through the developer immersed in the developer storage tank 61. The measured characteristic value of the developer is sent to the computing unit 2 via the signal lines 51 to 53 for measurement data. The component concentration of the developer is measured by calculating the component concentration in the computing unit 2 by using the multivariate analysis method.

圖8中雖顯示出測定部1與運算部2是分開構成之情況，但亦可為一體構成的濃度監視裝置。在此情況，浸漬於顯影液中的測定探針與配置在濃度監視裝置之測定部1內的測定裝置本體是被電纜等所連接。 Although FIG. 8 shows a case where the measurement unit 1 and the calculation unit 2 are separately constructed, they may be an integrated concentration monitoring device. In this case, the measuring probe immersed in the developer and the measuring device main body arranged in the measuring section 1 of the concentration monitoring device are connected by a cable or the like.

[第六實施形態] [Sixth Embodiment]

圖9係在具備並列配置的測定部1內之測定構件的情況之濃度監視裝置的示意圖。濃度監視裝置具備警報部WD，可在藉運算部2所算出之成分濃度中至少任一者偏離所設定之管理範圍時發出警報。 FIG. 9 is a schematic diagram of a concentration monitoring device in a case where the measuring means in the measuring section 1 arranged in parallel are provided. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

構成測定部1的各測定構件不受限於串列地連接之情況，亦可並列地連接。如圖9所示，測定構件11~13亦可分別獨立地具備取樣管路15a~15c、取樣 泵14a~14c、回流配管16a~16c等，亦可藉由在中途分歧的管路並列地連接。藉測定構件11~13所測定之顯影液的特性值被送到運算部2。藉由多變量分析法在運算部2中算出顯影液的成分濃度。 The measurement members constituting the measurement unit 1 are not limited to being connected in series, and may be connected in parallel. As shown in Figure 9, the measuring components 11-13 can also be independently equipped with sampling pipes 15a-15c and sampling The pumps 14a to 14c, the return pipes 16a to 16c, etc., may also be connected in parallel by pipes that branch in the middle. The characteristic values of the developer measured by the measuring members 11 to 13 are sent to the computing unit 2. The component concentration of the developer is calculated in the computing section 2 by a multivariate analysis method.

[第七實施形態] [Seventh Embodiment]

圖10係例如自動滴定裝置般在具備需要添加藥劑的測定裝置之情況下的濃度監視裝置的示意圖。圖10中，第三測定構件13是需要添加藥劑的測定裝置。濃度監視裝置具備警報部WD，可在藉運算部2所算出之成分濃度中至少任一者偏離所設定之管理範圍時發出警報。 Fig. 10 is a schematic diagram of a concentration monitoring device in a case where a measurement device that requires addition of a drug is provided, such as an automatic titration device. In FIG. 10, the third measurement member 13 is a measurement device that requires addition of a drug. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

在此情況，第三測定構件13除連接到取樣配管15、取樣泵14以外，還藉由送液配管18連接到添加試藥93。添加試藥係被送液泵17採液以供測定。測定後的顯影液係藉由廢液配管19被廢液(排放)。由於其他的測定動作、運算動作等和其他實施例相同，故予以省略。 In this case, in addition to being connected to the sampling pipe 15 and the sampling pump 14, the third measuring member 13 is also connected to the addition reagent 93 via the liquid feeding pipe 18. The reagent addition system is collected by the liquid delivery pump 17 for measurement. The developer after the measurement is discharged (discharged) through the waste liquid pipe 19. Since other measurement operations, calculation operations, etc. are the same as those of the other embodiments, they are omitted.

以上，如第一到第七實施形態所示，本發明的濃度監視裝置具備：測定部1，測定與顯影液的成分濃度有關之顯影液的複數個特性值；運算部2，依據藉測定部1所測定之顯影液的複數個特性值且藉由多變量分析法測定顯影液的成分濃度。 As described above, as shown in the first to seventh embodiments, the concentration monitoring device of the present invention includes: a measuring unit 1 that measures a plurality of characteristic values of the developer related to the component concentration of the developer; and a computing unit 2 based on the measuring unit 1. Measure multiple characteristic values of the developer and measure the component concentration of the developer by a multivariate analysis method.

本實施形態的濃度監視裝置A的測定部1可採取各種實施形態。由於作為測定構件使用的測定裝置因應於其測定裝置所採用的測定方式而有適合的設置 或連接的方法，故本發明的濃度監視裝置的測定部1只要因應其測定構件作成最合適的構成即可。 The measurement unit 1 of the concentration monitoring device A of this embodiment can take various embodiments. Since the measuring device used as the measuring component has a suitable setting according to the measuring method adopted by the measuring device Or the method of connection, so the measurement unit 1 of the concentration monitoring device of the present invention only needs to be configured most appropriately in accordance with the measurement member.

在測定部1內具備測定顯影液的複數個特性值所需之測定構件即可。測定部1具備溫度調節構件(未圖示)是理想的。雖理想的是視需要而適當地具備取樣泵14、送液泵17、廢液配管19等，但並非意指都必須是測定部1的內部零件。 What is necessary is just to equip the measuring part 1 with the measuring means required to measure the several characteristic value of a developer. It is desirable that the measurement unit 1 includes a temperature adjustment member (not shown). Although it is desirable to appropriately include the sampling pump 14, the liquid feeding pump 17, the waste liquid piping 19, etc., as necessary, it does not mean that all of them need to be internal parts of the measurement unit 1.

又，測定部1與運算部2可為一體，亦可為分開。測定部1與運算部2係以只要運算部2可接收以測定部1測定的顯影液的特性值之測定數據的方式相互連絡即可。測定部1與運算部2不受限於藉信號線連接的情況，亦可構成為能以無線方式收發數據(data)之情況。也沒有必要將複數個測定構件匯集在一個場所而構成測定部1，一個特定的測定構件被分開安置亦可。 In addition, the measurement unit 1 and the calculation unit 2 may be integrated or separate. The measuring unit 1 and the computing unit 2 may be connected to each other so long as the computing unit 2 can receive the measurement data of the characteristic value of the developer measured by the measuring unit 1. The measurement unit 1 and the calculation unit 2 are not limited to the case of being connected by a signal line, and may be configured to be capable of wirelessly transmitting and receiving data (data). There is also no need to gather a plurality of measurement members in one place to form the measurement section 1, and one specific measurement member may be separately arranged.

各測定構件不僅是取樣進行測定的方式，亦可為直接安裝於配管的方式，亦可將探針浸漬於液中的方式。各測定構件可串列地連接，亦可並列地連接。亦可藉各種組合來構成測定部1。 Each measurement member is not only a method of taking a sample for measurement, but also a method of directly installing in a pipe, or a method of immersing the probe in a liquid. The measurement members can be connected in series or in parallel. It is also possible to configure the measurement unit 1 by various combinations.

此外，在本實施形態之測定部1中之顯影液的複數個特性值的測定係不限其順序。在圖4到圖10為止的圖面中之測定部1內的各測定構件之配列、及「第一測定構件」、「第二測定構件」、…等之記載中的「第一」、「第二」、…等之用詞並非限定本發明中之測定的順序者。「第一」、「第二」、…等之用詞只不過是為了方便區別複數個測定構件的每一者而已。 In addition, the order of the measurement of the plural characteristic values of the developer in the measuring section 1 of the present embodiment is not limited. The arrangement of the measurement members in the measurement section 1 in the drawings from Fig. 4 to Fig. 10, and the descriptions of "first measurement member", "second measurement member", etc., "first", " The terms "second", etc. do not limit the order of determination in the present invention. The terms "first", "second", ... and so on are just for the convenience of distinguishing each of the plural measurement components.

又，本實施形態的濃度監視裝置的運算部2若含有利用多變量分析法的運算塊21，則亦可另外具有利用多變量分析法以外之手法(例如校準曲線法)的運算塊。此際，運算之順序不限。 In addition, if the calculation unit 2 of the concentration monitoring device of the present embodiment includes a calculation block 21 using a multivariate analysis method, it may additionally have a calculation block using a method other than the multivariate analysis method (for example, a calibration curve method). At this time, the order of operations is not limited.

本實施形態的濃度監視裝置中，透過構成測定部1的各測定構件以適合於其測定方式配置而設置連接，測定顯影液的複數個特性值，運算部2接收以測定部1所測定之顯影液的特性值之測定值，藉由多變量分析法(運算手法所包含)算出顯影液的成分濃度。 In the concentration monitoring device of this embodiment, the measurement members constituting the measurement section 1 are arranged and connected to suit the measurement method to measure a plurality of characteristic values of the developer, and the computing section 2 receives the development measured by the measurement section 1. The measured value of the characteristic value of the liquid is calculated by the multivariate analysis method (included in the calculation method) to calculate the component concentration of the developer.

以下，在第八實施形態及第九實施形態中，針對本實施形態的濃度監視裝置的應用例作說明。本實施形態的濃度監視裝置能作為一個零件應用於各種的裝置或系統。 Hereinafter, in the eighth embodiment and the ninth embodiment, an application example of the concentration monitoring device of this embodiment will be described. The concentration monitoring device of this embodiment can be applied to various devices or systems as a component.

[第八實施形態] [Eighth Embodiment]

圖11係使用了本實施形態的濃度監視裝置之顯影液管理裝置的示意圖。濃度監視裝置具備警報部WD。 Figure 11 is a schematic diagram of a developer management device using the concentration monitoring device of this embodiment. The concentration monitoring device includes an alarm unit WD.

本實施形態中，濃度監視裝置A係藉由運算數據用信號線54連接到控制控制閥41~43的控制部3(控制裝置)。控制部3(控制裝置)係藉由控制信號用信號線55~57連接到各控制閥41~43。控制閥41~43分別設置在用以從補充液貯留槽91、92輸送補充液之補充液用管路81、82及用以輸送純水之純水用管路83。 In the present embodiment, the concentration monitoring device A is connected to the control unit 3 (control device) that controls the control valves 41 to 43 via a signal line 54 for calculation data. The control part 3 (control device) is connected to each control valve 41-43 by the signal line 55-57 for control signals. The control valves 41 to 43 are respectively provided in the replenishing liquid pipes 81 and 82 for conveying the replenishing liquid from the replenishing liquid storage tanks 91 and 92 and the pure water pipe 83 for conveying pure water.

補充液貯留槽91、92係被氮氣加壓著，透過控制部3(控制裝置)開閉控制閥41~43，補充液通過合流管路84向顯影液補給。被補給的補充液係藉由循環泵74經由循環管路85返回顯影液貯留槽61並被攪拌。補充液的補給動作之方法、機構(mechanism)等，係於後述的顯影液管理方法、顯影液管理裝置等的實施例中作說明。 The replenishing liquid storage tanks 91 and 92 are pressurized by nitrogen gas, and the control valves 41 to 43 are opened and closed through the control unit 3 (control device), and the replenishing liquid is supplied to the developer through the confluence line 84. The replenishing liquid is returned to the developer storage tank 61 via the circulation line 85 by the circulation pump 74 and is stirred. The method, mechanism, etc. of the replenishing operation of the replenisher are described in the embodiments of the developer management method, developer management apparatus, etc. described later.

如此，本實施形態的濃度監視裝置透過與設在向顯影液輸送補給的補充液之管路上的控制閥及控制此等的控制裝置組合，可作為顯影液管理裝置的一個零件利用。 In this way, the concentration monitoring device of this embodiment can be used as a component of the developer management device by combining with the control valve provided in the pipeline for supplying the replenishing liquid to the developer and the control device for controlling these.

此外，所謂補充液意指，例如顯影液的原液、新液、再生液等。亦有包含純水的情況。所謂原液意指鹼成分濃度濃厚之未使用的顯影液(例如20~25%TMAH水溶液)。所謂新液意指鹼成分濃度是與在顯影製程使用的濃度相同濃度且未使用之顯影液(例如2.38%TMAH水溶液)。所謂再生液意指從使用過的顯影液去除不要物作成可再利用之顯影液。此等在作為補充液的用途、效果等上相異。例如，原液係用以提高鹼成分濃度之補充液，降低溶解光阻劑濃度及吸收二氧化碳濃度。新液係用以將鹼成分濃度維持或和緩地增減，降低溶解光阻劑濃度及吸收二氧化碳濃度之補充液。純水係用以降低各成分濃度之補充液。在以下的實施例之說明中亦相同。 In addition, the so-called replenishing liquid means, for example, the original liquid, fresh liquid, and regenerated liquid of the developer. There are also cases where pure water is included. The so-called stock solution refers to an unused developer solution (such as 20-25% TMAH aqueous solution) with a strong alkali component concentration. The so-called new solution means an unused developer (for example, 2.38% TMAH aqueous solution) with the same concentration of alkali component as the concentration used in the development process. The so-called regenerated liquid means to remove unnecessary materials from the used developer to make a reusable developer. These are different in the use and effect of the supplement liquid. For example, the stock solution is a replenishing solution used to increase the concentration of alkali components, reduce the concentration of dissolved photoresist and the concentration of carbon dioxide absorption. The new liquid is a supplementary liquid used to maintain or gently increase or decrease the concentration of alkali components, reduce the concentration of dissolved photoresist and the concentration of carbon dioxide absorption. Pure water is a replenisher used to reduce the concentration of each component. The same applies to the description of the following embodiments.

又，圖11中雖圖示了補充液係從補充液貯留槽91、92經由補充液用管路81、82作供給，純水係經由純水用管路83作供給的情況，但不受此所限。亦有 補充液係從補充液貯留槽91、92等送到調合槽(未圖示)，在那裡調製成既定的濃度之後再輸送到顯影液貯留槽61之情況。在此情況，控制閥41、42係設於從調合槽向顯影液貯留槽61作輸送的管路中途。亦有不向顯影液貯留槽61直接供給純水的情形，此時不存在純水用管路83、控制閥43等。在以下的實施例的說明及以下的圖面中亦相同。 11 illustrates the case where the supplementary liquid system is supplied from the supplementary liquid storage tanks 91 and 92 via the supplementary liquid lines 81 and 82, and the pure water system is supplied via the pure water pipeline 83, but it is not This is limited. There are also cases where the replenisher is sent from the replenisher storage tanks 91, 92, etc. to a mixing tank (not shown), where it is prepared to a predetermined concentration, and then sent to the developer storage tank 61. In this case, the control valves 41 and 42 are provided in the middle of the pipeline transporting from the mixing tank to the developer storage tank 61. There may be cases where pure water is not directly supplied to the developer storage tank 61, and there is no pure water pipeline 83, control valve 43, etc. at this time. The same applies to the description of the following embodiments and the following drawings.

補充液貯留於補充液貯留部C的補充液貯留槽91、92。補充液貯留槽91、92連接於具備加壓氣體用閥46、47之氮氣用管路86，藉由經此管路供給的氮氣而被加壓。又，在補充液貯留槽91、92分別連接補充液用管路81、82，透過通常為開啟狀態的閥44、45輸送補充液。補充液用管路81、82及純水用管路83具備有控制閥41~43，控制閥41~43係被控制部3控制開閉。透過控制閥動作，補充液貯留槽91、92所貯留之補充液被壓送，且被輸送純水。之後，補充液經由合流管路84與循環攪拌機構D合流且被補給到顯影液貯留槽61並被攪拌。 The replenishing liquid is stored in the replenishing liquid storage tanks 91 and 92 of the replenishing liquid storage portion C. The replenishing liquid storage tanks 91 and 92 are connected to a pipe 86 for nitrogen gas provided with valves 46 and 47 for pressurized gas, and are pressurized by nitrogen gas supplied through this pipe. In addition, the replenishing liquid pipes 81 and 82 are respectively connected to the replenishing liquid storage tanks 91 and 92, and the replenishing liquid is delivered through the valves 44 and 45 which are normally open. The replenishing liquid pipelines 81 and 82 and the pure water pipeline 83 are provided with control valves 41 to 43, and the control valves 41 to 43 are controlled to open and close by the control unit 3. Through the operation of the control valve, the replenishing liquid stored in the replenishing liquid storage tanks 91 and 92 is sent under pressure and pure water is delivered. After that, the replenishing liquid merges with the circulation stirring mechanism D via the joining pipe 84 and is replenished to the developer storage tank 61 and stirred.

當因為補給使得補充液貯留槽91、92內所貯留之補充液減少時，由於其內壓降低使供給量變不穩定，故維持成因應補充液之減少而適當開啟加壓氣體用閥46、47供給氮氣，以保持補充液貯留槽91、92的內壓。在補充液貯留槽91、92變空時，關閉閥44、45，和充滿補充液的新的補充液貯留槽作更換，或將另外準備的補充液再填充於變空的補充液貯留槽91、92。 When the replenishing liquid stored in the replenishing liquid storage tanks 91, 92 is reduced due to the replenishment, the supply amount becomes unstable due to the decrease in the internal pressure. Therefore, the maintenance factor should appropriately open the pressurized gas valves 46, 47 in response to the decrease of the replenishing liquid. Nitrogen gas is supplied to maintain the internal pressure of the replenishing liquid storage tanks 91 and 92. When the replenishing liquid storage tanks 91 and 92 become empty, close the valves 44 and 45 and replace them with a new replenishing liquid storage tank filled with the replenishing liquid, or refill the empty replenishing liquid storage tank 91 with a separately prepared replenishing liquid. , 92.

[第九實施形態] [Ninth Embodiment]

本實施形態的濃度監視裝置係可和顯示裝置DP組合而作為顯影液的成分濃度監視器、濃度監視裝置利用。亦可兼用作顯示裝置DP和警報部WD。圖12係用以顯示本發明的濃度監視裝置之應用事例的示意圖。如此，本發明的濃度監視裝置可作為零件應用於各種的裝置、系統等。 The concentration monitoring device of this embodiment can be combined with the display device DP and used as a component concentration monitor or concentration monitoring device of the developer. It can also be used as the display device DP and the alarm unit WD. Fig. 12 is a schematic diagram showing an application example of the concentration monitoring device of the present invention. In this way, the concentration monitoring device of the present invention can be applied to various devices, systems, etc. as parts.

以下，圖13到圖17係有關實施形態的顯影液管理方法。 Hereinafter, FIGS. 13 to 17 show the developer management method related to the embodiment.

本發明的顯影液管理方法包含：測定步驟，測定與鹼性顯影液的成分濃度有關之顯影液的複數個特性值；運算步驟，藉由多變量分析法從所測定之複數個特性值算出顯影液的成分濃度；及補給步驟，依據所測定之顯影液的特性值或算出之顯影液的成分濃度而向顯影液補給補充液。測定步驟及運算步驟係和在前述的顯影液的成分濃度測定方法中之測定步驟、運算步驟相同，故在以下的圖13到圖17的實施形態中省略其重複的說明。 The developer management method of the present invention includes: a measuring step of measuring a plurality of characteristic values of the developer related to the component concentration of the alkaline developer; an arithmetic step of calculating the developer from the measured characteristic values by a multivariate analysis method The component concentration of the liquid; and the replenishing step, based on the measured characteristic value of the developer or the calculated component concentration of the developer, to replenish the developer with the replenishing liquid. The measurement steps and calculation steps are the same as the measurement steps and calculation steps in the above-mentioned method for measuring the component concentration of the developer, so the repeated description will be omitted in the following embodiments in FIGS. 13 to 17.

又，以下的說明中，所謂「既定的管理值」意指，作為顯影液發揮最佳的液體性能時的特性值或成分濃度值，係依經驗或實驗等而預先知悉的特性值或成分濃度值。亦即，例如顯影後的基板上所形成之線寬或殘餘膜厚之類的成為顯影液的顯影性能的指標之數值是指以成為最好的狀態之特性值或成分濃度值之預知的值。「既定的管理區域」亦是這樣的管理值的範圍。在顯影液管理裝置的說明中亦相同。In addition, in the following description, the "predetermined management value" means the characteristic value or component concentration value when the developer exhibits the best liquid performance as a developer. It is a characteristic value or component concentration known in advance based on experience or experiment. value. That is, the value used as an indicator of the developing performance of the developer, such as the line width or the residual film thickness formed on the substrate after development, refers to the predicted value of the characteristic value or the component concentration value in the best state . The "established management area" is also the range of such management values. The same applies to the description of the developer management device.

圖13係藉由成分濃度管理顯影液的二個成分之顯影液管理方法的流程圖。本實施形態的顯影液管理方法係可較佳地適用於被管理成二氧化碳的吸收少的鹼性顯影液中，以顯影液的鹼成分濃度是成為既定的管理值及溶解光阻劑濃度是成為既定的管理值以下的方式管理顯影液之情況等。 FIG. 13 is a flowchart of a developer management method for managing two components of a developer by component concentration. The developer management method of this embodiment can be preferably applied to an alkaline developer that is managed so that the absorption of carbon dioxide is low. The concentration of the alkali component of the developer becomes the predetermined management value and the concentration of the dissolved photoresist becomes Manage the condition of the developer solution below the predetermined management value.

本實施形態中，作成將成分濃度A管理在既定的管理值A0，將成分濃度B管理在既定的管理值B0以下。成分濃度A係例如為鹼成分濃度，成分濃度B係例如為溶解光阻劑濃度。 In the present embodiment, the component concentration A is managed at a predetermined management value A 0 , and the component concentration B is managed below the predetermined management value B 0 . The component concentration A system is, for example, the alkali component concentration, and the component concentration B system is, for example, the dissolved photoresist concentration.

在測定步驟測定顯影液的特性值a、b，將其測定值am、bm送到運算步驟。在運算步驟中，藉由多變量分析法由測定值am、bm算出顯影液的成分濃度A、B。藉運算步驟所算出之成分濃度A、B被送到補給步驟。 In the measurement step, the characteristic values a and b of the developer are measured, and the measured values a m and b m are sent to the calculation step. In the calculation step, the component concentrations A and B of the developer are calculated from the measured values a m and b m by a multivariate analysis method. The component concentrations A and B calculated by the calculation step are sent to the replenishment step.

補給步驟包含調整成分濃度A的步驟及調整成分濃度B的步驟。 The replenishment step includes a step of adjusting the component concentration A and a step of adjusting the component concentration B.

首先，在調整成分濃度A的步驟中，判斷成分濃度A是否比其管理值A0大或小。在大時，將可發揮將成分濃度A稀釋的作用之補充液(例如顯影液新液、純水等)對顯影液作補給。在小時，將可發揮使成分濃度A變濃的作用之補充液(例如，顯影液原液、新液等)對顯影液作補給。在成分濃度A是和其管理值A0相同時，什麼都不做。 First, in the step of adjusting the component concentration A, it is determined whether the component concentration A is larger or smaller than its management value A 0 . When it is large, replenish the developer with a replenisher (for example, fresh developer solution, pure water, etc.) that can dilute the component concentration A. At the hour, the developer is replenished with a replenisher (for example, a stock solution of the developer, a new solution, etc.) that can increase the concentration of the component A. When the component concentration A is the same as its management value A 0 , nothing is done.

在調整成分濃度B的步驟中，判斷成分濃度B是否比其管理值B0大。在大時，將可發揮將成分濃 度B稀釋的作用之補充液(例如，顯影液新液不會改變鹼成分濃度，故而較佳)對顯影液作補給。在小時，什麼都不做。 In the step of adjusting the component concentration B, it is determined whether the component concentration B is greater than its management value B 0 . When it is large, a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

圖14係顯影液的二個成分中的一者藉成分濃度而另一者藉特性值作管理的情況之顯影液管理方法的流程圖。本實施形態的顯影液管理方法係可較佳地適用於被管理成二氧化碳的吸收少的鹼性顯影液中，以顯影液的鹼成分濃度可成為既定的管理值、及顯影液的特定波長(例如λ=560nm)中的吸光度可成為既定的管理值以下之方式管理顯影液之情況等。 FIG. 14 is a flowchart of a developer management method in the case where one of the two components of the developer is managed by the component concentration and the other is managed by the characteristic value. The developer management method of this embodiment can be preferably applied to an alkaline developer that is managed so that the absorption of carbon dioxide is low, and the concentration of the alkali component of the developer can be a predetermined management value and a specific wavelength of the developer ( For example, the absorbance in λ=560nm) can be managed in such a way as to be below the predetermined management value.

本實施形態中，將成分濃度A管理在既定的管理值A0，將顯影液的特性值b之測定值bm管理在既定的管理值b0以下。成分濃度A係例如為鹼成分濃度，特性值b係例如為在特定波長(例如λ=560nm)中之吸光度。 In the present embodiment, the component concentration A is managed to a predetermined management value A 0 , and the measured value b m of the characteristic value b of the developer is managed to be below the predetermined management value b 0 . The component concentration A is, for example, the alkali component concentration, and the characteristic value b is, for example, the absorbance at a specific wavelength (for example, λ=560 nm).

在測定步驟測定顯影液的特性值a、b，其測定值am、bm被送到運算步驟。藉由多變量分析法在運算步驟，由測定值am、bm算出顯影液的成分濃度A、B。藉運算步驟所算出之成分濃度A和藉測定步驟所測定之特性值b之測定值bm係被送到補給步驟。 In the measuring step, the characteristic values a and b of the developer are measured, and the measured values a m and b m are sent to the calculation step. Calculate the component concentrations A and B of the developer from the measured values a m and b m in the calculation step by the multivariate analysis method. The measured value b m of the component concentration A calculated by the calculation step and the characteristic value b measured by the measurement step is sent to the replenishment step.

補給步驟包含調整成分濃度A的步驟與調整特性值b的步驟。由於調整成分濃度A的步驟和圖13的情況相同，故予以省略其說明。 The replenishment step includes the step of adjusting the component concentration A and the step of adjusting the characteristic value b. Since the steps for adjusting the component concentration A are the same as in the case of FIG. 13, the description thereof will be omitted.

在調整特性值b的步驟中，其測定值bm和其管理值b0比較以判斷是否較大。在大時，將可發揮將 成分濃度B稀釋的作用之補充液(例如，顯影液新液不會改變鹼成分濃度，故而較佳)對顯影液作補給。在小時，什麼都不做。 In the step of adjusting the characteristic value b, the measured value b m is compared with the management value b 0 to determine whether it is larger. When it is large, a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

在特性值b與成分濃度B具有單調遞增之相關關係時，透過特性值b被管理成為其管理值b0以下，成分濃度B被管理成為其管理值B0以下。在特性值b與成分濃度B具有單調遞減之相關關係時，若反轉判斷的大小關係而運作的話，則同樣地能將成分濃度B管理成為其管理值B0以下。 When the characteristic value b and the component concentration B have a monotonically increasing correlation, the transmission characteristic value b is managed to be below its management value b 0 and the component concentration B is managed to be below its management value B 0 . When the characteristic value b and the component concentration B have a monotonically decreasing correlation, if the magnitude relationship of the determination is reversed and the operation is performed, the component concentration B can be managed to be below its management value B 0 in the same way.

圖15係顯影液的三個成分藉由成分濃度作管理之顯影液管理方法的流程圖。本實施形態的顯影液管理方法係可較佳地適用於，例如，在將顯影液的鹼成分濃度管理成為既定的管理值、溶解光阻劑濃度管理成為既定的管理值以下、及吸收二氧化碳濃度管理成為既定的管理值以下之情況等。 FIG. 15 is a flowchart of a developer management method in which the three components of the developer are managed by the component concentration. The developer management method of this embodiment can be preferably applied to, for example, the concentration of the alkali component of the developer is managed to a predetermined management value, the concentration of the dissolved photoresist is managed to be below the predetermined management value, and the concentration of carbon dioxide absorbed When the management becomes below the predetermined management value, etc.

補給步驟，係設為將成分濃度A管理在既定的管理值A0，成分濃度B管理在既定的管理值B0以下，成分濃度C管理在既定的管理值C0以下。成分濃度A係例如為鹼成分濃度，成分濃度B係例如為溶解光阻劑濃度、成分濃度C係例如為吸收二氧化碳濃度。 In the replenishment step, the component concentration A is managed at a predetermined management value A 0 , the component concentration B is managed at a predetermined management value B 0 or less, and the component concentration C is managed at a predetermined management value C 0 or less. The component concentration A system is, for example, the alkali component concentration, the component concentration B system is, for example, the dissolved photoresist concentration, and the component concentration C system is, for example, the carbon dioxide absorption concentration.

在測定步驟測定顯影液的特性值a、b、c、…，其測定值am、bm、cm、…被送到運算步驟。在運算步驟，藉由多變量分析法由測定值am、bm、cm、…算出顯影液的成分濃度A、B、C、…。藉運算步驟所算出之成分濃度A、B、C、…係被送到補給步驟。 In the measuring step, the characteristic values a, b, c, ... of the developer are measured, and the measured values a m , b m , c m , ... are sent to the calculation step. In the step of calculating, by multivariate analysis from the measured value a m, b m, c m , ... calculate the concentration of the developer components A, B, C, .... The component concentrations A, B, C, ... calculated by the calculation step are sent to the replenishment step.

補給步驟包含調整成分濃度A的步驟、調整成分濃度B的步驟及調整成分濃度C的步驟。 The replenishment step includes the step of adjusting the component concentration A, the step of adjusting the component concentration B, and the step of adjusting the component concentration C.

首先，在調整成分濃度A的步驟中，判斷成分濃度A是否比其管理值A0大或小。在大時，將可發揮將成分濃度A稀釋的作用之補充液(例如顯影液新液、純水等)對顯影液作補給。在小時，將可發揮使成分濃度A變濃的作用之補充液(例如顯影液原液、新液等)對顯影液作補給。在成分濃度A和其管理值A0相同時，什麼都不做。 First, in the step of adjusting the component concentration A, it is determined whether the component concentration A is larger or smaller than its management value A 0 . When it is large, replenish the developer with a replenisher (for example, fresh developer solution, pure water, etc.) that can dilute the component concentration A. At the hour, the developer is replenished with a replenisher (for example, a stock solution of the developer, a new solution, etc.) that can increase the concentration of the component A. When the component concentration A and its management value A 0 are the same, nothing is done.

在調整成分濃度B的步驟中，判斷成分濃度B是否比其管理值B0大。在大時，將可發揮將成分濃度B稀釋的作用之補充液(例如顯影液新液不會改變鹼成分濃度，故而較佳)對顯影液作補給。在小時，什麼都不做。 In the step of adjusting the component concentration B, it is determined whether the component concentration B is greater than its management value B 0 . When it is large, replenish the developer with a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is better). Do nothing at the hour.

在調整成分濃度C的步驟中，判斷成分濃度C是否比其管理值C0大。在大時，將可發揮將成分濃度C稀釋的作用之補充液(例如，顯影液新液不會改變鹼成分濃度，故而較佳)對顯影液作補給。在小時，什麼都不做。 In the step of adjusting the component concentration C, it is determined whether the component concentration C is greater than its management value C 0 . When it is large, a replenisher that can dilute the component concentration C (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

圖16係顯影液的三個成分中的一個藉由特性值而其他二個藉由成分濃度作管理之顯影液管理方法的流程圖。本實施形態的顯影液管理方法係可較佳地適用於以顯影液的鹼成分濃度可成為既定的管理值、顯影液的特定波長(例如λ=560nm)中的吸光度可成為既定的管理值以下、及顯影液的吸收二氧化碳濃度可成為既定的管理值以下的方式管理顯影液之情況等。 FIG. 16 is a flowchart of a developer management method in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration. The developer management method of this embodiment can be preferably applied to the fact that the alkali component concentration of the developer can be a predetermined management value, and the absorbance at a specific wavelength (e.g. λ=560nm) of the developer can be below the predetermined management value. , And the developer's absorbed carbon dioxide concentration can be controlled below the predetermined management value.

本實施形態中，設為將成分濃度A管理在既定的管理值A0，顯影液的特性值b之測定值bm管理在既定的管理值b0以下，成分濃度C管理在既定的管理值C0以下。成分濃度A係例如為鹼成分濃度，特性值b係例如為在特定波長(例如λ=560nm)中之吸光度，成分濃度C係例如為吸收二氧化碳濃度。 In this embodiment, it is assumed that the component concentration A is managed at the predetermined management value A 0 , the measured value b m of the characteristic value b of the developer is managed at the predetermined management value b 0 or less, and the component concentration C is managed at the predetermined management value. Below C 0 . The component concentration A is, for example, the alkali component concentration, the characteristic value b is, for example, the absorbance at a specific wavelength (for example, λ=560 nm), and the component concentration C is, for example, the carbon dioxide absorption concentration.

在測定步驟測定顯影液的特性值a、b、c，其測定值am、bm、cm被送到運算步驟。在運算步驟中，藉由多變量分析法由測定值am、bm、cm算出顯影液的成分濃度A、B、C。藉運算步驟所算出之成分濃度A、C及在測定步驟所測定的特性值b之測定值bm係被送到補給步驟。 Characteristics of the developer measured in the measurement step values a, b, c, the measured values a m, b m, c m is sent to the calculating step. In the operation step, by multivariate analysis from the measured value a m, b m, c m is calculated concentration of the developer components A, B, C. The component concentrations A and C calculated by the calculation step and the measured value b m of the characteristic value b measured in the measurement step are sent to the replenishment step.

補給步驟包含調整成分濃度A的步驟、調整特性值b的步驟及調整成分濃度C的步驟。由於調整成分濃度A的步驟及調整成分濃度C的步驟和圖15相同，故予以省略其說明。 The replenishment step includes the step of adjusting the component concentration A, the step of adjusting the characteristic value b, and the step of adjusting the component concentration C. Since the step of adjusting the component concentration A and the step of adjusting the component concentration C are the same as in FIG. 15, the description thereof will be omitted.

在調整特性值b的步驟中，其測定值bm和其管理值b0比較判斷是否較大。在大時，將可發揮將成分濃度B稀釋的作用之補充液(例如，顯影液新液不會改變鹼成分濃度，故而較佳)對顯影液作補給。在小時，什麼都不做。 In the step of adjusting the characteristic value b, the measured value b m is compared with the management value b 0 to determine whether it is larger. When it is large, a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

在特性值b與成分濃度B具有單調遞增之相關關係時，透過特性值b被管理成為其管理值b0以下，成分濃度B被管理成為其管理值B0以下。在特性值b與成分濃度B具有單調遞減之相關關係時，若反轉判 斷的大小關係(亦即bm<b0)而運作的話，則同樣地能將成分濃度B管理成為其管理值B0以下。 When the characteristic value b and the component concentration B have a monotonically increasing correlation, the transmission characteristic value b is managed to be below its management value b 0 and the component concentration B is managed to be below its management value B 0 . When the characteristic value b and the component concentration B have a monotonically decreasing correlation, if the magnitude relationship of the judgment is reversed (that is, b m <b 0 ), the component concentration B can be managed as its management value B. Below 0 .

圖17係顯影液的三個成分中的二個藉由特性值而另一個藉由成分濃度作管理之顯影液管理方法的流程圖。本實施形態的顯影液管理方法係可較佳地適用於以顯影液的導電率可成為既定的管理值、顯影液的特定波長(例如λ=560nm)中的吸光度可成為既定的管理值以下、及顯影液的吸收二氧化碳濃度可成為既定的管理值以下的方式管理顯影液之情況等。 FIG. 17 is a flowchart of a developer management method in which two of the three components of the developer are managed by characteristic values and the other is managed by the component concentration. The developer management method of this embodiment can be preferably applied to the fact that the conductivity of the developer can be a predetermined management value, and the absorbance at a specific wavelength (for example, λ=560nm) of the developer can be below the predetermined management value, And the concentration of carbon dioxide absorbed by the developer can be managed in such a way that the developer can be controlled below the predetermined management value.

本實施形態中，設為將顯影液的特性值a之測定值am管理在既定的管理值a0，顯影液的特性值b之測定值bm管理在既定的管理值b0以下，成分濃度C管理在既定的管理值C0以下。特性值a係例如為導電率，特性值b係例如為在特定波長(例如λ=560nm)中之吸光度，成分濃度C係例如為吸收二氧化碳濃度。 In the present embodiment, it is assumed that the measured value a m of the characteristic value a of the developer is managed at a predetermined management value a 0 , and the measured value b m of the characteristic value b of the developer is managed below the predetermined management value b 0 . The concentration C is managed below the predetermined management value C 0 . The characteristic value a is, for example, electrical conductivity, the characteristic value b is, for example, the absorbance at a specific wavelength (for example, λ=560 nm), and the component concentration C is, for example, the concentration of absorbed carbon dioxide.

在測定步驟測定顯影液的特性值a、b、c，其測定值am、bm、cm被送到運算步驟。在運算步驟中，藉由多變量分析法由測定值am、bm、cm算出顯影液的成分濃度A、B、C。在測定步驟所測定之特性值a之測定值am、特性值b之測定值bm及藉運算步驟所算出之成分濃度C係被送到補給步驟。 Characteristics of the developer measured in the measurement step values a, b, c, the measured values a m, b m, c m is sent to the calculating step. In the operation step, by multivariate analysis from the measured value a m, b m, c m is calculated concentration of the developer components A, B, C. Measured characteristic value of the measurement step of measuring a value of a m, b is a value measured characteristic values of m and b calculated by the calculating step based component concentration C is supplied to the supply step.

補給步驟包含調整特性值a的步驟、調整特性值b的步驟及調整成分濃度C的步驟。由於調整特性值b的步驟及調整成分濃度C的步驟和圖16相同，故予以省略其說明。 The replenishment step includes the step of adjusting the characteristic value a, the step of adjusting the characteristic value b, and the step of adjusting the component concentration C. Since the step of adjusting the characteristic value b and the step of adjusting the component concentration C are the same as those in FIG. 16, the description thereof will be omitted.

在調整特性值a的步驟中，其測定值am和其管理值a0比較以判斷是較大或小。在大時，將可發揮將成分濃度A稀釋的作用之補充液(例如顯影液原液或新液)對顯影液作補給。在小時，將可發揮使成分濃度A變濃的作用之補充液(例如顯影液新液或純水)對顯影液作補給。在相同時，什麼都不做。 In the step of adjusting the characteristic value a, the measured value a m is compared with the management value a 0 to determine whether it is larger or smaller. When it is large, replenish the developer with a replenisher that can dilute the component concentration A (for example, the original developer solution or a new solution). At small hours, the developer is replenished with a replenisher (for example, fresh developer solution or pure water) that can increase the concentration of component A. Do nothing at the same time.

在特性值a與成分濃度A具有單調遞增之相關關係時，透過特性值a被維持成其管理值a0使成分濃度A被管理成為其管理值A0。在特性值a與成分濃度A具有單調遞少之相關關係時，若反轉判斷的大小關係而運作的話，則同樣地能將成分濃度A管理成為其管理值A0。 When the characteristic value a and the component concentration A have a monotonically increasing correlation, the characteristic value a is maintained at its management value a 0 so that the component concentration A is managed to its management value A 0 . When the characteristic value a and the component concentration A have a monotonously low correlation, if the magnitude relationship of the judgment is reversed and the operation is performed, the component concentration A can be managed to the management value A 0 in the same manner.

以上，圖13至圖17所示的顯影液管理方法包含：測定步驟，測定與顯影液的成分濃度有關之顯影液的複數個特性值；運算步驟，依據所測定之複數個特性值藉由多變量分析法算出顯影液的成分濃度；及補給步驟，依據從所測定之顯影液的複數個特性值及所算出之顯影液的成分濃度中所選擇的管理對象項目之測定值或算出值，向顯影液補充補充液。 Above, the developer management method shown in FIGS. 13 to 17 includes: a measuring step of measuring a plurality of characteristic values of the developer related to the component concentration of the developer; an arithmetic step of measuring a plurality of characteristic values based on the measured characteristic values The variable analysis method calculates the component concentration of the developer; and the replenishment step is based on the measured value or calculated value of the management target item selected from the measured plural characteristic values of the developer and the calculated component concentration of the developer. Developer replenishes replenisher.

測定步驟更包含：測定特性值a之測定步驟、測定特性值b之測定步驟、測定特性值c之測定步驟、…等。但此等步驟之順序不限。也可同時被測定。又，溫度調整步驟、試藥添加步驟、廢液步驟等亦可因應測定手法而包含適當的必要步驟。 The measuring step further includes: a measuring step of measuring the characteristic value a, a measuring step of measuring the characteristic value b, a measuring step of measuring the characteristic value c, etc. However, the order of these steps is not limited. It can also be measured at the same time. In addition, the temperature adjustment step, the reagent addition step, the waste liquid step, etc. may include appropriate necessary steps in accordance with the measurement method.

運算步驟係只要含有利用多變量分析法算出成分濃度的運算步驟即可。亦可含有利用與多變量分析法相異的運算方法(例如校準曲線法)算出成分濃度之步驟等。 The calculation step should just include a calculation step for calculating the component concentration using a multivariate analysis method. It may also include a step for calculating the component concentration using a calculation method different from the multivariate analysis method (for example, a calibration curve method).

補給步驟包含：將管理對象項目(顯影液的特性值或成分濃度中任一者)作為控制量，且以此可成為既定的管理值或既定的管理值以下或管理區域內之方式向顯影液補給補充液之調整成分濃度A的步驟、調整成分濃度B的步驟、調整成分濃度C的步驟、…。其順序不受圖面所示的順序所限定。 The replenishment step includes: Regarding the management target item (either the characteristic value or the component concentration of the developer) as the control amount, and using this to become the predetermined management value or below the predetermined management value or within the management area The step of adjusting component concentration A, the step of adjusting component concentration B, the step of adjusting component concentration C,... The order is not limited by the order shown in the figure.

又，控制的方式可採用使控制量符合目標值的控制所能使用的各種控制方法。特別是以比例控制(P控制)(Proportional Control)、積分控制(I控制)(Integral Control)、微分控制(D控制)(Differential Control)、及組合此等控制而成的控制(PI控制(Proportional-Integral Control)等)為佳。更佳為適合PID控制。 In addition, as the control method, various control methods that can be used for the control to make the control amount conform to the target value can be adopted. Especially proportional control (P control) (Proportional Control), integral control (I control) (Integral Control), differential control (D control) (Differential Control), and a combination of these controls (PI control (Proportional Control) -Integral Control) etc.) is better. More preferably, it is suitable for PID control.

在上述圖13至圖17的實施形態中，透過重複測定步驟、運算步驟、補給步驟，顯影液的成分濃度A維持在其管理值A0，被管理成顯影液的成分濃度B係其管理值B0以下，成分濃度C係其管理值C0以下。因此，藉由本發明的顯影液管理方法，可維持最佳的顯影性能，可實現所期望的線寬或殘餘膜厚。 In the embodiment shown in FIGS. 13 to 17 above, by repeating the measurement steps, calculation steps, and replenishment steps, the component concentration A of the developer is maintained at its management value A 0 , and the component concentration B of the developer is managed to be its management value Below B 0 , the component concentration C is below its management value C 0 . Therefore, with the developer management method of the present invention, the best development performance can be maintained, and the desired line width or residual film thickness can be achieved.

以下，第十到第十七實施形態係有關本發明的顯影液管理裝置。 Hereinafter, the tenth to seventeenth embodiments relate to the developer management device of the present invention.

本實施形態的顯影液管理裝置具備：測定部1，測定與鹼性顯影液的成分濃度有關之顯影液的複數個特性值；運算部2，藉由多變量分析法從藉測定部1所測定之複數個特性值算出顯影液的成分濃度；及控制部3，依據藉測定部1所測定之顯影液的特性值或藉運算部2所算出之顯影液的成分濃度向設於輸送要向顯影液補給的補充液之管路上之控制閥41~43發出控制信號。由於本發明的顯影液管理裝置之測定部1及運算部2和在前述之顯影液的成分濃度測定裝置中的測定部1、運算部2相同，故在以下從第十到第十七實施形態中省略其重複的說明。 The developer management device of this embodiment is provided with: a measuring unit 1 which measures plural characteristic values of the developer related to the component concentration of the alkaline developer; and a computing unit 2 which measures from the measuring unit 1 by a multivariate analysis method Calculate the component concentration of the developer from the plurality of characteristic values; and the control section 3, based on the characteristic value of the developer measured by the measuring section 1 or the developer’s component concentration calculated by the calculating section 2 The control valves 41~43 on the pipeline of the replenishing liquid for liquid replenishment send out control signals. Since the measuring section 1 and the calculating section 2 of the developer management device of the present invention are the same as the measuring section 1 and the calculating section 2 in the aforementioned developer component concentration measuring device, the tenth to seventeenth embodiments are described below. Repetitive descriptions are omitted.

[第十實施形態] [Tenth Embodiment]

圖18係用以說明本發明的顯影液管理裝置的顯影製程的示意圖。本發明的顯影液管理裝置E是連同顯影製程設備B、補充液貯留部C、循環攪拌機構D等一起被圖示。 FIG. 18 is a schematic diagram for explaining the development process of the developer management device of the present invention. The developer management device E of the present invention is illustrated together with the development process equipment B, the replenishing liquid storage portion C, the circulating stirring mechanism D, and the like.

本實施形態的顯影液管理裝置E具備：測定部1，具備測定顯影液的複數個特性值之複數個測定構件11~13；運算部2，含有利用多變量分析法的運算塊21；控制部3，將顯影液的特性值或成分濃度中任一者作為控制量且使其成為既定的管理值或管理區域內之方式作控制；及警報部WD。又，本實施形態的顯影液管理裝置具備和控制部3連接而被控制之控制閥41~43。 The developer management device E of the present embodiment includes: a measuring section 1 including a plurality of measuring members 11 to 13 for measuring a plurality of characteristic values of the developer; a calculation section 2 including a calculation block 21 using a multivariate analysis method; and a control section 3. Regarding any of the characteristic value or component concentration of the developer as the control quantity and making it into a predetermined management value or within the management area for control; and the alarm unit WD. In addition, the developer management device of the present embodiment includes control valves 41 to 43 that are connected to the control unit 3 and controlled.

顯影液管理裝置E藉由取樣配管15連接到顯影液貯留槽61。藉取樣泵14所取樣的顯影液通過取樣配管15導至測定部1內。在測定部1內，各測定構件11~13測定顯影液的特性值。測定後的顯影液通過回流配管16返回顯影液貯留槽61。 The developer management device E is connected to the developer storage tank 61 through the sampling pipe 15. The developer sampled by the sampling pump 14 is guided into the measurement section 1 through the sampling pipe 15. In the measuring section 1, the measuring members 11 to 13 measure the characteristic value of the developer. The developer after the measurement is returned to the developer storage tank 61 through the return pipe 16.

運算部2係接收一組被測定部1測定之顯影液的複數個特性值之測定值。運算部2係從所接收之一組的測定值藉由多變量分析法來算出顯影液的成分濃度。 The computing unit 2 receives a set of measured values of a plurality of characteristic values of the developer measured by the measuring unit 1. The arithmetic unit 2 calculates the component concentration of the developer by a multivariate analysis method from the received set of measured values.

關於測定動作、運算動作的詳情，由於和前述的現像液的濃度監視裝置相同，所以省略，故以下針對控制動作進行說明。 The details of the measurement operation and arithmetic operation are the same as those of the above-mentioned concentration monitoring device for the imaging liquid, so they are omitted, so the control operation will be described below.

顯影液管理裝置E係連接到管路81~83(含純水在內設為補充液)輸送要補給到顯影液的補充液。各管路81~83連接到在顯影液管理裝置E內被控制部3控制其動作之控制閥41~43。 The developer management device E is connected to the pipes 81 to 83 (replenishing liquid including pure water) and transports the replenishing liquid to be replenished to the developer. The pipes 81 to 83 are connected to control valves 41 to 43 whose operations are controlled by the control unit 3 in the developer management device E.

控制部3接收來自測定部1的顯影液的特性值之測定值、及由運算部2所算出的成分濃度。控制部3係將所接收之顯影液的特性值或成分濃度當作控制量，依據此控制量，對控制閥41~43發出控制信號。控制係以例如其控制量成為既定的管理值或成為既定的管理區域內的方式進行。 The control section 3 receives the measured value of the characteristic value of the developer from the measurement section 1 and the component concentration calculated by the calculation section 2. The control unit 3 regards the characteristic value or component concentration of the received developer as the control quantity, and sends control signals to the control valves 41 to 43 according to the control quantity. The control system is performed so that, for example, the control amount becomes a predetermined management value or within a predetermined management area.

控制部3具備控制塊。例如，若顯影液管理裝置E是管理顯影液的三個成分濃度A、B、C者的話，則控制部3具備用以控制成分濃度A之控制塊31、用以控制成分濃度B之控制塊32、用以控制成分濃度C之控制塊33。若要管理的成分濃度是二個，則控制塊二個即可，又，若要管理的成分濃度比三個還多則對應其再具備同樣的控制塊。如此，控制部3可對控制閥41~43發出必要的控制信號。 The control unit 3 includes a control block. For example, if the developer management device E manages the three component concentrations A, B, and C of the developer, the control unit 3 includes a control block 31 for controlling the component concentration A and a control block for controlling the component concentration B 32. A control block 33 for controlling the component concentration C. If the concentration of the component to be managed is two, then two control blocks are sufficient. If the concentration of the component to be managed is more than three, the same control block should be provided for it. In this way, the control unit 3 can issue necessary control signals to the control valves 41 to 43.

控制閥41~43是例如在接收「開」信號的期間進行開啟的控制閥，在是預先作了流量調節俾於閥開時可輸送既定流量的開閉控制閥之情況，控制部3在既定時間範圍將「開」信號送往設置在輸送應補給的補充液之管路上的控制閥，藉以向顯影液補給必要的量程度之顯影液管理所需的補充液。 The control valves 41 to 43 are, for example, control valves that are opened during the reception of an "open" signal. When the flow rate is adjusted in advance so that the valve can deliver a predetermined flow rate when the valve is opened, the control unit 3 is used for a predetermined time. The range sends the "on" signal to the control valve set on the pipeline that transports the replenishing liquid that should be replenished, so as to replenish the developer with the necessary amount of replenishing liquid required for developer management.

控制閥的控制動作不受此例所限。在控制閥是依開閉切換信號切換閥之開狀態和閉狀態之情況下，透過控制部3將脈衝的開閉切換信號以既定時間間隔送往控制閥，向顯影液補給僅必要量的所需的補充液。 The control action of the control valve is not limited by this example. In the case that the control valve switches between the open state and the closed state of the valve according to the open/close switching signal, the pulsed open/close switching signal is sent to the control valve at a predetermined time interval through the control unit 3, and only the necessary amount of the required amount is supplied to the developer. Replenishing fluid.

再者，控制閥41~43亦可為能控制閥之開度者，亦可為單純的流量調整閥(針閥)和開閉控制閥之組合。控制閥41~43亦可為電磁閥，亦可為空氣壓操作閥(空氣操作閥)。 Furthermore, the control valves 41 to 43 may be those capable of controlling the opening degree of the valve, or may be a combination of a simple flow control valve (needle valve) and an on-off control valve. The control valves 41 to 43 may also be solenoid valves or air pressure operated valves (air operated valves).

透過控制閥41~43基於控制部3所發出的控制信號進行動作，向顯影液補給顯影液管理所需的量之補充液。控制部3係依據從所接收的控制量(顯影液的特性值或成分濃度)求得之補充液的種類與其必要的補給量，向應控制的控制閥發出控制信號俾輸送必要的補給量。 The penetration control valves 41 to 43 operate based on the control signal issued by the control unit 3 to replenish the developer with an amount of replenishing liquid required for developer management. The control unit 3 sends a control signal to the control valve to be controlled to deliver the necessary replenishment amount based on the type of replenishing solution and the necessary replenishment amount obtained from the received control amount (the characteristic value or component concentration of the developer).

如此，藉由本實施形態的顯影液管理裝置，依據所測定之顯影液的特性值或所算出之顯影液的成分濃度，能以此等成為既定的管理值或成為既定的管理區域內之方式維持管理顯影液。 In this way, with the developer management device of this embodiment, the measured characteristic value of the developer or the calculated component concentration of the developer can be maintained in such a way as to become a predetermined management value or within a predetermined management area. Manage the developer.

更具體言之，如下那樣的顯影液管理是可能的。但是，以下例舉的顯影液管理係為例示，非受此所限者。 More specifically, the following developer management is possible. However, the developer management system exemplified below is an example and is not limited to this.

第一、係以針對重複使用之鹼性顯影液的鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度各自可成為既定的管理值之方式向顯影液補給補充液之顯影液管理。例如，依據本發明的顯影液管理裝置，可將2.38%TMAH水溶液的鹼成分濃度管理成為2.375~2.390(wt%)的範圍內之既定的管理值較佳，更佳為2.380(wt%)，可將溶解光阻劑濃度管理成為0.40(wt%)以下的既定的管理值較佳，更佳為0.15(wt%)，可將吸收二氧化碳濃度管理成為0.40(wt%)以下的既定的管理值較佳，更佳為0.25(wt%)。 First, it is the developer management that replenishes the developer with the replenishing solution so that the concentration of the alkali component, the concentration of the dissolved photoresist and the concentration of the carbon dioxide absorbed can each become a predetermined management value for the reused alkaline developer. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), The dissolved photoresist concentration can be managed to a predetermined management value below 0.40 (wt%), preferably 0.15 (wt%), and the absorbed carbon dioxide concentration can be managed to a predetermined management value below 0.40 (wt%) Preferably, it is more preferably 0.25 (wt%).

第二、係以重複使用之鹼性顯影液的鹼成分濃度可成為既定的管理值、且溶解光阻劑濃度及吸收二氧化碳濃度各自可成為既定的管理值以下之方式向顯影液補給補充液之顯影液管理。例如，依據本發明的顯影液管理裝置，可將2.38%TMAH水溶液的鹼成分濃度管理成為2.375~2.390(wt%)的範圍內的既定的管理值較佳，更佳為2.380(wt%)，可將溶解光阻劑濃度管理成為0.40(wt%)以下較佳，可將吸收二氧化碳濃度管理成為0.40(wt%)以下較佳。 Second, it is to replenish the developer with the replenishment solution in such a way that the alkali component concentration of the repeatedly used alkaline developer can become the established management value, and the dissolved photoresist concentration and the absorbed carbon dioxide concentration can each become below the established management value. Developer management. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), The concentration of the dissolved photoresist can be controlled to 0.40 (wt%) or less, and the concentration of carbon dioxide absorbed can be controlled to 0.40 (wt%) or less.

第三、係以針對重複使用之鹼性顯影液的鹼成分濃度、特定波長中的吸光度及吸收二氧化碳濃度各自可成為既定的管理值之方式向顯影液補給補充液之顯影液管理。例如，依據本發明的顯影液管理裝置，可將2.38%TMAH水溶液的鹼成分濃度管理成為2.375~2.390(wt%)的範圍內的既定的管理值較佳，更佳為2.380(wt%)，可將波長λ=560nm中的吸光度(槽(cell)光路長d=10mm)管理成為1.30(Abs.)以下的既定的管理值較佳，更佳為0.50(Abs.)，可將吸收二氧化碳濃度管理成為0.40(wt%)以下的既定的管理值較佳，更佳為0.25(wt%)。 Thirdly, it is the developer management that replenishes the developer with the replenisher so that the concentration of the alkali component, the absorbance at a specific wavelength, and the concentration of carbon dioxide absorbed by the repeatedly used alkaline developer can each become a predetermined management value. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), The absorbance in wavelength λ=560nm (cell optical path length d=10mm) can be managed to a predetermined management value below 1.30 (Abs.), preferably 0.50 (Abs.), which can reduce the absorption of carbon dioxide concentration It is better to manage to a predetermined management value of 0.40 (wt%) or less, and more preferably 0.25 (wt%).

第四、係以重複使用之鹼性顯影液的鹼成分濃度可成為既定的管理值、特定波長中的吸光度可成為既定的管理區域內、及吸收二氧化碳濃度可成為既定的管理值以下之方式向顯影液補給補充液之顯影液管理。例如，依據本發明的顯影液管理裝置，可將2.38%TMAH水溶液的鹼成分濃度管理成為2.375~2.390(wt%)的範圍內的既定的管理值較佳，更佳為2.380(wt%)，可將波長λ=560nm中的吸光度(槽光路長d=10mm)管理成為1.30(Abs.)以下較佳，更佳為0.65(Abs.)以下，可將吸收二氧化碳濃度管理成為0.40(wt%)以下較佳。 Fourth, the concentration of the alkali component of the repeatedly used alkaline developer can become the predetermined management value, the absorbance at a specific wavelength can be within the predetermined management area, and the absorbed carbon dioxide concentration can become below the predetermined management value. Developer management of developer replenishment replenisher. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), Absorbance at wavelength λ=560nm (groove optical path length d=10mm) can be managed to be 1.30 (Abs.) or less, more preferably 0.65 (Abs.) or less, and the absorbed carbon dioxide concentration can be managed to 0.40 (wt%) The following is better.

第五、係以重複使用之鹼性顯影液的導電率、特定波長中的吸光度及吸收二氧化碳濃度各自可成為既定的管理值之方式向顯影液補給補充液之顯影液管理。例如，依據本發明的顯影液管理裝置，可將2.38%TMAH水溶液的導電率管理成為54.47~54.75(mS/cm)的範圍內的既定的管理值較佳，更佳為54.58(mS/cm)，可將波長λ=560nm中的吸光度(槽光路長d=10mm)管理成為1.3(Abs.)以下的既定的管理值較佳，更佳為0.50(Abs.)，可將吸收二氧化碳濃度管理成為0.40(wt%)以下的既定的管理值較佳，更佳為0.25(wt%)。 Fifth, the developer management that replenishes the developer with replenishing liquid so that the conductivity of the repeatedly used alkaline developer, the absorbance at a specific wavelength, and the concentration of carbon dioxide absorbed can each become a predetermined management value. For example, according to the developer management device of the present invention, the conductivity of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 54.47~54.75 (mS/cm), preferably 54.58 (mS/cm) , The absorbance in the wavelength λ=560nm (slot optical path length d=10mm) can be managed to a predetermined management value below 1.3 (Abs.), preferably 0.50 (Abs.), and the absorbed carbon dioxide concentration can be managed to A predetermined management value of 0.40 (wt%) or less is preferable, and 0.25 (wt%) is more preferable.

第六、係以重複使用之鹼性顯影液的導電率可成為既定的管理值、特定波長中的吸光度可成為既定的管理區域內、及吸收二氧化碳濃度可成為既定的管理值以下之方式向顯影液補給補充液之顯影液管理。例如，依據本發明的顯影液管理裝置，可將2.38%TMAH水溶液的導電率管理成為54.47~54.75(mS/cm)的範圍內的既定的管理值較佳，更佳為54.58(mS/cm)，可將波長λ=560nm中的吸光度(槽光路長d=10mm)管理成為1.30(Abs.)以下較佳，更佳為0.65(Abs.)以下，可將吸收二氧化碳濃度管理成為0.40(wt%)以下較佳。 Sixth, it is developed in such a way that the conductivity of the repeatedly used alkaline developer can become the established management value, the absorbance at a specific wavelength can be within the established management area, and the absorbed carbon dioxide concentration can become below the established management value. Liquid replenishment replenishing liquid developer management. For example, according to the developer management device of the present invention, the conductivity of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 54.47~54.75 (mS/cm), preferably 54.58 (mS/cm) , The absorbance in the wavelength λ=560nm (the optical path length of the groove d=10mm) can be managed to be 1.30 (Abs.) or less, more preferably 0.65 (Abs.) or less, and the absorbed carbon dioxide concentration can be managed to 0.40 (wt%) ) The following are preferred.

因此，依據本實施形態的顯影液管理裝置，與習知者相比，由於能將顯影液的各成分濃度或各特性值高精度地管理既定的管理值或管理區域內，故可將顯影液維持在最佳的顯影性能，可實現所期望的線寬或殘餘膜厚。又，警報部WD在藉運算部2所算出之成分濃度中至少任一者偏離所設定之管理範圍時發出警報。 Therefore, according to the developer management device of this embodiment, the concentration of each component or characteristic value of the developer can be managed with high accuracy in a predetermined management value or management area, compared with the prior art. Maintain the best development performance, can achieve the desired line width or residual film thickness. In addition, the alarm unit WD issues an alarm when at least one of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

[第十一實施形態] [Eleventh Embodiment]

圖19係用以說明設於輸送要向顯影液補給的補充液之管路上之控制閥41~43是位在本實施形態的顯影液管理裝置的外部之實施形態的顯影液管理裝置的示意圖。 Fig. 19 is a schematic diagram for explaining that the control valves 41 to 43 provided on the pipeline for conveying the replenishing liquid to be replenished to the developer are located outside the developer management device of this embodiment.

本實施形態的顯影液管理裝置E具備：測定部1，具備測定顯影液的複數個特性值之複數個測定構件；運算部2，含有利用多變量分析法的運算塊21；控制部3，將顯影液的特性值或成分濃度中任一者作為控制量且使其成為既定的管理值或管理區域內之方式向設於補充液的補給管路上之控制閥41~43發出控制信號；及警報部WD。 The developer management device E of the present embodiment includes: a measuring section 1 including a plurality of measurement members for measuring a plurality of characteristic values of the developer; a calculation section 2 including a calculation block 21 using a multivariate analysis method; a control section 3 Either the characteristic value or the component concentration of the developer is used as the control quantity and it becomes the established management value or within the management area to send a control signal to the control valves 41~43 arranged on the replenishing liquid supply line; and WD.

本實施形態中，被控制部3控制的控制閥41~43並非顯影液管理裝置E的內部零件。以和顯影液管理裝置E分開而設置在輸送補充液的管路上。顯影液管理裝置E未被連接到輸送補充液的此等管路上。 In this embodiment, the control valves 41 to 43 controlled by the control unit 3 are not internal parts of the developer management device E. Separately from the developer management device E, it is installed in the pipeline for conveying the replenisher. The developer management device E is not connected to these pipelines that transport the replenisher.

其他的構成、動作等係和第十實施形態相同，故予以省略。 The other configurations, operations, etc. are the same as those of the tenth embodiment, so they are omitted.

[第十二實施形態] [Twelfth Embodiment]

圖20係具備一併擁有運算功能和控制功能的運算控制部23之顯影液管理裝置E的示意圖。 FIG. 20 is a schematic diagram of a developer management device E provided with an arithmetic control unit 23 having arithmetic function and control function together.

本發明的顯影液管理裝置E不受限於運算部2和控制部3構成為分開的裝置之情況。亦可構成為一併擁有運算功能和控制功能之一體的運算控制部23。作為運算控制部23，例如可舉出電腦等之多功能裝置。顯影液管理裝置E具備警報部WD。 The developer management device E of the present invention is not limited to the case where the calculation section 2 and the control section 3 are configured as separate devices. It may also be configured as the arithmetic control unit 23 that has one of the arithmetic function and the control function. As the calculation control unit 23, for example, a multi-function device such as a computer can be cited. The developer management device E includes an alarm unit WD.

電腦具備有輸入/輸出功能、收發功能、運算功能、控制功能、顯示功能等之非常多樣的功能。因此，本發明的顯影液管理裝置E之運算功能、控制功能可藉由電腦實現。運算控制部23只要連接到測定部1及控制閥41~43即可。此時，若將是從藉由多變量分析法所測定之顯影液的特性值算出成分濃度之運算處理程式、和是對控制閥41~43發出控制信號俾控制量(顯影液的特性值或成分濃度)成為既定的管理值或既定的管理區域內的控制程式安裝於電腦的話，則可將顯影液維持管理在既定的狀態。 The computer has a wide variety of functions such as input/output functions, sending and receiving functions, calculation functions, control functions, and display functions. Therefore, the calculation function and control function of the developer management device E of the present invention can be realized by a computer. The calculation control unit 23 only needs to be connected to the measurement unit 1 and the control valves 41 to 43. At this time, if it is an arithmetic processing program that calculates the component concentration from the characteristic value of the developer measured by the multivariate analysis method, and sends a control signal to the control valves 41 to 43 to control the amount (the characteristic value of the developer or If the component concentration) becomes a predetermined management value or a control program in a predetermined management area is installed in a computer, the developer can be maintained and managed in a predetermined state.

其他的構成、動作等係和第十實施形態相同，故予以省略。 The other configurations, operations, etc. are the same as those of the tenth embodiment, so they are omitted.

[第十三實施形態] [Thirteenth Embodiment]

圖21係管理顯影液的二個成分之顯影液管理裝置的示意圖。本實施形態的顯影液管理裝置E係可較佳地適用於管理被管理成二氧化碳的吸收較少之鹼性顯影液的鹼成分濃度和溶解光阻劑濃度之情況等。 Figure 21 is a schematic diagram of a developer management device that manages two components of a developer. The developer management device E of the present embodiment can be suitably used to manage the concentration of the alkali component and the concentration of the dissolved photoresist in an alkaline developer that is managed to absorb less carbon dioxide.

若設為第一測定構件11是測定與顯影液的成分中至少鹼成分濃度有關之顯影液的特性值的測定構件(例如測定導電率之導電率計)、且第二測定構件12是測定與顯影液的成分中至少溶解光阻劑濃度有關之顯影液的特性值的測定構件(例如測定λ=560nm中的吸光度之吸光光度計)的話，由於運算部2含有利用多變量分析法的運算塊21，故可由藉多變量分析法所測定之顯影液的特性值，算出顯影液的鹼成分濃度及溶解光阻劑濃度。 If it is assumed that the first measuring member 11 is a measuring member that measures the characteristic value of the developer related to the concentration of at least the alkali component in the components of the developer (for example, a conductivity meter for measuring electrical conductivity), and the second measuring member 12 is to measure and If the component of the developer solution at least dissolves the characteristic value of the developer solution related to the photoresist concentration (for example, an absorbance photometer that measures the absorbance at λ=560nm), the calculation unit 2 contains a calculation block using a multivariate analysis method. 21. Therefore, the concentration of the alkali component and the concentration of the dissolved photoresist in the developer can be calculated from the characteristic value of the developer measured by the multivariate analysis method.

於是，在控制塊31是以顯影液的導電率或鹼成分濃度可成為既定的管理值之方式向控制閥發出控制信號之控制塊，且控制塊32是以顯影液的特定波長(例如λ=560nm)中的吸光度或溶解光阻劑濃度可成為既定的管理值或管理區域內之方式向控制閥發出控制信號之控制塊時，由於控制部3係以可接收所測定之顯影液的特性值與所算出之顯影液的成分濃度的方式和測定部1及運算部2連接，故本實施態樣的顯影液管理裝置E，能以使顯影液的鹼成分濃度成為既定的管理值、使溶解光阻劑濃度成為既定的管理值或管理區域內的方式維持管理顯影液。 Therefore, the control block 31 is a control block that sends a control signal to the control valve in such a way that the conductivity or alkali component concentration of the developer can become a predetermined management value, and the control block 32 is a specific wavelength of the developer (for example, λ= When the absorbance or dissolved photoresist concentration in 560nm) can become a predetermined management value or a control block that sends a control signal to the control valve in the management area, because the control unit 3 can receive the measured characteristic value of the developer It is connected to the measuring section 1 and the computing section 2 with the calculated component concentration of the developer. Therefore, the developer management device E of this embodiment can make the concentration of the alkali component of the developer a predetermined management value and dissolve The developer is maintained and managed so that the photoresist concentration becomes a predetermined management value or within the management area.

其他的詳情係和其他實施形態相同，故予以省略。 The other details are the same as the other embodiments, so they are omitted.

[第十四實施形態] [Fourteenth Embodiment]

圖22係顯影液的二個成分藉由成分濃度作管理之顯影液管理裝置的示意圖。本實施形態的顯影液管理裝置係可較佳地適用於將經管理成不吸收二氧化碳的鹼性顯影液的鹼成分濃度和溶解光阻劑濃度管理成管理濃度值的情況等。 Fig. 22 is a schematic diagram of a developer management device in which two components of a developer are managed by component concentrations. The developer management device of the present embodiment can be preferably applied to a case where the alkali component concentration and the dissolved photoresist concentration of an alkaline developer managed to not absorb carbon dioxide are managed to manage concentration values.

若設為第一測定構件11是測定與顯影液的成分中至少鹼成分濃度有關之顯影液的特性值的測定構件(例如測定導電率之導電率計)、且第二測定構件12是測定與顯影液的成分中至少溶解光阻劑濃度有關之顯影液的特性值的測定構件(例如測定λ=560nm中的吸光度之吸光光度計)的話，由於運算部2含有利用多變量分析 法的運算塊21，故可由藉多變量分析法所測定之顯影液的特性值算出顯影液的鹼成分濃度及溶解光阻劑濃度。 If it is assumed that the first measuring member 11 is a measuring member that measures the characteristic value of the developer related to the concentration of at least the alkali component in the components of the developer (for example, a conductivity meter for measuring electrical conductivity), and the second measuring member 12 is to measure and If the components of the developer solution at least dissolve the characteristic value of the developer solution related to the photoresist concentration (for example, an absorbance photometer that measures the absorbance at λ=560nm), the calculation unit 2 contains the use of multivariate analysis The calculation block 21 of the method can calculate the alkali component concentration and the dissolved photoresist concentration of the developer from the characteristic value of the developer measured by the multivariate analysis method.

於是，若設為控制塊31是以鹼成分濃度可成為既定的管理值之方式向控制閥發出控制信號的控制塊，且控制塊32是以溶解光阻劑濃度可成為既定的管理值或管理值以下之方式向控制閥發出控制信號的控制塊的話，由於控制部3係以可接收所算出之顯影液的成分濃度的方式和運算部2連接，故依據本實施態樣的顯影液管理裝置E，能以使顯影液的鹼成分濃度成為既定的管理值、使溶解光阻劑濃度成為既定的管理值或管理值以下的方式維持管理顯影液。 Therefore, if the control block 31 is a control block that sends a control signal to the control valve so that the alkali component concentration can become a predetermined management value, and the control block 32 is a dissolved photoresist concentration that can become a predetermined management value or management If the control block sends a control signal to the control valve below the value, since the control section 3 is connected to the calculation section 2 in a manner that can receive the calculated component concentration of the developer, the developer management device according to this embodiment E. The developer can be maintained and managed so that the concentration of the alkali component of the developer becomes a predetermined management value, and the concentration of the dissolved photoresist becomes the predetermined management value or less.

其他的詳情係和其他實施形態相同，故予以省略。 The other details are the same as the other embodiments, so they are omitted.

[第十五實施形態] [Fifteenth Embodiment]

圖23係顯影液的三個成分中的二個藉由特性值而另一個藉由成分濃度作管理的顯影液管理裝置的示意圖。本實施形態的顯影液管理裝置係可較佳地適用於鹼性顯影液的鹼成分濃度藉由導電率、溶解光阻劑濃度藉由特定波長(例如λ=560nm)中的吸光度作管理、及吸收二氧化碳濃度藉由濃度作管理的情況等。 FIG. 23 is a schematic diagram of a developer management device in which two of the three components of the developer are managed by characteristic values and the other by the component concentration. The developer management device of this embodiment is preferably suitable for the management of the alkali component concentration of the alkaline developer by the conductivity, the dissolved photoresist concentration by the absorbance in a specific wavelength (for example, λ=560nm), and The concentration of absorbed carbon dioxide is managed by the concentration, etc.

若設為第一測定構件11是測定與顯影液的成分中至少鹼成分濃度有關之顯影液的特性值的測定構件(例如，測定導電率之導電率計)、第二測定構件12是測定與顯影液的成分中至少溶解光阻劑濃度有關之顯影液的特性值的測定構件(例如，測定λ=560nm中的吸光度 之吸光光度計)、及第三測定構件是測定與顯影液的成分中至少吸收二氧化碳濃度有關之顯影液的特性值的測定構件(例如，測定密度之密度計)的話，由於運算部2含有利用多變量分析法的運算塊21，故可由藉多變量分析法所測定之顯影液的特性值，算出顯影液的鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度。 If it is assumed that the first measuring member 11 is a measuring member for measuring the characteristic value of the developer related to at least the concentration of the alkali component in the components of the developer (for example, a conductivity meter for measuring conductivity), the second measuring member 12 is for measuring and The component of the developer solution at least dissolves the characteristic value of the developer solution related to the photoresist concentration (for example, measuring the absorbance in λ=560nm The absorbance photometer), and the third measuring means are measuring means for measuring the characteristic value of the developer related to at least the concentration of carbon dioxide absorbed in the components of the developer (for example, a densitometer for measuring density), because the calculation unit 2 contains The operation block 21 of the multivariate analysis method can calculate the alkali component concentration, the dissolved photoresist concentration and the absorbed carbon dioxide concentration of the developer from the characteristic values of the developer measured by the multivariate analysis method.

於是，在控制塊31是以顯影液的導電率可成為既定的管理值的方式向控制閥發出控制信號的控制塊、控制塊32是以顯影液的特性波長(例如λ=560nm)中的吸光度可成為既定的管理值或管理區域內的方式向控制閥發出控制信號的控制塊、且控制塊33是以吸收二氧化碳濃度可成為既定的管理值或管理值以下的方式向控制閥發出控制信號的控制塊時，由於控制部3係以可接收所測定之顯影液的特性值的方式和測定部1連接、且可接收所算出之顯影液的成分濃度的方式和運算部2連接，故依據本實施態樣的顯影液管理裝置E，能以使顯影液的鹼成分濃度成為既定的管理值、使溶解光阻劑濃度成為既定的管理值或管理值以下、及使吸收二氧化碳濃度成為既定的管理值或管理值以下的方式維持管理顯影液。 Therefore, the control block 31 is a control block that sends a control signal to the control valve so that the conductivity of the developer can become a predetermined management value, and the control block 32 is the absorbance in the characteristic wavelength of the developer (for example, λ=560nm). It can be a control block that sends a control signal to the control valve in a manner within a predetermined management value or a management area, and the control block 33 sends a control signal to the control valve in a manner that the absorbed carbon dioxide concentration can become a predetermined management value or below the management value When controlling the block, since the control section 3 is connected to the measuring section 1 in a manner that can receive the measured characteristic value of the developer, and is connected to the computing section 2 in a manner that can receive the calculated component concentration of the developer, it is based on this The embodiment of the developer management device E can manage the alkali component concentration of the developer to the predetermined management value, the dissolved photoresist concentration to be the predetermined management value or less, and the absorbed carbon dioxide concentration to be the predetermined management The developer is maintained and managed below the value or management value.

其他的詳情係和其他實施形態相同，故予以省略。 The other details are the same as the other embodiments, so they are omitted.

[第十六實施形態] [Sixteenth Embodiment]

圖24係顯影液的三個成分中的一個藉由特性值而另二個藉由成分濃度作管理之顯影液管理裝置的 示意圖。本實施形態的顯影液管理裝置係可較佳地適用於鹼性顯影液的鹼成分濃度和吸收二氧化碳濃度藉由濃度作管理、及溶解光阻劑濃度藉由特定波長(例如，λ=560nm)中的吸光度作管理的情況等。 Figure 24 is the development of a developer management device in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration Schematic. The developer management device of this embodiment is preferably suitable for the management of the alkali component concentration and the absorbed carbon dioxide concentration of the alkaline developer by the concentration, and the dissolved photoresist concentration by the specific wavelength (for example, λ=560nm) In the case of management, etc.

若設為第一測定構件11是測定與顯影液的成分中至少鹼成分濃度有關之顯影液的特性值得測定構件(例如，測定導電率之導電率計)、第二測定構件12是測定與顯影液的成分中至少溶解光阻劑濃度有關之顯影液的特性值的測定構件(例如，測定λ=560nm中的吸光度之吸光光度計)、且第三測定構件是測定與顯影液的成分中至少吸收二氧化碳濃度有關之顯影液的特性值的測定構件(例如測定密度之密度計)的話，由於運算部2含有利用多變量分析法的運算塊21，故可從藉多變量分析法所測定之顯影液的特性值，算出顯影液的鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度。 If it is assumed that the first measuring member 11 is a measuring member for measuring the characteristic value of the developer related to at least the concentration of the alkali component in the components of the developer (for example, a conductivity meter for measuring conductivity), the second measuring member 12 is for measuring and developing The component of the liquid at least dissolves the characteristic value of the developer related to the concentration of the photoresist (for example, an absorbance photometer that measures the absorbance at λ=560nm), and the third measuring means measures at least the component of the developer In the case of a measuring member that absorbs the characteristic value of the developer related to the carbon dioxide concentration (for example, a densitometer for measuring density), since the calculation section 2 includes a calculation block 21 using a multivariate analysis method, it can be obtained from the development measured by the multivariate analysis method. The characteristic value of the liquid, the alkali component concentration, the dissolved photoresist concentration and the carbon dioxide absorption concentration of the developer are calculated.

於是，在控制塊31是以鹼成分濃度可成為既定的管理值的方式向控制閥發出控制信號的控制塊、控制塊32是以顯影液的特性波長(例如，λ=560nm)中的吸光度可成為既定的管理值或管理區域內的方式向控制閥發出控制信號的控制塊，控制塊33是以吸收二氧化碳濃度可成為既定的管理值或管理值以下的方式向控制閥發出控制信號的控制塊時，由於控制部3係以可接收所測定之顯影液的特性值的方式和測定部1連接、可接收所算出之顯影液的成分濃度的方式和運算部2連接，故依據本實施態樣的顯影液管理裝置E，能以使顯影液的 鹼成分濃度成為既定的管理值、使溶解光阻劑濃度成為既定的管理值或管理值以下、及使吸收二氧化碳濃度成為既定的管理值或管理值以下的方式維持管理顯影液。 Therefore, the control block 31 is a control block that sends a control signal to the control valve so that the alkali component concentration can become a predetermined management value, and the control block 32 is the absorbance at the characteristic wavelength of the developer (for example, λ=560nm). A control block that sends a control signal to the control valve when it becomes a predetermined management value or within a management area. The control block 33 is a control block that sends a control signal to the control valve so that the concentration of carbon dioxide absorbed can become the predetermined management value or below the management value. In this case, since the control section 3 is connected to the measuring section 1 in a manner that can receive the measured characteristic value of the developer, and is connected to the computing section 2 in a manner that can receive the calculated component concentration of the developer, it is based on this embodiment. The developer management device E can make the developer The developer is maintained and managed so that the alkali component concentration becomes a predetermined management value, the dissolved photoresist concentration becomes the predetermined management value or less, and the absorbed carbon dioxide concentration becomes the predetermined management value or less.

其他的詳情係和其他實施形態同樣，故予以省略。 The other details are the same as the other embodiments, so they are omitted.

[第十七實施形態] [Seventeenth Embodiment]

圖25係顯影液的三個成分藉由成分濃度作管理之顯影液管理裝置的示意圖。本實施形態的顯影液管理裝置係可較佳地適用於藉由濃度管理鹼性顯影液的鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度的情況等。 FIG. 25 is a schematic diagram of a developer management device in which three components of a developer are managed by component concentrations. The developer management device of this embodiment can be preferably applied to the case where the concentration of the alkali component, the concentration of the dissolved photoresist, the concentration of carbon dioxide absorption, etc. of the alkaline developer are managed by the concentration.

若設為第一測定構件11是測定與顯影液的成分中至少鹼成分濃度有關之顯影液的特性值的測定構件(例如測定導電率之導電率計)、第二測定構件12是測定與顯影液的成分中至少溶解光阻劑濃度有關之顯影液的特性值的測定構件(例如測定λ=560nm中的吸光度之吸光光度計)、且第三測定構件是測定與顯影液的成分中至少吸收二氧化碳濃度有關之顯影液的特性值的測定構件(例如測定密度之密度計)的話，由於運算部2含有利用多變量分析法的運算塊21，故可從藉多變量分析法所測定之顯影液的特性值，算出顯影液的鹼成分濃度、溶解光阻劑濃度及吸收二氧化碳濃度。 If it is assumed that the first measuring member 11 is a measuring member for measuring the characteristic value of the developer related to at least the concentration of the alkali component in the components of the developer (for example, a conductivity meter for measuring conductivity), the second measuring member 12 is for measuring and developing The component of the liquid at least dissolves the characteristic value of the developer related to the concentration of the photoresist (for example, an absorbance photometer that measures the absorbance at λ=560nm), and the third measuring component measures at least the absorption in the component of the developer. In the case of a measuring component (such as a densitometer for measuring density) of the characteristic value of the developer related to the carbon dioxide concentration, since the calculation section 2 contains the calculation block 21 using the multivariate analysis method, it can be obtained from the developer measured by the multivariate analysis method. Calculate the alkali component concentration, dissolved photoresist concentration, and carbon dioxide absorption concentration of the developer.

於是，在控制塊31是以鹼成分濃度可成為既定的管理值的方式向控制閥發出控制信號的控制塊、控制塊32是以容器光阻劑濃度可成為既定的管理值或管理值以下的方式向控制閥發出控制信號的控制塊、且控制塊33是以吸收二氧化碳濃度可成為既定的管理值或管理值以下的方式向控制閥發出控制信號的控制塊時，由於控制部3係以可接收所算出之顯影液的成分濃度的方式和運算部2連接，故依據本實施態樣的顯影液管理裝置E，能以使顯影液的鹼成分濃度成為既定的管理值、使溶解光阻劑濃度成為既定的管理值或管理值以下、及使吸收二氧化碳濃度成為既定的管理值或管理值以下的方式維持管理顯影液。 Therefore, the control block 31 is a control block that sends a control signal to the control valve so that the alkali component concentration can become a predetermined management value, and the control block 32 is such that the container photoresist concentration can become a predetermined management value or below the management value. When the control block sends a control signal to the control valve, and the control block 33 is a control block that sends a control signal to the control valve so that the concentration of carbon dioxide absorbed can become a predetermined management value or below, the control unit 3 can The method of receiving the calculated component concentration of the developer is connected to the calculation unit 2. Therefore, the developer management device E according to this embodiment can make the concentration of the alkali component of the developer reach a predetermined management value and dissolve the photoresist The developer is maintained and managed so that the concentration becomes a predetermined management value or less, and the absorbed carbon dioxide concentration becomes a predetermined management value or less.

其他的詳情係和其他實施形態同樣，故予以省略。 The other details are the same as the other embodiments, so they are omitted.

以上，如第十到第十七實施形態所示，本實施形態的顯影液管理裝置具備：測定部1，測定與鹼性顯影液的成分濃度有關之顯影液的複數個特性值；運算部2，藉由多變量分析法從藉測定部1所測定之複數個特性值算出顯影液的成分濃度；及控制部3，依據藉測定部1所測定之顯影液的特性值或藉運算部2所算出之顯影液的成分濃度向設於輸送要補給到顯影液的補充液之管路上之控制閥41~43發出控制信號。 As described above, as shown in the tenth to seventeenth embodiments, the developer management device of this embodiment includes: a measuring unit 1 that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer; and a computing unit 2 , Calculate the component concentration of the developer from the plurality of characteristic values measured by the measuring section 1 by the multivariate analysis method; and the control section 3, based on the characteristic value of the developer measured by the measuring section 1 or the calculation section 2 The calculated component concentration of the developer sends control signals to the control valves 41 to 43 provided on the pipeline for conveying the replenishing liquid to be replenished to the developer.

本實施形態的顯影液管理裝置中的測定部1及運算部2，係和顯影液的濃度監視裝置中的測定部1及運算部2同樣地可採用各種態樣。 The measurement unit 1 and the calculation unit 2 in the developer management device of the present embodiment can adopt various aspects similarly to the measurement unit 1 and the calculation unit 2 in the developer concentration monitoring device.

本實施形態的顯影液管理裝置中的控制部3沒必要設置成是與運算部2分開的裝置，亦能被安裝成一體的裝置(例如電腦)的控制功能和運算功能。又， 如同圖11，控制部3亦能與測定部1、運算部2分開構成。控制部3只要是以可接收成為控制量的藉由測定部1所測定之特性值或藉由運算部2所算出之成分濃度的方式與測定部1、運算部2相互連絡即可。如此一來，則可依據所接收的特性值或成分濃度發出必要的控制信號。 The control unit 3 in the developer management device of this embodiment does not need to be a separate device from the computing unit 2, and can also be installed as an integrated device (such as a computer) for the control function and computing function. Moreover, like FIG. 11, the control unit 3 can also be configured separately from the measurement unit 1 and the calculation unit 2. The control unit 3 only needs to communicate with the measurement unit 1 and the calculation unit 2 so as to be able to receive the characteristic value measured by the measurement unit 1 or the component concentration calculated by the calculation unit 2 as the control quantity. In this way, the necessary control signal can be sent out according to the received characteristic value or component concentration.

針對用以輸送補充液的管路，也可連接於本實施形態的顯影液管理裝置E，也可不連接。控制閥也可以不是顯影液管理裝置E的內部零件。若是以藉由控制部3的控制信號而控制的方式與控制部3連絡的話，則亦可設置於顯影液管理裝置E的外部。 Regarding the pipeline for conveying the replenisher, it may be connected to the developer management device E of this embodiment or not. The control valve may not be an internal part of the developer management device E. If the control unit 3 is connected to the control unit 3 by the control signal of the control unit 3, it can also be installed outside the developer management device E.

如以上所述，依據本發明的顯影液管理裝置，可將顯影液的各成分濃度或各特性值管理在既定的管理值或管理範圍內。因此，藉由本發明的顯影液管理裝置，可維持最佳的顯影性能，可實現所期望的線寬或殘餘膜厚。 As described above, according to the developer management device of the present invention, the concentration of each component or the characteristic value of the developer can be managed within a predetermined management value or management range. Therefore, with the developer management device of the present invention, the best development performance can be maintained, and the desired line width or residual film thickness can be achieved.

依據本發明的顯影液管理裝置，由於顯影液的各成分濃度被精確控制成既定的狀態，故能使顯影液的顯影性能更加精確而成為固定地作維護管理。因此，可期待將光阻劑顯影時的顯影速度固定且穩定化，使利用顯影處理的線寬或殘餘膜厚被固定化，提升製品品質，同時可期待有助益於實現更加微細化及高積體化。 According to the developer management device of the present invention, since the concentration of each component of the developer is accurately controlled to a predetermined state, the development performance of the developer can be made more accurate and fixed for maintenance and management. Therefore, it can be expected that the development speed during photoresist development can be fixed and stabilized, the line width or residual film thickness of the development process can be fixed, and the product quality can be improved. At the same time, it can be expected to help achieve more miniaturization and high Integration.

依據本發明的顯影液管理裝置，由於顯影液被自動維持在始終最佳的顯影性能，故使製品良率提升，同時變得不需要顯影液的更換作業，可期待有助益於減低運轉成本或廢液成本。 According to the developer management device of the present invention, since the developer is automatically maintained at the best developing performance at all times, the product yield is improved, and at the same time, the replacement of the developer is unnecessary, which can be expected to help reduce operating costs. Or waste liquid cost.

1:測定部 1: Measurement department

2:運算部 2: Computing Department

11:第一測定構件 11: The first measurement component

12:第二測定構件 12: The second measuring component

14:取樣泵 14: Sampling pump

15:取樣配管 15: Sampling piping

16:回流配管 16: Return piping

21:運算塊 21: Operation block

51、52:測定數據用信號線 51, 52: Signal line for measurement data

61:顯影液貯留槽 61: Developer storage tank

62:溢流槽 62: overflow trough

63:液面計 63: Liquid level gauge

64:顯影室罩 64: developing room cover

65:滾輪式輸送機 65: Roller conveyor

66:基板 66: substrate

67:顯影液噴灑頭 67: Developer spray head

71:廢液泵 71: Waste Liquid Pump

72:循環泵 72: circulation pump

73:過濾器 73: filter

80:顯影液管路 80: Developer pipeline

A:成分濃度測定裝置 A: Component concentration measuring device

B:顯影製程設備 B: Development process equipment

WD:警報部 WD: Alarm Department

Claims (12)

一種顯影液的濃度監視裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值；運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃度；及警報部，在藉前述運算部所算出之前述成分濃度中至少一者偏離所設定之管理範圍時發出警報。 A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and an arithmetic unit based on the aforementioned measurement by the measuring unit A plurality of characteristic values are calculated by a multivariate analysis method to calculate the component concentration of the developer; and an alarm unit that issues an alarm when at least one of the component concentrations calculated by the calculation unit deviates from the set management range. 如請求項1之顯影液的濃度監視裝置，其中作為前述警報部，至少具備以下任一者：傳送警報信號的外部輸出信號端子、發出警報音的警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子。 For example, the developer concentration monitoring device of claim 1, wherein as the aforementioned alarm unit, at least one of the following is provided: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, and a warning lamp that lights or flashes light , The display device to display the warning, and the relay terminal to switch the opening and closing of the contact. 一種顯影液的濃度監視裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值；及運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃度，按各前述成分濃度具備在藉前述運算部所算出之前述成分濃度偏離所設定之管理範圍時發出警報的警報部。 A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and an arithmetic unit based on the measurement by the measuring unit The plurality of characteristic values calculate the component concentration of the developer by a multivariate analysis method, and each component concentration is provided with an alarm unit that generates an alarm when the component concentration calculated by the calculation unit deviates from the set management range. 如請求項3之顯影液的濃度監視裝置，其中作為前述警報部，至少具備以下任一者： 傳送警報信號的外部輸出信號端子、發出警報音的警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子。 For example, the developer concentration monitoring device of claim 3, wherein as the aforementioned alarm unit, at least one of the following is provided: An external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, a display device that displays a warning, and a relay terminal that switches the contacts on and off. 一種顯影液管理裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值；運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃度；警報部，在藉前述運算部所算出之前述成分濃度中至少一者偏離所設定之管理範圍時發出警報；及控制部，依據從藉前述測定部所測定之前述顯影液的複數個特性值及藉前述運算部所算出之前述顯影液的成分濃度中所選擇之管理對象項目的測定值或算出值，對設在用以輸送要被補給到前述顯影液的補充液之管路上之控制閥發出控制信號。 A developer management device comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of a developer that is repeatedly used showing alkalinity; and an arithmetic unit based on the plurality of characteristic values measured by the measuring unit The characteristic value is calculated by the multivariate analysis method of the component concentration of the developer; the alarm unit, when at least one of the component concentrations calculated by the calculation unit deviates from the set management range; and the control unit, based on The measured value or calculated value of the management target item selected from the plurality of characteristic values of the developer measured by the measuring unit and the component concentration of the developer calculated by the calculating unit are set for conveying The control valve on the pipeline of the replenishing liquid to be replenished to the aforementioned developer sends a control signal. 如請求項5之顯影液管理裝置，其中作為警報部，至少具備以下任一者：傳送警報信號的外部輸出信號端子、發出警報音的警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子。 For example, the developer management device of claim 5, which, as an alarm unit, has at least one of the following: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, and a warning display The display device, and the relay terminal for switching the opening and closing of the contact. 如請求項5或6之顯影液管理裝置，其中前述成分濃度是前述顯影液的鹼成分的濃度及光阻劑的濃度，前述測定部具備：第一測定構件，測定與前述顯影液的成分中至少 鹼成分的濃度有關之前述顯影液的特性值；及第二測定構件，測定與前述顯影液的成分中至少溶解於前述顯影液的光阻劑的濃度有關之前述顯影液的特性值，前述運算部具備算出前述顯影液的鹼成分的濃度及光阻劑的濃度之運算塊。 According to the developer management device of claim 5 or 6, wherein the component concentration is the concentration of the alkali component of the developer and the concentration of the photoresist, and the measuring unit includes: a first measuring member that measures the components of the developer at least The characteristic value of the developer related to the concentration of the alkali component; and a second measuring means for measuring the characteristic value of the developer related to the concentration of the photoresist at least dissolved in the developer in the component of the developer, and the aforementioned calculation The section is provided with a calculation block for calculating the concentration of the alkali component of the developer and the concentration of the photoresist. 如請求項5或6之顯影液管理裝置，其中前述成分濃度是前述顯影液的鹼成分的濃度、光阻劑的濃度及二氧化碳的濃度，前述測定部具備：第一測定構件，測定與前述顯影液的成分中至少鹼成分的濃度有關的前述顯影液的特性值；第二測定構件，測定與前述顯影液的成分中至少溶解於前述顯影液的光阻劑的濃度有關之前述顯影液的特性值；及第三測定構件，測定與前述顯影液的成分中至少前述顯影液所吸收的二氧化碳的濃度有關之前述顯影液的特性值，前述運算部具備算出前述顯影液的鹼成分的濃度、光阻劑的濃度及二氧化碳的濃度之運算塊。 According to the developer management device of claim 5 or 6, wherein the component concentration is the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide, and the measurement unit includes: a first measurement means for measuring and developing The characteristic value of the developer related to the concentration of at least the alkali component among the components of the liquid; the second measuring means measures the characteristic of the developer related to the concentration of the photoresist at least dissolved in the developer in the component of the developer Value; and a third measuring means for measuring the characteristic value of the developer related to at least the concentration of carbon dioxide absorbed by the developer among the components of the developer, and the calculation unit is equipped to calculate the concentration of the alkali component of the developer, light The calculation block of the concentration of the resist and the concentration of carbon dioxide. 一種顯影液管理裝置，具備：測定部，測定與重複使用之呈現鹼性的顯影液的成分濃度有關之前述顯影液的複數個特性值；運算部，依據藉前述測定部所測定之前述複數個特性值，藉由多變量分析法算出前述顯影液的成分濃 度；及控制部，依據從藉前述測定部所測定之前述顯影液的複數個特性值及藉前述運算部所算出之前述顯影液的成分濃度中所選擇之管理對象項目的測定值或算出值，對設在用以輸送要被補給到前述顯影液的補充液之管路上之控制閥發出控制信號，按各前述成分濃度而具備在藉前述運算部所算出之前述成分濃度偏離所設定之管理範圍時發出警報的警報部。 A developer management device comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of a developer that is repeatedly used showing alkalinity; and an arithmetic unit based on the plurality of characteristic values measured by the measuring unit The characteristic value is calculated by the multivariate analysis method to calculate the component concentration of the aforementioned developer Degree; and the control unit, based on the measured value or calculated value of the management target item selected from the plurality of characteristic values of the developer measured by the measuring unit and the component concentration of the developer calculated by the calculating unit , To send a control signal to the control valve set on the pipeline for conveying the replenishing liquid to be replenished to the developer, and to control the deviation of the component concentration calculated by the calculation unit according to the concentration of each component The alarm section that issues an alarm when it is in the range. 如請求項9之顯影液管理裝置，其中作為警報部，至少具備以下任一者：傳送警報信號的外部輸出信號端子、發出警報音的警報裝置、使光點亮或閃爍的警告燈、顯示警告的顯示裝置、及切換接點的開閉之繼電器端子。 For example, the developer management device of claim 9, which, as an alarm unit, has at least one of the following: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, and a warning display The display device, and the relay terminal for switching the opening and closing of the contact. 如請求項9或10之顯影液管理裝置，其中前述成分濃度是前述顯影液的鹼成分的濃度及光阻劑的濃度，前述測定部具備：第一測定構件，測定與前述顯影液的成分中至少鹼成分的濃度有關之前述顯影液的特性值；及第二測定構件，測定與前述顯影液的成分中至少溶解於前述顯影液的光阻劑的濃度有關之前述顯影液的特性值，前述運算部具備算出前述顯影液的鹼成分的濃度及光阻劑的濃度之運算塊。 According to the developer management device of claim 9 or 10, wherein the component concentration is the concentration of the alkali component of the developer and the concentration of the photoresist, and the measurement unit includes: a first measuring member that measures the concentration of the component in the developer At least the characteristic value of the developer related to the concentration of the alkali component; and a second measuring means for measuring the characteristic value of the developer related to the concentration of the photoresist at least dissolved in the developer in the component of the developer; The calculation unit includes a calculation block for calculating the concentration of the alkali component of the developer and the concentration of the photoresist. 如請求項9或10之顯影液管理裝置，其中前述成分 濃度是前述顯影液的鹼成分的濃度、光阻劑的濃度及二氧化碳的濃度，前述測定部具備：第一測定構件，測定與前述顯影液的成分中至少鹼成分的濃度有關的前述顯影液的特性值；第二測定構件，測定與前述顯影液的成分中至少溶解於前述顯影液的光阻劑的濃度有關之前述顯影液的特性值；及第三測定構件，測定與前述顯影液的成分中至少前述顯影液所吸收的二氧化碳的濃度有關之前述顯影液的特性值，前述運算部具備算出前述顯影液的鹼成分的濃度、光阻劑的濃度及二氧化碳的濃度之運算塊。 Such as the developer management device of claim 9 or 10, wherein the aforementioned components The concentration is the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide. The measurement unit includes: a first measuring means for measuring the concentration of the developer related to the concentration of at least the alkali component in the component of the developer Characteristic value; a second measuring means for measuring the characteristic value of the developer in relation to the concentration of at least the photoresist dissolved in the developer among the components of the developer; and a third measuring means for measuring the composition of the developer Among them, the characteristic value of the developer is related to at least the concentration of carbon dioxide absorbed by the developer, and the calculation unit includes a calculation block for calculating the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide.
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