TW201827950A

TW201827950A - Developing apparatus capable of maintaining desired developing performance and maintaining a desired line width and residual film thickness of a wiring pattern on a substrate

Info

Publication number: TW201827950A
Application number: TW106141778A
Authority: TW
Inventors: 中川俊元
Original assignee: 日商平間理化硏究所股份有限公司
Priority date: 2017-01-23
Filing date: 2017-11-30
Publication date: 2018-08-01
Also published as: CN108345169A; JP2018120901A; KR20180087126A

Abstract

Provided is a developing apparatus capable of maintaining desired developing performance and maintaining a desired line width and residual film thickness of a wiring pattern on a substrate. The developing apparatus comprises a developing solution formulating device that mixes a developing stock solution containing a main component of an alkaline developing solution with pure water, and formulates the developing solution with a set concentration into a developing new solution; a developing new solution pipeline for conveying the developing new solution replenished from the developing solution formulating device to the repeatedly used developing solution; a developing stock solution pipeline for conveying the developing stock solution replenished to the repeatedly used developing solution; a pure water pipeline for conveying the pure water replenished to the repeatedly used developing solution; and a developing solution management device that manages in a manner of setting an alkaline component concentration of the repeatedly used developing solution or a conductivity of the developing solution as a predetermined management value or be within a predetermined management range.

Description

顯影裝置 Developing device

本發明係關於顯影裝置，尤其係關於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)顯影而使用之顯影裝置。 The present invention relates to a developing device, and more particularly, to a developing device used for developing a photoresist film in a development process of a circuit board of a semiconductor or a liquid crystal panel, and the like.

在實現半導體或液晶面板等的微細配線加工之光微影(photolithography)的顯影製程中，係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 fine wiring processing such as semiconductors and liquid crystal panels, an alkaline developer (hereinafter referred to as "alkaline developer") is used as a film to be formed on a substrate. The medicinal solution on which the photoresist is dissolved.

在半導體或液晶面板基板的製程中，近年來，晶圓或玻璃基板的大型化與配線加工的微細化及高積體化已有長足進展。在這種狀況下，為了實現大型基板之配線加工的微細化及高積體化，便需要更加高精確地測定鹼性顯影液之主要成分的濃度來維持管理顯影液。 In the manufacturing process of semiconductor or liquid crystal panel substrates, in recent years, the size of wafers or glass substrates and the miniaturization and high integration of wiring processing have made great progress. Under these circumstances, in order to realize miniaturization and high integration of wiring processing of large substrates, it is necessary to more accurately measure the concentration of the main components of the alkaline developer to maintain and manage the developer.

習知之鹼性顯影液的成分濃度之測定，係利用在鹼性顯影液之鹼成分的濃度(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這點(例如專利文獻1)。 The measurement of the component concentration of the conventional alkaline developer is based on the fact that a good linear relationship can be obtained between the concentration of the alkaline component of the alkaline developer (hereinafter referred to as "alkaline component concentration") and the electrical conductivity ( For example, Patent Document 1).

然而，近年來，鹼性顯影液接觸空氣的機會因顯影處理而增加，因鹼性顯影液會吸收空氣中的二氧化碳，所以鹼性顯影液之二氧化碳的吸收量會增加。當吸收的二氧化碳濃度變高，習知的顯影液管理方法，便發生無法維持預定的線寬加工等的問題。 However, in recent years, the exposure of the alkaline developer to air has increased due to the development process. Since the alkaline developer has absorbed carbon dioxide in the air, the amount of carbon dioxide absorbed by the alkaline developer has increased. When the concentration of the absorbed carbon dioxide becomes high, the conventional developer management method suffers problems such as failure to maintain a predetermined line width processing.

造成上述問題的原因，係由於因二氧化碳的吸收而生成碳酸鹽的反應消耗了鹼性顯影液中具顯影活性的鹼性成分。此外，還由於因光阻劑的溶解而生成光阻劑鹽的反應消耗了鹼性顯影液中具顯影活性的鹼性成分。 The reason for the above problem is that the reaction of generating carbonate due to the absorption of carbon dioxide consumes the alkaline component with developing activity in the alkaline developing solution. In addition, the reaction of generating a photoresist salt due to the dissolution of the photoresist consumes an alkaline component having a developing activity in the alkaline developing solution.

針對上述問題點，已有嘗試各種欲將因消耗而減少的鹼性成分補充的顯影液管理。關於該些嘗試的做法，係藉由測定碳酸鹽濃度，以補充液補充被生成碳酸鹽的反應所消耗掉的鹼性成分使具顯影活性的鹼性成分的濃度維持一定。針對因光阻劑的溶解而消耗掉的鹼性成分也是相同的作法。該些嘗試係從形成碳酸鹽和光阻劑鹽的鹼性成分係失去顯影活性而處於失去活性的觀點出發(例如，專利文獻2)。 In response to the above-mentioned problems, various attempts have been made to manage the developer solution to supplement the alkaline components that have been reduced due to consumption. With regard to these attempts, the concentration of the alkaline component having a developing activity is maintained constant by measuring the carbonate concentration and supplementing the alkaline component consumed by the carbonate-producing reaction with a replenishment solution. The same applies to the alkaline components consumed by the dissolution of the photoresist. These attempts have been made from the viewpoint that the alkaline components that form carbonates and photoresist salts have lost the developing activity and are inactive (for example, Patent Document 2).

先前技術文獻Prior art 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 Japanese Patent Laid-Open No. 2008-283162

然而，上述各種的顯影液管理的嘗試依然難以實現令人滿意的顯影液管理，難以在顯示裝置中維持所期望的顯影性能。 However, the above-mentioned various attempts of developer management are still difficult to achieve satisfactory developer management, and it is difficult to maintain desired developing performance in a display device.

本案的發明人在針對顯影液管理致力研究後，獲得了以下發現。亦即，藉由管理顯影液的導電率值，能夠實現一併考慮到碳酸鹽和阻劑鹽亦有一部分在顯影液中游離而幫助顯影作用、及該些原本被認為是失去活性的成分對顯影作用之幫助的顯影液管理，還有，此方式的導電率的管理值係依吸收二氧化碳濃度及溶解光阻劑濃度而有各種不同的值。 The inventors of the present case have made the following findings after intensive research on developer management. That is, by managing the conductivity value of the developing solution, it is possible to realize that the carbonate and the resist salt are also partially released in the developing solution to help the developing effect, and the components that were originally considered to be inactive are The management of the developing solution assisted by the developing effect, and the management value of the conductivity of this method have various values depending on the concentration of the absorbed carbon dioxide and the concentration of the dissolved photoresist.

這是基於形成碳酸鹽和光阻劑鹽的鹼性成分並非失去活性，有一部分游離而幫助顯影作用這點、以及從具顯影活性的鹼性成分和碳酸鹽及阻劑鹽游離出而幫助顯影作用的成分皆對導電率有作用的觀點。亦即，本案的發明人發現利用顯影液的導電率值進行管理，來將具有顯影作用的成分總體進行最佳化管理，而發想出本發明。 This is based on the fact that the basic components that form the carbonate and photoresist salt do not lose their activity, and some of them are released to assist the development, and that the alkaline components and carbonate and inhibitor salts that have development activity are released to assist the development. All components have an effect on conductivity. That is, the inventors of the present invention have found out that the present invention has been optimized by managing the overall conductivity of the components having a developing effect by using the conductivity value of the developing solution for management.

本發明係為解決上述課題而研創者，目的在提供一種可對光阻劑達成預定的顯影性能之顯影裝置。 The present invention was developed by a researcher to solve the above-mentioned problems, and an object thereof is to provide a developing device capable of achieving a predetermined developing performance for a photoresist.

為了達成前述目的，本發明的顯影裝置係具備：顯影液調製裝置，係將含有呈現鹼性之顯影液的主成分之顯影原液與純水混合，將所設定之濃度的前述顯影液調製作為顯影新液；顯影新液用管路，供補給自前述顯影液調製裝置的前述顯影新液輸送至重複使用的前述顯影液；顯影原液用管路，係輸送會被補給到前述重複使用的前述顯影液之前述顯影原液；純水用管路，輸送會被補給至前述重複使用的前述顯影液的純水；及顯影液管理裝置，以前述重複使用之前述顯影液的鹼成分濃度或前述顯影液的導電率成為預定的管理值或管理範圍之方式進行管理。 In order to achieve the aforementioned object, the developing device of the present invention is provided with a developing solution preparing device that mixes a developing stock solution containing a main component of a developing solution exhibiting alkalinity with pure water, and prepares the developing solution of a predetermined concentration as a developing device. New liquid; a pipeline for developing a new solution for supplying the developing new solution from the developer preparing device to the reused developer; a pipeline for developing a raw solution which is replenished to the previously developed developer for reuse The aforementioned developing stock solution of the liquid; a pipeline for pure water that transports pure water that will be replenished to the aforementioned developer solution that is reused; and a developer management device that controls the alkali component concentration of the developer solution that is reused or the developer solution It is managed in such a manner that the conductivity becomes a predetermined management value or management range.

根據本發明的顯影裝置，因不論顯影液成為怎樣的溶解光阻劑濃度及吸收二氧化碳濃度，顯影液中對顯影作用具有活性的成分都可維持一定，故可維持所期望的顯影性能，而能夠實現可維持所期望的顯影性能例如基板上的配線圖案的線寬及殘膜厚度之顯影處理。 According to the developing device of the present invention, regardless of the concentration of the photoresist dissolved in the developing solution and the concentration of carbon dioxide absorbed, the active components in the developing solution that are active in the developing action can be maintained constant, so that the desired developing performance can be maintained and the A development process capable of maintaining desired development performance such as a line width of a wiring pattern on a substrate and a residual film thickness is realized.

為了達成前述目的，在本發明的顯影裝置中，前述顯影液管理裝置進一步具備控制手段，該控制手段具備：數據記憶部，係儲存有導電率數據，該導電率數據係按以前述重複使用之前述顯影液的溶解光阻劑濃度及吸收二氧化碳濃度為指標而特定的每個濃度區域，具有已預先確認會成為預定的顯影性能之前述重複使用之前述顯影液的導電率值；及控制部，以藉由前述重複使用之前述顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值而特定的濃度區域之儲存於前述數據記憶部的前述導電率值作為控制目標值，以前述重複使用之前述顯影液的導電率成為前述控制目標值的方式，對設置於前述顯影新液用管路的控制閥、設置於前述顯影原液用管路的控制閥及設置於前述純水用管路的控制閥中的至少任一者發出控制信號。 In order to achieve the foregoing object, in the developing device of the present invention, the developer management device further includes a control means, the control means includes: a data storage section that stores conductivity data, and the conductivity data is based on the above-mentioned repeated use. Each concentration region specified by the dissolved photoresist concentration and the absorbed carbon dioxide concentration of the developer as an index has a conductivity value of the developer that has been previously confirmed to be a predetermined developing performance for repeated use; and a control unit, The conductivity value stored in the data storage unit in the specific concentration region specified by the measurement value of the dissolved photoresist concentration and the measurement value of the absorbed carbon dioxide concentration of the developer used repeatedly is used as the control target value. In the manner in which the conductivity of the developer used repeatedly becomes the control target value, a control valve provided in the pipeline for the new developing solution, a control valve provided in the pipeline for the original developing solution, and a tube provided for the pure water At least any one of the control valves of the circuit sends a control signal.

根據本發明的顯影裝置，因不論顯影液成為怎樣的溶解光阻劑濃度及吸收二氧化碳濃度，顯影液中對顯影作用具有活性的成分都可維持一定，故可維持所期望的顯影性能，而能夠實現可維持基板上的配線圖案之所期望的線寬及殘膜厚度之顯影處理。 According to the developing device of the present invention, regardless of the concentration of the photoresist dissolved in the developing solution and the concentration of carbon dioxide absorbed, the active components in the developing solution that are active in the developing action can be maintained constant, so that the desired developing performance can be maintained and the Realization of a development process capable of maintaining a desired line width and a residual film thickness of a wiring pattern on a substrate.

根據本發明之顯影裝置的較佳態樣，前述顯影液管理裝置進一步具備複數個測定裝置，該複數個測定裝置係測定前述重複使用之前述顯影液的複數個特性值，該複數個特性值係包含與前述重複使用之前述顯影液的溶解光阻劑濃度有相關之前述重複使用之前述顯影液的特性值、和與前述重複使用之前述顯影液的吸收二氧化碳濃度有相關之前述重複使用之前述顯影液的特性值；前述顯影液管理裝置的前述控制手段進一步具備運算部，該運算部係從藉由前述複數個測定裝置所測得之前述顯影液的複數個特性值，藉由多變量分析法，算出前述重複使用之前述顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。 According to a preferred aspect of the developing device of the present invention, the developer management device further includes a plurality of measuring devices, the plurality of measuring devices measure a plurality of characteristic values of the repeatedly used developer solution, and the plurality of characteristic values are It includes the characteristic values of the previously-used developing solution related to the dissolved photoresist concentration of the previously-used developing solution and the previously-used repeatedly-used previously-used developer solution in relation to the absorbed carbon dioxide concentration of the previously-used developer. Characteristic value of the developing solution; the control means of the developing solution management device further includes a calculation unit, which uses a plurality of characteristic values of the developing solution measured by the plurality of measuring devices, and performs multivariate analysis Method to calculate the measurement value of the dissolved photoresist concentration and the measurement value of the absorbed carbon dioxide concentration of the developer used repeatedly.

根據本發明之顯影裝置的較佳態樣，前述顯影液管理裝置進一步具備：複數個測定裝置，其係測定前述重複使用之前述顯影液的複數個特性值，該複數個特性值包含與前述重複使用之前述顯影液的溶解光阻劑濃度有相關之前述重複使用的前述顯影液的特性值、和與前述重複使用之前述顯影液的吸收二氧化碳濃度有相關之前述重複使用的前述顯影液的特性值；以及運算手段，其係從藉由前述複數個測定裝置所測得之前述重複使用之前述顯影液的複數個特性值，使用多變量分析法，算出前述重複使用之前述顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。 According to a preferred aspect of the developing device of the present invention, the developer management device further includes: a plurality of measuring devices that measure a plurality of characteristic values of the developer that is repeatedly used, and the plurality of characteristic values include the same as the repetitions. The dissolved photoresist concentration of the developer used has a characteristic value of the developer that is used repeatedly and a characteristic of the developer that is used repeatedly that is related to the carbon dioxide absorption of the developer used repeatedly. And a calculation means for calculating the dissolved light of the reused developer using the multivariate analysis method from a plurality of characteristic values of the reused developer previously measured by the plurality of measuring devices. The measured value of the resist concentration and the measured value of the absorbed carbon dioxide concentration.

根據本發明的顯影裝置的較佳態樣，前述顯影液管理裝置進一步具備密度計；前述顯影液管理裝置的前述控制手段進一步具備運算部，該運算部係依據前述重複使用之前述顯影液的吸收二氧化碳濃度與密度之間的對應關係，從藉前述密度計所測得之前述重複使用之前述顯影液的密度值，算出前述重複使用之前述顯影液的吸收二氧化碳濃度。 According to a preferred aspect of the developing device of the present invention, the developer management device further includes a densitometer; the control means of the developer management device further includes a calculation unit that is based on the absorption of the developer that is repeatedly used. The corresponding relationship between the carbon dioxide concentration and the density is to calculate the absorbed carbon dioxide concentration of the repeatedly used developing solution from the density value of the repeatedly used developing solution measured by the densitometer.

根據本發明的顯影裝置的較佳態樣，前述顯影液管理裝置進一步具備：密度計；及運算手段，係依據前述重複使用之前述顯影液的吸收二氧化碳濃度與密度之間的對應關係，從藉前述密度計所測得之前述重複使用之前述顯影液的密度值，算出前述重複使用之前述顯影液的吸收二氧化碳濃度。 According to a preferred aspect of the developing device of the present invention, the developer management device further includes: a density meter; and a computing means based on a correspondence relationship between the carbon dioxide concentration and the density of the developer that is repeatedly used, and borrows The density value of the reused developer solution measured by the density meter is used to calculate the carbon dioxide absorption concentration of the reused developer solution.

本發明的顯影裝置，前述顯影液管理裝置進一步具備控制手段，該控制手段具備：數據記憶部，係儲存有鹼成分濃度數據，該鹼成分濃度數據係以與前述重複使用之前述顯影液的溶解光阻劑濃度有相關的吸光度及吸收二氧化碳濃度為指標而特定的每個濃度區域，具有已預先確認會成為預定的顯影性能之前述重複使用的前述顯影液的鹼成分濃度值；以及控制部，以藉由前述重複使用之前述顯影液的吸光度及吸收二氧化碳濃度的測定值而特定的濃度區域之儲存於前述數據記憶部的前述鹼成分濃度值作為控制目標值，以前述重複使用的前述顯影液的鹼成分濃度成為前述控制目標值的方式，對設置於前述顯影新液用管路的控制閥、設置於前述顯影原液用管路的控制閥及設置於前述純水用管路的控制閥中的至少任一者發出控制信號。 In the developing device of the present invention, the developing solution management device further includes control means including a data storage unit that stores alkali component concentration data, and the alkali component concentration data is dissolved with the developer that is repeatedly used. The concentration of the photoresist has a specific absorbance and carbon dioxide absorption concentration as indicators, and each concentration region has an alkali component concentration value of the aforementioned developing solution that has been previously confirmed to be a predetermined developing performance for repeated use; and a control section, The concentration value of the alkali component stored in the data storage unit in a specific concentration region based on the measured values of absorbance and carbon dioxide concentration of the developer used repeatedly is used as a control target value, and the developer used repeatedly is used In the manner in which the concentration of the alkali component becomes the control target value, the control valve provided in the pipeline for the new developing solution, the control valve provided in the pipeline for the original developing solution, and the control valve provided in the pipeline for pure water At least any one of the control signals.

根據本發明的顯影裝置，因不論顯影液變成了怎樣的溶解光阻劑濃度及吸收二氧化碳濃度，顯影液中對顯影作用具活性的成分仍可維持一定，所以能夠實現可維持所期望的顯影性能，且可維持基板上之配線圖案的所期望線寬及殘膜厚度之顯影處理。 According to the developing device of the present invention, no matter what the concentration of the photoresist is dissolved in the developing solution and the concentration of carbon dioxide is absorbed, the active components in the developing solution that are active to the development can be maintained constant, so that the desired developing performance can be maintained And can maintain the desired line width and residual film thickness of the wiring pattern on the substrate.

A‧‧‧顯影製程設備 A‧‧‧Development process equipment

B‧‧‧補充液貯留部 B‧‧‧ Reservoir storage section

C‧‧‧循環攪拌機構 C‧‧‧Circulation stirring mechanism

D‧‧‧顯影液管理裝置 D‧‧‧Developer management device

1‧‧‧測定部 1‧‧‧Measurement Department

11‧‧‧導電率計 11‧‧‧Conductivity meter

12‧‧‧第1濃度測定手段 12‧‧‧ the first concentration measurement method

12A‧‧‧第1特性值測定手段 12A‧‧‧The first characteristic value measuring method

13‧‧‧第2濃度測定手段 13‧‧‧Second concentration measurement method

13A‧‧‧第2特性值測定手段 13A‧‧‧The second characteristic value measuring method

13B‧‧‧密度計 13B‧‧‧ Density Meter

14‧‧‧取樣泵 14‧‧‧ sampling pump

15‧‧‧取樣配管 15‧‧‧Sampling piping

16‧‧‧出口側配管 16‧‧‧Outlet side piping

21‧‧‧控制手段(例如電腦) 21‧‧‧ Control means (e.g. computer)

23‧‧‧數據記憶部 23‧‧‧Data Memory Department

31‧‧‧控制部 31‧‧‧Control Department

32、33‧‧‧運算部 32, 33‧‧‧ Computing Department

36、37‧‧‧運算手段 36, 37‧‧‧ Computing methods

41~43、48~50‧‧‧控制閥 41 ~ 43, 48 ~ 50‧‧‧Control valve

44、45、46、47‧‧‧閥 44, 45, 46, 47‧‧‧ valves

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

62‧‧‧溢流槽 62‧‧‧ Overflow trough

63‧‧‧液面計 63‧‧‧ level meter

64‧‧‧顯影室罩 64‧‧‧Developing 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 liquid pump

72、74‧‧‧循環泵 72, 74‧‧‧Circulation pump

73、75‧‧‧過濾器 73, 75‧‧‧ filters

80‧‧‧顯影液管路 80‧‧‧Developer solution line

81‧‧‧顯影原液用管路 81‧‧‧Tube for developing stock solution

82‧‧‧顯影新液用管路 82‧‧‧Pipe for developing new liquid

83‧‧‧純水用管路 83‧‧‧Pure water pipeline

84‧‧‧合流管路 84‧‧‧ Confluence pipeline

85‧‧‧循環管路 85‧‧‧Circulation pipeline

86‧‧‧氮氣用管路 86‧‧‧Pipe for nitrogen

91‧‧‧顯影原液貯留槽 91‧‧‧Developing stock solution storage tank

92‧‧‧顯影液調製裝置 92‧‧‧Developer preparation device

圖1係用以說明第一實施形態的顯影裝置的示意圖。 FIG. 1 is a schematic diagram for explaining a developing device according to the first embodiment.

圖2係用以說明第二實施形態的顯影裝置的示意圖。 FIG. 2 is a schematic diagram for explaining a developing device according to a second embodiment.

圖3係用以說明第三實施形態的顯影裝置的示意圖。 Fig. 3 is a schematic diagram for explaining a developing device according to a third embodiment.

圖4係用以說明第四實施形態的顯影裝置的示意圖。 FIG. 4 is a schematic diagram for explaining a developing device according to a fourth embodiment.

圖5係表示顯影液的吸收二氧化碳濃度與密度的關係之圖表(graph)。 FIG. 5 is a graph showing the relationship between the concentration of absorbed carbon dioxide and the density of the developer.

圖6係用以說明第五實施形態的顯影裝置的示意圖。 FIG. 6 is a schematic diagram for explaining a developing device according to a fifth embodiment.

用以實施發明的形態A form for implementing the invention

以下，適當參照圖式，詳細說明本發明較佳的實施形態。然而，此等實施形態所記載之裝置等的形狀、大小、尺寸比、其相對配置等，只要無特定的記載，則不僅限定於圖示本發明範圍之構成。僅單純作為說明例而示意性圖示而已。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as appropriate. However, the shape, size, size ratio, relative arrangement, etc. of the devices and the like described in these embodiments are not limited to the configuration of the scope of the present invention as long as there is no specific description. It is merely schematically shown as an illustrative example.

本發明的顯影裝置具備：顯影液調製裝置，係將含有呈現鹼性之顯影液的主成分之顯影原液與純水混合，調製所設定之濃度的前述顯影液作為顯影新液；顯影新液用管路，係將補給自前述顯影液調製裝置的前述顯影新液輸送至重複使用的前述顯影液；顯影原液用管路，係輸送會被補充至前述重複使用的前述顯影液的前述顯影原液；純水用管路，係輸送會被補充至前述重複使用的前述顯影液的純水；以及顯影液管理裝置，係以前述重複使用之前述顯影液的鹼成分濃度或前述顯影液的導電率成為預定的管理值或管理範圍之方式進行管理。 The developing device of the present invention includes a developing solution preparing device that mixes a developing raw solution containing a main component of a developing solution exhibiting alkalinity with pure water, and prepares the aforementioned developing solution at a set concentration as a new developing solution; The pipeline is used to transport the new developing solution replenished from the developing solution preparing device to the previously used developing solution; the pipeline for the developing solution is used to transport the developing solution that will be replenished to the previously used developing solution; The pipeline for pure water transports pure water that is replenished to the developer that is reused; and the developer management device is based on the alkali component concentration of the developer that is reused or the conductivity of the developer. Management in the manner of predetermined management value or management range.

說明關於包含於顯影裝置的顯影液管理裝置。 The developer management device included in the developing device will be described.

又，以下的說明中，就顯影液的具體例而言，係適當使用在半導體或液晶面板基板的製程中主要使用之2.38wt%的氫氧化四甲銨(tetramethyl ammonium hydroxide)水溶液(以下，將氫氧化四甲銨稱為TMAH。)，來進行說明。然而，本發明適用的顯影液不限於此。就本發明之顯影液的管理方法和裝置所能適用的其他顯影液的例子而言，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銨(trimethyl monoethanol ammonium hydroxide)(choline：膽鹼)等的有機化合物水溶液。 In the following description, as a specific example of the developer, a 2.38 wt% tetramethyl ammonium hydroxide aqueous solution (hereinafter, referred to as “mainly used” in a semiconductor or liquid crystal panel substrate manufacturing process is appropriately used. Tetramethylammonium hydroxide is called TMAH.). However, the developing solution to which the present invention is applicable is not limited to this. Examples of other developing solutions to which the developing solution management method and apparatus of the present invention can be applied include aqueous solutions of inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, and sodium silicate, and hydroxide Aqueous organic compounds such as trimethyl monoethanol ammonium hydroxide (choline).

以下說明中，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比濃度(wt%)計算的濃度。所謂的「溶解光阻劑濃度」係指將溶解的光阻劑換算為光阻劑的量時的濃度，所謂的「吸收二氧化碳濃度」係指將所吸收的二氧化碳換算為二氧化碳的量時的濃度。 In the following description, the concentration of a component such as the concentration of an alkali component, the concentration of a dissolved photoresist, and the concentration of absorbed carbon dioxide is a concentration calculated using a weight percent concentration (wt%). The so-called "dissolved photoresist concentration" means the concentration when the dissolved photoresist is converted into the amount of the photoresist, and the so-called "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，係藉由以顯影液將曝光處理後之光阻劑膜的不要部分溶解來進行顯影。溶解於顯影液的光阻劑會與顯影液的鹼成分之間生成光阻劑鹽。因此，若沒有適當地管理顯影液，則隨著顯影處理進行，顯影液就會因具有顯影活性的鹼成分被消耗而劣化，使得顯影性能愈益惡化。同時，在顯影液中，溶解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, development is performed by dissolving an unnecessary portion of the photoresist film after the exposure process with a developing solution. A photoresist salt dissolved between the photoresist dissolved in the developing solution and the alkali component of the developing solution. Therefore, if the developing solution is not appropriately managed, as the developing process proceeds, the developing solution is degraded due to the consumption of an alkaline component having developing activity, and the developing performance is deteriorated. At the same time, in the developing solution, the dissolved photoresist gradually accumulates in the form of a photoresist salt with an alkali component.

溶解於顯影液的光阻劑係在顯影液中顯現界面活性作用。因此，溶解於顯影液的光阻劑，可提高供顯影處理用之光阻劑膜對顯影液的浸潤性(wettability)，並改善顯影液與光阻劑膜的親和度。因此，在適度含有光阻劑的顯影液中，顯影液亦遍佈光阻劑膜的微細凹部內，而可對具有微細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 can improve the wettability of the photoresist film for the developing process to the developing solution, and improve the affinity between the developing solution and the photoresist film. Therefore, in a developing solution containing a photoresist moderately, the developing solution is also spread throughout the fine recesses of the photoresist film, and the photoresist film having fine unevenness can be favorably developed.

此外，在近年來的顯影處理中，伴隨基板大型化，大量的顯影液被重複使用，所以顯影液曝露於空氣的機會也增加。可是，鹼性顯影液一旦曝露於空氣中就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產生碳酸鹽。因此，若沒有適當地管理顯影液，顯影液中具有顯影活性的鹼成分便會被所吸收的二氧化碳消耗而減少。同時，在顯影液中，所吸收的二氧化碳係以與鹼性成分生成的碳酸鹽之形式而逐漸累積。 In addition, in recent development processes, a large number of developing solutions have been repeatedly used as the substrate becomes larger. Therefore, the opportunity for the developing solution to be exposed to air has also increased. However, once the alkaline developer is exposed to air, it absorbs carbon dioxide in the air. Carbon dioxide is absorbed between the absorbed carbon dioxide and the alkaline components of the developing solution. Therefore, if the developer is not properly managed, the alkali component having developing activity in the developer will be consumed by the absorbed carbon dioxide and reduced. At the same time, in the developing solution, the absorbed carbon dioxide gradually accumulates in the form of carbonates generated with alkaline components.

然而，因顯影液中的碳酸鹽在顯影液中係呈鹼性，故具有顯影作用。 However, since the carbonate in the developing solution is alkaline in the developing solution, it has a developing effect.

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存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 described above, unlike the previous recognition that the developing activity of the developing process is deactivated, the photoresist dissolved in the developing solution and the absorbed carbon dioxide actually contribute to the developing performance of the developing solution. Therefore, it is necessary to manage the developer solution that maintains the dissolved photoresist and carbon dioxide absorption at the optimal concentration while allowing the dissolved photoresist to be dissolved in the developer and absorb carbon dioxide, rather than dissolving the photoresist. And absorb the carbon dioxide completely remove the developer management.

又，關於生成於顯影液中的光阻劑鹽或碳酸鹽，其有一部分解離而生成光阻劑離子、碳酸離子或碳酸氫離子等各種自由離子。此外，這些自由離子會以各種貢獻率(contributing rate)影響著顯影液的導電率。 In addition, the photoresist salt or carbonate generated in the developing solution is partially dissociated to generate various free ions such as photoresist ions, carbonate ions, or bicarbonate ions. In addition, these free ions can affect the conductivity of the developer at various contributing rates.

關於上述各點，本案的發明人在針對顯影液管理致力研究後，獲得了以下發現。亦即，藉由管理顯影液的導電率值，能夠實現一併考慮到碳酸鹽和阻劑鹽亦有一部分在顯影液中游離而幫助顯影作用、及該些原本被認為是失去活性的成分對顯影作用之幫助的顯影液管理，還有，此方式的導電率的管理值係依吸收二氧化碳濃度及溶解光阻劑濃度而有各種不同的值。 Regarding the above-mentioned points, the inventors of the present invention have made the following findings after intensive research on developer management. That is, by managing the conductivity value of the developing solution, it is possible to realize that the carbonate and the resist salt are also partially released in the developing solution to help the developing effect, and the components that were originally considered to be inactive are The management of the developing solution assisted by the developing effect, and the management value of the conductivity of this method have various values depending on the concentration of the absorbed carbon dioxide and the concentration of the dissolved photoresist.

於是，發明人係設想以TMAH水溶液作為顯影液進行管理之情況，使溶解光阻劑濃度、吸收二氧化碳濃度作各種變化，而求取了對光阻劑的所期望顯影性能與顯影液的導電率值之關係。 Therefore, the inventor envisioned a case where the TMAH aqueous solution was used as a developing solution, and the concentration of the dissolved photoresist and the concentration of absorbed carbon dioxide were variously changed, and the desired developing performance of the photoresist and the conductivity of the developing solution were determined. Value relationship.

調製了使吸收二氧化碳濃度在0.0~1.3(wt%)之間變化，使溶解光阻劑濃度在0.0~0.40(wt%)(相當於波長560nm的吸光度0.0~1.3(abs))(以下有同樣將濃度與吸光度並行陳述的情形)之間變化之TMAH水溶液的顯影液試樣(sample)。本案的發明人係進行了如下的實驗：針對這些試樣，測定顯影液的導電率、吸收二氧化碳濃度及溶解光阻劑濃度，確認顯影性能、導電率、吸收二氧化碳濃度、及與溶解光阻劑濃度成分之關係。建立了以吸收二氧化碳濃度作為一個項目排列在縱向或橫向，並以溶解光阻劑濃度作為另一項目排列在橫向或縱向之矩陣(組合表)。就吸收二氧化碳濃度與溶解光阻劑濃度的每個組合，求得滿足對光阻劑的所期望顯影性能之顯影液的導電率，填入各欄而完成了矩陣(matrix)。 It is adjusted to change the absorbed carbon dioxide concentration between 0.0 to 1.3 (wt%) and the dissolved photoresist concentration to 0.0 to 0.40 (wt%) (equivalent to an absorbance of 0.0 to 1.3 (abs) at a wavelength of 560 nm) (the same applies to the following) A developer sample of a TMAH aqueous solution in which the concentration and the absorbance are stated in parallel). The inventors of this case conducted the following experiments: for these samples, the conductivity of the developing solution, the concentration of absorbed carbon dioxide, and the concentration of dissolved photoresist were measured, and the developing performance, the conductivity, the concentration of absorbed carbon dioxide, and the dissolved photoresist were confirmed. Relationship between concentration components. A matrix (combination table) of absorbing carbon dioxide concentration as one item arranged in the vertical or horizontal direction and dissolved photoresist concentration as another item arranged in the horizontal or vertical direction was established. For each combination of absorbed carbon dioxide concentration and dissolved photoresist concentration, the conductivity of the developing solution that satisfies the desired development performance for the photoresist is obtained, and the matrix is completed by filling in each column.

此處，所謂預定的顯影性能，係指實現欲以在顯影製程實現之基板上的配線圖案的線寬和殘膜厚度時的顯影液之顯影性能。 Here, the predetermined development performance refers to the development performance of the developer when the line width and the residual film thickness of the wiring pattern on the substrate to be realized in the development process are achieved.

例舉具代表性的各試樣的吸收二氧化碳濃度、溶解光阻劑濃度及導電率的測定結果。在吸收二氧化碳濃度為0.0(wt%)且溶解光阻劑濃度為0.0(wt%)(相當於0.0(abs))時(所謂的新液)，可發揮預定的顯影性能之顯影液的導電率為54.58(mS/cm)。 The measurement results of the representative carbon dioxide absorption concentration, dissolved photoresist concentration, and electrical conductivity are exemplified. When the carbon dioxide concentration is 0.0 (wt%) and the dissolved photoresist concentration is 0.0 (wt%) (equivalent to 0.0 (abs)) (the so-called new liquid), the conductivity of the developing solution that can exhibit the predetermined developing performance It was 54.58 (mS / cm).

在吸收二氧化碳濃度為0.0(wt%)且溶解光阻劑濃度為0.25(wt%)(相當於0.8abs)時，可發揮預定的顯影性能之顯影液的導電率為54.55(mS/cm)，在溶解光阻劑濃度為0.40(wt%)(相當於1.3abs)時，顯影液的導電率為54.53(mS/cm)。 When the carbon dioxide absorption is 0.0 (wt%) and the dissolved photoresist concentration is 0.25 (wt%) (equivalent to 0.8abs), the conductivity of the developing solution that can exert the predetermined developing performance is 54.55 (mS / cm). When the dissolved photoresist concentration is 0.40 (wt%) (equivalent to 1.3 abs), the conductivity of the developing solution is 54.53 (mS / cm).

又，在溶解光阻劑濃度為0.0(wt%)(相當於0.0(abs))且吸收二氧化碳濃度為0.6(wt%)時，顯影液的導電率為54.60(mS/cm)，在吸收二氧化碳濃度為1.3(wt%)時，顯影液的導電率為54.75(mS/cm)。 In addition, when the dissolved photoresist concentration is 0.0 (wt%) (equivalent to 0.0 (abs)) and the absorbed carbon dioxide concentration is 0.6 (wt%), the conductivity of the developing solution is 54.60 (mS / cm), and the absorbed carbon dioxide When the concentration is 1.3 (wt%), the conductivity of the developer is 54.75 (mS / cm).

又，在吸收二氧化碳濃度為0.6(wt%)且溶解光阻劑濃度為0.22(wt%)(相當於0.7abs)時，顯影液的導電率為54.60(mS/cm)，在溶解光阻劑濃度為0.40(wt%)(相當於1.3abs)時，顯影液的導電率為54.58(mS/cm)。 When the carbon dioxide concentration is 0.6 (wt%) and the dissolved photoresist concentration is 0.22 (wt%) (equivalent to 0.7abs), the conductivity of the developer is 54.60 (mS / cm), and the photoresist is dissolved. When the concentration is 0.40 (wt%) (equivalent to 1.3 abs), the conductivity of the developer is 54.58 (mS / cm).

又，在吸收二氧化碳濃度為1.3(wt%)且溶解光阻劑濃度為0.22(wt%)(相當於0.7abs)時，顯影液的導電率為54.75(mS/cm)，在溶解光阻劑濃度為0.40(wt%)(相當於1.3abs)時，顯影液的導電率為54.75(mS/cm)。 When the concentration of carbon dioxide absorption is 1.3 (wt%) and the dissolved photoresist concentration is 0.22 (wt%) (equivalent to 0.7abs), the conductivity of the developer is 54.75 (mS / cm), and the photoresist is dissolved in When the concentration is 0.40 (wt%) (equivalent to 1.3 abs), the conductivity of the developer is 54.75 (mS / cm).

此外，在上述的實驗中，在某濃度區域中，可觀察到當吸收二氧化碳濃度變大時，導電率的管理值有變大的傾向，當溶解光阻劑濃度變大時，導電率的管理值有變小的傾向。 In addition, in the above experiment, in a certain concentration region, it can be observed that when the concentration of absorbed carbon dioxide becomes larger, the management value of the conductivity tends to become larger, and when the concentration of the dissolved photoresist becomes larger, the management of the conductivity becomes larger. The value tends to become smaller.

上述的實驗中，各試樣的顯影液的導電率係使用藉導電率計所測得的值。吸收二氧化碳濃度係使用藉由滴定分析法所測得的值。溶解光阻劑濃度係採用重量調製值。滴定係以鹽酸作為滴定試藥的中和滴定。關於滴定裝置，係使用三菱化學Analytech(Mitsubishi Chemical Analytech)公司製的自動滴定裝置GT-200。 In the experiments described above, the conductivity of the developer of each sample was a value measured using a conductivity meter. The absorbed carbon dioxide concentration is a value measured by titration analysis. The dissolved photoresist concentration is a weight modulation value. The titration is a neutralization titration using hydrochloric acid as a titration reagent. As the titration device, an automatic titration device GT-200 manufactured by Mitsubishi Chemical Analytech was used.

另外，上述的導電率、吸收二氧化碳濃度、及溶解光阻劑濃度乃係用於找出導電率、吸收二氧化碳濃度及溶解光阻劑濃度與顯影性能間的關係性的數值，故不以各該數值為限。 In addition, the above-mentioned conductivity, carbon dioxide absorption concentration, and dissolved photoresist concentration are values used to find the relationship between the conductivity, carbon dioxide absorption, dissolved photoresist concentration, and development performance, so they are not described separately. The value is limited.

如上所述，能夠理解到可發揮顯影性能的導電率係依吸收二氧化碳濃度及溶解光阻劑濃度而有各種不同的值。如此，在顯影液的管理中，在含有吸收二氧化碳及溶解光阻劑的顯影液中，係以導電率作為管理值，再測定吸收二氧化碳濃度及溶解光阻劑濃度，藉由根據各測定結果使導電率的管理值不同，即可使預定的顯影性能發揮。 As described above, it can be understood that the conductivity exhibiting the developing performance has various values depending on the concentration of the absorbed carbon dioxide and the concentration of the dissolved photoresist. In this way, in the management of the developer, in the developer containing carbon dioxide absorption and dissolution of the photoresist, the conductivity is used as the management value, and then the concentration of the carbon dioxide absorption and the dissolution of the photoresist are measured. Different management values of the electrical conductivity can achieve predetermined development performance.

亦即，將按以顯影液的溶解光阻劑濃度及吸收二氧化碳濃度為指標而特定的每個濃度區域具有已預先確認會成為預定顯影性能的顯影液導電率值的導電率數據(矩陣)加以記憶，藉由利用導電率數據(矩陣)，便可進行能夠令預定之顯影性能發揮出來的顯影液管理。 That is, the conductivity data (matrix) of each concentration region specified with the concentration of the dissolved photoresist in the developer and the concentration of absorbed carbon dioxide as the developer having the conductivity value of the developer that has been confirmed to be a predetermined development performance is added. By using the conductivity data (matrix) in the memory, it is possible to perform a developer management capable of exhibiting a predetermined developing performance.

又，發明人針對顯影液管理致力研究後，獲得了以下的見解：藉由管理顯影液的鹼成分濃度值，可實現一併考量到碳酸鹽或阻劑鹽也有一部分在顯影液中游離而幫助顯影作用、以及被認為會失去活性的這些成分對顯影作用的幫助之顯影液管理；又，這樣的鹼成分濃度的管理值係依吸收二氧化碳濃度及與溶解光阻劑濃度有相關關係的吸光度而有各種不同的值。 In addition, the inventors have made research on the management of the developer, and obtained the following insights: By managing the concentration value of the alkali component of the developer, it is possible to consider that the carbonate or the inhibitor salt is also partially released in the developer and help The developer function and the developer management of these components that are considered to be inactive for the development effect; and the management value of the alkali component concentration is based on the absorbance of carbon dioxide concentration and the absorbance that is related to the concentration of the dissolved photoresist. There are various values.

於是，發明人係設想以TMAH水溶液作為顯影液進行管理之情況，使根據呈鹼性的顯影液導電率所測定的鹼成分濃度、與顯影液的溶解光阻劑濃度具有相關關係的吸光度、及顯影液的吸收二氧化碳濃度作多種變化，求取了對於光阻劑之所期望的顯影性能與顯影液的鹼成分濃度之關係。 Therefore, the inventor envisages a case where the TMAH aqueous solution is used as a developing solution for management, so that the concentration of the alkali component measured based on the conductivity of the developing solution that is alkaline, the absorbance having a correlation with the concentration of the dissolved photoresist in the developing solution, and The concentration of carbon dioxide absorbed by the developing solution was changed variously, and the relationship between the desired developing performance for the photoresist and the concentration of the alkali component of the developing solution was determined.

調製了使吸收二氧化碳濃度在0.0~1.3(wt%)之間變化，使與溶解光阻劑濃度有相關關係的吸光度在0.0~1.3(abs)之間變化之TMAH水溶液的顯影液試樣。本案發明人係進行了以下的實驗：針對這些試樣測定顯影液的鹼成分濃度、吸收二氧化碳濃度及吸光度，確認顯影性能、鹼成分濃度、吸收二氧化碳濃度及與吸光度之關係。作成以吸收二氧化碳濃度為一個項目排列在縱向或橫向，並以吸光度為另一項目排列在橫向或縱向之矩陣(組合表)。就吸收二氧化碳濃度與吸光度的每個組合，求得滿足對光阻劑之所期望的顯影性能之顯影液的鹼成分濃度，填入各欄而完成矩陣。 A developer solution sample of a TMAH aqueous solution was prepared to change the concentration of absorbed carbon dioxide between 0.0 to 1.3 (wt%), and change the absorbance related to the dissolved photoresist concentration between 0.0 to 1.3 (abs). The inventors of this case performed the following experiments: The alkali component concentration, carbon dioxide absorption concentration, and absorbance of the developer were measured for these samples, and the development performance, alkali component concentration, carbon dioxide absorption concentration, and relationship with absorbance were confirmed. Create a matrix (combination table) that arranges one item in the vertical or horizontal direction for absorbing carbon dioxide concentration and arranges it in the horizontal or vertical direction for the other item. For each combination of absorbed carbon dioxide concentration and absorbance, the alkali component concentration of the developing solution that satisfies the desired developing performance for the photoresist is obtained, and the matrix is completed by filling in each column.

此處，所謂預定的顯影性能，係指實現欲以顯影製程實現之基板上的配線圖案的線寬或殘膜厚度時之顯影液的顯影性能。 Here, the predetermined development performance refers to the development performance of the developer when the line width or the residual film thickness of the wiring pattern on the substrate to be realized by the development process is achieved.

例舉具代表性之各試樣的吸收二氧化碳濃度、吸光度及鹼成分濃度的測定結果。在吸收二氧化碳濃度為0.0(wt%)且吸光度為0.0(abs)的情況(所謂新液)，可發揮預定的顯影性能之顯影液的鹼成分濃度為2.380(wt%)。 The measurement results of the representative carbon dioxide absorption concentration, absorbance, and alkali component concentration are exemplified. In the case where the concentration of carbon dioxide is 0.0 (wt%) and the absorbance is 0.0 (abs) (so-called new solution), the alkali component concentration of the developing solution that can exhibit a predetermined developing performance is 2.380 (wt%).

在吸收二氧化碳濃度為0.0(wt%)，而吸光度為0.8abs時，可發揮預定的顯影性能之顯影液的鹼成分濃度為2.379(wt%)；在吸光度為1.3abs時，顯影液的鹼成分濃度為2.378(wt%)。 When the absorption carbon dioxide concentration is 0.0 (wt%) and the absorbance is 0.8abs, the alkali component concentration of the developing solution that can exert the predetermined development performance is 2.379 (wt%); when the absorbance is 1.3abs, the alkali component of the developing solution The concentration was 2.378 (wt%).

又，在吸光度為0.0(abs)，而吸收二氧化碳濃度為0.6(wt%)時，顯影液的鹼成分濃度為2.381(wt%)，在吸收二氧化碳濃度為1.3(wt%)時，顯影液的鹼成分濃度為2.388(wt%)。 In addition, when the absorbance is 0.0 (abs) and the absorbed carbon dioxide concentration is 0.6 (wt%), the alkali component concentration of the developing solution is 2.381 (wt%). When the absorbed carbon dioxide concentration is 1.3 (wt%), the The alkali component concentration was 2.388 (wt%).

又，在吸收二氧化碳濃度為0.6(wt%)，而吸光度為0.7abs時，顯影液的鹼成分濃度為2.381(wt%)，在吸光度為1.3abs時，顯影液的鹼成分濃度為2.380(wt%)。 In addition, when the concentration of absorbed carbon dioxide was 0.6 (wt%) and the absorbance was 0.7 abs, the alkali component concentration of the developing solution was 2.381 (wt%), and when the absorbance was 1.3 abs, the alkali component concentration of the developing solution was 2.380 (wt %).

又，在吸收二氧化碳濃度為1.3(wt%)，而吸光度為0.7abs時，顯影液的鹼成分濃度為2.388(wt%)，在吸光度為1.3abs時，顯影液的鹼成分濃度為2.388(wt%)。 In addition, when the concentration of absorbed carbon dioxide was 1.3 (wt%) and the absorbance was 0.7 abs, the alkali component concentration of the developing solution was 2.388 (wt%). When the absorbance was 1.3 abs, the alkali component concentration of the developing solution was 2.388 (wt %).

此外，在上述實驗中，在某濃度區域中，可觀察到當吸收二氧化碳濃度變大時，鹼成分濃度的管理值有變大的傾向，當吸光度變大時，鹼成分濃度的管理值有變小的傾向。 In addition, in the above experiment, in a certain concentration region, it can be observed that when the concentration of absorbed carbon dioxide becomes larger, the management value of the alkali component concentration tends to become larger, and when the absorbance becomes larger, the management value of the alkali component concentration changes. Small tendency.

上述的實驗中，各試樣之顯影液的鹼成分濃度，係可藉由以導電率計測定導電率來求得。具體而言，係將TMAH水溶液的新液(顯影前的TMAH水溶液)的鹼成分濃度與導電率值的相關關係(例如線性關係)預先以校準曲線(calibration curve)作成。依據此校準曲線，可從導電率值求得鹼成分濃度。 In the experiments described above, the alkali component concentration of the developer in each sample can be determined by measuring the conductivity with a conductivity meter. Specifically, a correlation (for example, a linear relationship) between the alkali component concentration of a new TMAH aqueous solution (TMAH aqueous solution before development) and the conductivity value is prepared in advance as a calibration curve. Based on this calibration curve, the alkali component concentration can be obtained from the conductivity value.

吸收二氧化碳濃度係使用藉由滴定分析法所測得的值。滴定係以鹽酸作為滴定試藥之中和滴定。滴定裝置係使用三菱化學Analytech公司製的自動滴定裝置GT-200。吸光度的測定是使用吸光光度計。 The absorbed carbon dioxide concentration is a value measured by titration analysis. Titration uses hydrochloric acid as the titration reagent for neutralization and titration. The titration device used was an automatic titration device GT-200 made by Mitsubishi Chemical Analytech. The absorbance was measured using an absorbance photometer.

此外，上述的鹼成分濃度、吸收二氧化碳濃度及吸光度係用於找出鹼成分濃度、吸收二氧化碳濃度及吸光度與顯影性能的關係性，故不限定於各數值。 The above-mentioned alkali component concentration, absorbed carbon dioxide concentration, and absorbance are used to find the relationship between the alkali component concentration, the absorbed carbon dioxide concentration, and the absorbance and the developing performance, and therefore are not limited to the respective values.

如上所述，能夠理解到可發揮顯影性能的鹼成分濃度係依吸收二氧化碳濃度及吸光度而有諸多差異。如此，在顯影液的管理中，在包含有吸收二氧化碳及溶解光阻劑的顯影液中，以鹼成分濃度作為顯影液的管理值，再測定吸收二氧化碳濃度及吸光度，根據各測定結果使鹼成分濃度的管理值不同，藉此便可使預定的顯影性能發揮。 As described above, it can be understood that there are many differences in the concentration of the alkali component that can exhibit the developing performance depending on the concentration of absorbed carbon dioxide and the absorbance. In this way, in the management of the developer, in the developer containing carbon dioxide absorption and dissolving the photoresist, the alkali component concentration is used as the management value of the developer, and then the carbon dioxide absorption concentration and absorbance are measured, and the alkali component is made based on the results of each measurement. The density management value is different, so that predetermined development performance can be exhibited.

亦即，按以顯影液的吸光度及吸收二氧化碳濃度為指標而特定的濃度區域，將具有已預先確認會成為預定顯影性能的顯影液的鹼成分濃度值之鹼成分濃度數據(矩陣)加以記憶，藉由利用鹼成分濃度數據(矩陣)，便可使預定的顯影性能發揮。 That is, the alkali component concentration data (matrix) having the alkali component concentration value of the developing solution which has been confirmed to be a predetermined developing performance in advance is memorized in a specific concentration area using the absorbance and carbon dioxide concentration of the developing solution as indicators, By using the alkali component concentration data (matrix), predetermined development performance can be exhibited.

接著，針對具體的實施例，參照圖式進行說明。 Next, specific embodiments will be described with reference to the drawings.

[第一實施形態] [First Embodiment]

圖1係用以說明顯影裝置的示意圖。實施形態的顯影裝置具備：顯影液調製裝置92、顯影新液用管路82、顯影原液用管路81、純水用管路83和顯影液管理裝置D。 FIG. 1 is a schematic diagram for explaining a developing device. The developing device of the embodiment includes a developing solution preparing device 92, a developing new solution line 82, a developing original solution line 81, a pure water line 83, and a developing solution management device D.

首先，就顯影製程設備A簡單說明。 First, the developing process equipment A will be described briefly.

顯影製程設備A主要係包含：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。在顯影液貯留槽61中貯留有顯影液。顯影液係接收補充液的補充而進行組成管理。顯影液貯留槽61具有液面計63及溢流槽62，藉以管理因補給補充液所導致的液量增加。顯影液貯留槽61與顯影液噴灑頭67係藉顯影液管路80連接。貯留在顯影液貯留槽61內的顯影液係藉由設在顯影液管路80的循環泵72經由過濾器73輸送到顯影液噴灑頭67。滾輪式輸送機65係裝設在顯影液貯留槽61的上方，用來搬送成膜有光阻劑膜的基板66。顯影液係從顯影液噴灑頭67滴下。藉滾輪式輸送機65搬送的基板66則藉由通過滴下的顯影液中而浸於顯影液。然後，顯影液被回收至顯影液貯留槽61，再度被貯留。依此方式，顯影液在顯影製程中循環並重複使用。另外，也有透過使小型玻璃基板的顯影室內充滿氮氣等，而施以不吸收空氣中的二氧化碳之處理的情況。此外，劣化的顯影液則透過使廢液泵71作動而以廢液處理(排放：(drain))。顯影工程設備B只要能夠顯影，就不受限於圖1所示之構成。 The development process equipment A mainly includes: a developer storage tank 61, an overflow tank 62, a development chamber hood 64, a roller conveyor 65, a developer nozzle 67, and the like. A developer is stored in the developer storage tank 61. The developer system receives the replenishment of the replenisher and manages the composition. The developer storage tank 61 includes a liquid level meter 63 and an overflow tank 62 to manage the increase in the amount of liquid caused by the replenishment of the replenishing liquid. The developing solution storage tank 61 is connected to the developing solution spraying head 67 through a developing solution line 80. The developer stored in the developer storage tank 61 is sent to the developer spray head 67 via a filter 73 by a circulation pump 72 provided in the developer solution line 80. The roller conveyor 65 is installed above the developer storage tank 61 and is used to transport a substrate 66 formed with a photoresist film. The developer is dripped from the developer spray head 67. The substrate 66 conveyed by the roller conveyor 65 is immersed in the developer by dropping the developer. Then, the developer is collected in the developer storage tank 61 and stored again. In this way, the developer is circulated and reused during the development process. In addition, there may be a case where the developing chamber of a small glass substrate is filled with nitrogen or the like, and a treatment that does not absorb carbon dioxide in the air is applied. In addition, the degraded developer is treated with waste liquid by operating the waste liquid pump 71 (drain). The development engineering equipment B is not limited to the configuration shown in FIG. 1 as long as it can develop.

就循環攪拌機構C進行說明。循環攪拌機構C主要係用於將貯留於顯影液貯留槽61內的顯影液加以循環攪拌。 The circulating stirring mechanism C will be described. The circulating stirring mechanism C is mainly used for circulating stirring of the developer stored in the developer storage tank 61.

顯影液貯留槽61的底部與顯影液貯留槽61的側部，係藉由中途設有循環泵74和過濾器75的循環管路85連接。一旦使循環泵74作動，貯留於顯影液貯留槽61的顯影液則經由循環管路85循環。顯影液經由循環管路85從顯影液貯留槽61的側部返回顯影液貯留槽61，並攪拌所貯留的顯影液。 The bottom of the developer storage tank 61 and the side of the developer storage tank 61 are connected by a circulation line 85 provided with a circulation pump 74 and a filter 75 in the middle. When the circulation pump 74 is operated, the developer stored in the developer storage tank 61 circulates through the circulation line 85. The developer is returned from the side of the developer storage tank 61 to the developer storage tank 61 via the circulation line 85, and the stored developer is stirred.

又，當補充液經由合流管路84流入循環管路85時，此流入的補充液會一邊與在循環管路85內循環的顯影液混合，一邊被供給至顯影液貯留槽61內。 When the supplementary liquid flows into the circulation line 85 through the merging line 84, the inflowing supplemental liquid is supplied into the developer storage tank 61 while being mixed with the developer liquid circulating in the circulation line 85.

其次，就本實施形態的顯影液管理裝置D進行說明。本實施形態的顯影液管理裝置D乃係如下方式的顯影液管理裝置：利用就以呈鹼性的顯影液之溶解光阻劑濃度及吸收二氧化碳濃度為指標而特定的每個濃度區域具有已預先確認會成為預定顯影性能之顯影液的導電率值之導電率數據(data)，以藉由顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值所特定之濃度區域的導電率作為控制目標值，對顯影液補給補充液以使顯影液的導電率成為控制目標值。 Next, the developer management device D of this embodiment will be described. The developer management device D of this embodiment is a developer management device in which each concentration region specified by using the concentration of the dissolved photoresist and the concentration of the absorbed carbon dioxide of the developer in an alkaline state has a predetermined value. Conductivity data (data) for confirming the conductivity value of the developing solution that has a predetermined developing performance, and the conductivity in the concentration range specified by the measured value of the dissolved photoresist concentration of the developing solution and the measured value of the absorbed carbon dioxide concentration As the control target value, the developer is replenished with a replenisher so that the conductivity of the developer becomes the control target value.

顯影液管理裝置D具備有測定部1和控制手段21。顯影液管理裝置D係藉由取樣配管15及出口側配管16而與顯影液貯留槽61連接。 The developer management device D includes a measurement unit 1 and a control unit 21. The developer management device D is connected to the developer storage tank 61 via a sampling pipe 15 and an outlet-side pipe 16.

測定部1具備有：取樣泵14、導電率計11、用於測定溶解光阻劑濃度的第1濃度測定手段12、及用於測定吸收二氧化碳濃度的第2濃度測定手段13。導電率計11、第1濃度測定手段12及第2濃度測定手段13係以串列方式連接於取樣泵14的後段。為了提高測定精度，測定部1係以復具備有使所取樣的顯影液穩定在預定溫度之溫度調節手段(未圖示)較佳。此時，溫度調節手段係以設在測定手段前較佳。取樣配管15係連接於顯影液管理裝置D之測定部1的取樣泵14，出口側配管16係與測定手段末端的配管連接。 The measurement unit 1 includes a sampling pump 14, a conductivity meter 11, a first concentration measuring means 12 for measuring the concentration of the dissolved photoresist, and a second concentration measuring means 13 for measuring the concentration of the absorbed carbon dioxide. The conductivity meter 11, the first concentration measuring means 12, and the second concentration measuring means 13 are connected in series to the rear stage of the sampling pump 14. In order to improve the measurement accuracy, it is preferable that the measurement unit 1 be further provided with a temperature adjustment means (not shown) that stabilizes the sampled developer solution at a predetermined temperature. In this case, it is preferable to set the temperature adjustment means before the measurement means. The sampling pipe 15 is connected to the sampling pump 14 of the measurement unit 1 of the developer management device D, and the outlet-side pipe 16 is connected to a pipe at the end of the measuring means.

又，圖1中雖係圖示導電率計11、第1濃度測定手段12及第2濃度測定手段13以串列方式連接的態樣，但導電率計11、第1濃度測定手段12及第2濃度測定手段13的連接並未限定於此。亦可為以並列方式連接，亦可分別獨立地具備輸送路徑來進行測定。關於導電率計11、第1濃度測定手段12及第2濃度測定手段13的順序，不特別論其先後。只要配合各測定手段的特徵適當以最佳順序來進行測定即可。 In FIG. 1, the conductivity meter 11, the first concentration measuring means 12, and the second concentration measuring means 13 are connected in series, but the conductivity meter 11, the first concentration measuring means 12 and the first The connection of the 2 concentration measuring means 13 is not limited to this. The measurement may be performed by connecting them in parallel, or by separately providing a transport path. Regarding the order of the conductivity meter 11, the first concentration measuring means 12, and the second concentration measuring means 13, the order is not particularly discussed. It is only necessary to perform the measurement in an optimal order in accordance with the characteristics of each measurement means.

控制手段21具備有數據記憶部23和控制部31。在數據記憶部23中，儲存了導電率數據，該導電率數據係就以呈現鹼性之顯影液的溶解光阻劑濃度及吸收二氧化碳濃度作為指標而特定的每個濃度區域。具有已預先確認會成為預定的顯影性能之所使用的顯影液之導電率值。 The control means 21 includes a data storage section 23 and a control section 31. In the data storage section 23, conductivity data is stored, and the conductivity data is specified for each concentration region with the dissolved photoresist concentration and the carbon dioxide absorption concentration of the developing solution exhibiting alkalinity as indicators. It has a conductivity value of a developer used in advance, which has been confirmed to be a predetermined developing performance.

控制手段21係藉信號線而與測定部1的導電率計11、第1濃度測定手段12、及第2濃度測定手段13連接。以測定部1測定的導電率值、溶解光阻劑濃度值、及吸收二氧化碳濃度值係朝控制手段21傳送。 The control means 21 is connected to the conductivity meter 11, the first concentration measurement means 12, and the second concentration measurement means 13 of the measurement unit 1 via a signal line. The conductivity value, the dissolved photoresist concentration value, and the absorbed carbon dioxide concentration value measured by the measurement unit 1 are transmitted to the control means 21.

控制手段21的控制部31係藉信號線而與設置在將補充液輸送到顯影液的管路之控制閥41~43連接。圖1中，控制閥41~43係以顯影液管理裝置D的內部零件的形式被顯示，但控制閥41~43並不是本實施形態之顯影液管理裝置D的必要零件。控制部31係控制控制閥41~43的作動，以可補給補充液至顯影液的方式與控制閥41~43聯絡即可。控制閥41~43亦可存在於顯影液管理裝置D外。 The control unit 31 of the control means 21 is connected to control valves 41 to 43 provided in a pipeline for supplying the replenishing liquid to the developing liquid via a signal line. In FIG. 1, the control valves 41 to 43 are shown as internal parts of the developer management device D, but the control valves 41 to 43 are not essential parts of the developer management device D of this embodiment. The control unit 31 controls the operation of the control valves 41 to 43 and communicates with the control valves 41 to 43 so as to replenish the replenishing liquid to the developer. The control valves 41 to 43 may exist outside the developer management device D.

接著，就本實施形態的顯影液管理裝置D的動作進行說明。 Next, the operation of the developer management device D according to this embodiment will be described.

取樣自顯影液貯留槽61的顯影液係輸送到測定部1內，施以溫度調節。然後，顯影液被輸送到導電率計11、第1濃度測定手段12及第2濃度測定手段13，以測定導電率、溶解光阻劑濃度及吸收二氧化碳濃度。各測定數據被傳送到控制手段21。 The developer sampled from the developer storage tank 61 is transported into the measurement unit 1 and subjected to temperature adjustment. Then, the developing solution is sent to the conductivity meter 11, the first concentration measuring means 12, and the second concentration measuring means 13 to measure the conductivity, the concentration of the dissolved photoresist, and the concentration of absorbed carbon dioxide. Each measurement data is transmitted to the control means 21.

控制部31中設定有導電率的管理值，該導電率的管理值係與以顯影液的溶解光阻劑濃度及吸收二氧化碳濃度為指標而特定的每個濃度區域具有已預先確認會成為預定的顯影性能之顯影液的導電率值對應。控制部31係藉由接收自測定部1的測定數據，依以下的方式執行控制。 The control unit 31 sets a management value of the conductivity, and the management value of the conductivity is determined in advance for each concentration region specified with the dissolved photoresist concentration of the developing solution and the concentration of the absorbed carbon dioxide as predetermined. Corresponds to the conductivity value of the developing solution. The control unit 31 performs control in the following manner based on the measurement data received from the measurement unit 1.

控制部31係根據接受自測定部1的溶解光阻劑濃度及吸收二氧化碳濃度，求取記憶於數據記憶部23的導電率數據中之藉由所測定的溶解光阻劑濃度及所測定的吸收二氧化碳濃度而特定的濃度區域之導電率值。並且，將所求出的導電率值設定作為顯影液導電率的控制目標值。 The control unit 31 obtains the measured dissolved photoresist concentration and the measured absorption from the conductivity data stored in the data storage unit 23 based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration received from the measurement unit 1. Carbon dioxide concentration and conductivity value in a specific concentration range. Then, the obtained conductivity value is set as a control target value of the conductivity of the developing solution.

控制部31係將自測定部1接收之測得的導電率、與設定作為控制目標值的導電率加以比較，並按照比較結果進行如下的管理。亦即，當設定為控制目標值的導電率與所測得的導電率相同時，基本上不對顯影液添加補充液。再者，設定作為控制目標值的導電率大於所測定的導電率時，只要補給產生使導電率提高之作用的補充液至顯影液即可。此外，設定作為控制目標值的導電率小於所測定的導電率時，只要補給產生使導電率下降之作用的補充液至顯影液即可。 The control unit 31 compares the measured conductivity received from the measurement unit 1 with the conductivity set as a control target value, and performs the following management based on the comparison result. That is, when the conductivity set to the control target value is the same as the measured conductivity, the replenishing liquid is not substantially added to the developing solution. In addition, when the conductivity which is a control target value is set to be larger than the measured conductivity, it is only necessary to supply a replenishing liquid which produces an effect of improving the conductivity to a developing solution. In addition, when the conductivity which is set as the control target value is smaller than the measured conductivity, it is only necessary to replenish the developer solution with a replenishing solution that causes the conductivity to decrease.

此處，就補給至顯影液的補充液而言，例如有顯影液之原液或新液、純水等。 Here, the replenishing liquid replenished to the developing solution includes, for example, an original solution or a fresh solution of the developing solution, and pure water.

補充液係貯留在補充液貯留部B的顯影原液貯留槽91及顯影液調製裝置92。顯影原液貯留槽91及顯影液調製裝置92，係連接有具備閥46、47的氮氣用管路86，受到經由該管路所供給的氮氣加壓。又，顯影原液貯留槽91及顯影液調製裝置92係分別連接有顯影原液用管路81及顯影新液用管路82，並經由通常呈開啟狀態的閥44、45被輸送補充液。顯影原液用管路81、顯影新液用管路82及純水用管路83裝設有控制閥41~43，控制閥41~43係藉控制部31施行開閉控制。藉由控制閥動作，壓送貯留於顯影原液貯留槽91及顯影液調製裝置92的補充液，並輸送純水。然後，補充液係經由合流管路84而與循環攪拌機構C合流，補給到顯影液貯留槽61進行攪拌。 The replenishing solution is a developing solution storage tank 91 and a developing solution preparing device 92 stored in the replenishing solution storage section B. The developing stock solution storage tank 91 and the developing solution preparation device 92 are connected to a nitrogen pipe 86 having valves 46 and 47, and are pressurized by nitrogen gas supplied through the pipes. Further, the developing stock solution storage tank 91 and the developing solution preparation device 92 are connected to a developing stock solution pipe 81 and a new development solution pipe 82, respectively, and are supplied with replenishment liquid through valves 44 and 45 which are normally opened. Control valves 41 to 43 are installed in the developing original liquid pipeline 81, the new developing liquid pipeline 82, and the pure water pipeline 83. The control valves 41 to 43 are controlled by the control unit 31 for opening and closing. When the control valve is operated, the replenishment liquid stored in the developing stock solution storage tank 91 and the developer preparation device 92 is pressure-fed, and pure water is delivered. Then, the replenishing liquid is merged with the circulation stirring mechanism C through the merging line 84, and is replenished to the developer storage tank 61 and stirred.

當因補給使得貯留於顯影原液貯留槽91及顯影液調製裝置92內的補充液減少時，其內壓便會下降，導致供給量變得不穩定，故會因應補充液的減少適當地開啟閥46、47來供給氮氣，以使顯影原液貯留槽91及顯影液調製裝置92的內壓得以保持的方式來加以維持。 When the replenishment liquid stored in the developing stock solution storage tank 91 and the developer preparation device 92 decreases due to replenishment, the internal pressure of the replenishment liquid will decrease and the supply amount will become unstable. Therefore, the valve 46 will be opened appropriately in response to the decrease in replenishment liquid And 47 are supplied with nitrogen gas so as to maintain the internal pressures of the developing solution storage tank 91 and the developing solution preparing device 92.

圖1係顯示顯影液調製裝置92受到氮氣加壓而自顯影液調製裝置92壓送顯影新液之態樣，但並未限定於此。顯影裝置中，有顯影工程設備A設在高層階，顯影液調製裝置92設在低層階，以分階的方式設置之情況。此時，顯影新液自顯影液調製裝置92的輸送多藉由送液泵來進行。以下說明的圖2~4、6中亦相同。 FIG. 1 shows a state in which the developing solution preparation device 92 is pressurized by nitrogen and the new developing solution is pressure-fed from the developing solution preparation device 92, but it is not limited thereto. In the developing device, the development engineering equipment A is set at a high level, and the developer preparation device 92 is set at a low level, and may be installed in a stepwise manner. At this time, the conveyance of the fresh developing solution from the developing solution preparing device 92 is often performed by a liquid feeding pump. The same applies to FIGS. 2 to 4 and 6 described below.

如圖1所示，顯影原液貯留槽91係連接有具有控制閥48的顯影原液供給用管路，顯影液調製裝置92係連接有具有控制閥49的顯影原液供給用管路、及具有控制閥50的純水用管路。 As shown in FIG. 1, the developing stock solution storage tank 91 is connected to a developing stock solution supply pipe having a control valve 48, and the developer preparation device 92 is connected to a development stock solution supply pipe having a control valve 49 and a control valve. 50 for pure water.

當顯影原液貯留槽91及顯影液調製裝置92空了的時候，將閥44、45關閉，再填充至顯影原液貯留槽91及顯影液調製裝置92。 When the developing stock solution storage tank 91 and the developing solution preparation device 92 are empty, the valves 44 and 45 are closed, and the developing stock solution storage tank 91 and the developing solution preparation device 92 are filled again.

控制閥41~43的控制係以例如下述方式進行。只要控制閥打開時流通的流量有受到調整，則藉由管理打開控制閥的時間，即可補給應補給之液量的補充液。控制部31係根據從測定部1所接收到的所測得的導電率與設定為控制目標值的導電率，對控制閥發出使控制閥打開預定時間的控制信號，以使應補給的液量的補充液流動。 The control of the control valves 41 to 43 is performed in the following manner, for example. As long as the flow rate is adjusted when the control valve is opened, the amount of replenishment liquid can be replenished by managing the opening time of the control valve. The control unit 31 sends a control signal to the control valve to open the control valve for a predetermined time based on the measured conductivity received from the measurement unit 1 and the conductivity set as the control target value, so that the amount of fluid to be replenished The make-up fluid flows.

控制的方式係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)、及組合這些的控制(PI控制等)(Proportional-Integral Control)較佳。PID控制(Proportional-Integral-Differential Control)很適合，為更佳。 The control method can adopt various control methods that can be used for controlling the control amount to meet the target value. In particular, 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, etc.) (Proportional-Integral Control) is better. PID control (Proportional-Integral-Differential Control) is very suitable and better.

如以上所述，根據包含本實施形態的顯影液管理裝置D之顯影裝置，因不論顯影液會成為何種溶解光阻劑濃度及吸收二氧化碳濃度，都可藉由以顯影液中之導電率來管理顯影液，來維持對顯影作用具有活性的成分，故可維持期望的顯影性能，能夠實現可維持基板上之配線圖案之所期望的線寬及殘膜厚度的顯影處理。 As described above, according to the developing device including the developing solution management device D of this embodiment, it is possible to obtain the conductivity of the developing solution by using the conductivity of the developing solution, regardless of the concentration of the dissolved photoresist and the concentration of carbon dioxide absorbed by the developing solution. The developer is managed to maintain a component that is active for development, so that it can maintain desired development performance, and can achieve a development process that can maintain the desired line width and residual film thickness of the wiring pattern on the substrate.

此外，依據本實施形態之顯影液管理裝置D，係使用預先確認過顯影性能的顯影液之導電率值之導電率數據作為控制目標管理值，藉此即使顯影液之溶解光阻劑濃度為0.0至0.40(wt%)(相當於0.0至1.3(abs))，且吸收二氧化碳濃度為0.0至1.3(wt%)，仍可作為具有所期望之顯影活性的顯影液來使用。亦即，依據本實施形態之顯影液管理裝置D，即使顯影液之溶解光阻劑濃度為0.25(wt%)以上(相當於0.8(abs))，且吸收二氧化碳濃度為0.6(wt%)以上，顯影液也可使用而不需以廢液處理，顯影液的廢液量可減少。 In addition, according to the developer management device D of this embodiment, the conductivity data of the conductivity value of the developer whose performance has been confirmed in advance is used as the control target management value, so that even if the developer has a dissolved photoresist concentration of 0.0, To 0.40 (wt%) (equivalent to 0.0 to 1.3 (abs)), and the carbon dioxide absorption concentration is 0.0 to 1.3 (wt%), it can still be used as a developing solution having a desired developing activity. That is, according to the developing solution management device D of this embodiment, even if the concentration of the dissolved photoresist in the developing solution is 0.25 (wt%) or more (equivalent to 0.8 (abs)), and the concentration of absorbed carbon dioxide is 0.6 (wt%) or more The developing solution can also be used without treatment with waste solution, and the amount of waste solution of the developing solution can be reduced.

以上，說明了使用顯影液的導電率、吸收二氧化碳濃度、及溶解光阻劑濃度與導電率數據的例子。但並不以此為限，可使用顯影液的鹼成分濃度、吸收二氧化碳濃度及吸光度、與鹼成分濃度數據，來管理顯影液。 Hereinabove, the examples using the conductivity of the developer, the concentration of absorbed carbon dioxide, and the dissolved photoresist concentration and conductivity data have been described. However, it is not limited to this, and the developer may be managed using the alkali component concentration, carbon dioxide absorption and absorbance, and alkali component concentration data of the developer.

[第二實施形態] [Second Embodiment]

圖2係用以說明顯影裝置的示意圖。此外，有在與第一實施形態的構成同樣之構成附上相同符號以省略說明之情況。 FIG. 2 is a schematic diagram for explaining a developing device. In addition, the same configurations as those of the first embodiment may be assigned the same reference numerals, and descriptions thereof may be omitted.

顯影液管理裝置D的測定部1具備有：導電率計11；及複數個測定裝置，係測定與顯影液的溶解光阻劑濃度有相關之顯影液的特性值及與顯影液的吸收二氧化碳濃度有相關之顯影液的特性值。例如，作為測定與溶解光阻劑濃度有相關之顯影液的特性值之第1特性值測定手段12A，例如具備有測定λ=560nm中的吸光度之吸光光度計。作為測定與吸收二氧化碳濃度有相關之顯影液的特性值之第2特性值測定手段13A，係具備有測定顯影液的密度之密度計。 The measurement unit 1 of the developer management device D includes: a conductivity meter 11; and a plurality of measurement devices for measuring a characteristic value of the developer that is related to the dissolved photoresist concentration of the developer and a carbon dioxide concentration absorbed by the developer. There are relevant characteristics of the developer. For example, as the first characteristic value measuring means 12A for measuring the characteristic value of the developing solution related to the dissolved photoresist concentration, for example, an absorbance photometer for measuring the absorbance at λ = 560 nm is provided. As the second characteristic value measuring means 13A for measuring the characteristic value of the developing solution related to the concentration of absorbed carbon dioxide, a density meter for measuring the density of the developing solution is provided.

此處，所謂的「有相關」之顯影液的特性值係指：該特性值與該成分濃度有關，特性值會因應其成分濃度的變化而改變的關係。例如，顯影液的成分濃度中至少與成分濃度A有相關之顯影液的特性值a係指：當藉由以成分濃度為變數的函數來求取特性值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 characteristic value of the “correlated” developer refers to a relationship in which the characteristic value is related to the concentration of the component, and the characteristic value changes in response to a change in the component concentration. For example, a characteristic value a of a developing solution in which the component concentration of the developing solution is at least related to the component concentration A means that when the characteristic value a is obtained by using the function of the component concentration as a variable, one of the variables includes at least the component Concentration A. The characteristic value a may be only a function of the component concentration A, but in general, in addition to the component concentration A, it is also formed as a multivariate function using the component concentration B or C as a variable, and a multivariate analysis method (for example, multiple regression analysis Law) is of great significance.

控制手段21具備有：數據記憶部23、控制部31及運算部32。運算部32係從藉測定部1所測得的顯影液的複數個特性值，藉由多變量分析法，算出顯影液之溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。 The control means 21 includes a data storage section 23, a control section 31, and a calculation section 32. The calculation unit 32 calculates the measured value of the dissolved photoresist concentration and the measured value of the absorbed carbon dioxide concentration of the developing solution from a plurality of characteristic values of the developing solution measured by the measuring unit 1 by a multivariate analysis method.

本實施形態中，自顯影液貯留槽61取樣的顯影液被輸送到測定部1內，進行溫度調節。顯影液之後會被輸送到導電率計11、第1特性值測定手段12A及第2特性值測定手段13A，來測定導電率、吸光度及密度。各測定數據被傳送到控制手段21。 In this embodiment, the developer sampled from the developer storage tank 61 is transported to the measurement unit 1 and temperature-adjusted. The developing solution is then sent to the conductivity meter 11, the first characteristic value measuring means 12A, and the second characteristic value measuring means 13A to measure the conductivity, absorbance, and density. Each measurement data is transmitted to the control means 21.

運算部32係從藉測定部1所測得的吸光度、及密度，藉由多變量分析法，算出顯影液之溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。此時，從導電率、吸光度及密度，藉由多變量分析，也可算出溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。 The computing unit 32 calculates the measured value of the dissolved photoresist concentration in the developer and the measured value of the absorbed carbon dioxide concentration from the absorbance and density measured by the measuring unit 1 by a multivariate analysis method. At this time, from the conductivity, absorbance, and density, the measured value of the dissolved photoresist concentration and the measured value of the absorbed carbon dioxide concentration can also be calculated by multivariate analysis.

控制部31係根據藉運算部32所算出之溶解光阻劑濃度和吸收二氧化碳濃度，求取數據記憶部23所記憶的導電率數據中之藉由所測得的溶解光阻劑濃度及所測得的吸收二氧化碳濃度而特定之濃度區域的導電率值。將所求得的導電率值設定作為顯影液導電率的控制目標值。 The control section 31 obtains the measured dissolved photoresist concentration and the measured photoconductivity from the conductivity data stored in the data storage section 23 based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration calculated by the calculation section 32. The obtained carbon dioxide concentration is a conductivity value in a specific concentration range. The obtained conductivity value is set as a control target value of the developer conductivity.

由於其他的構成、動作等係與第一實施形態同樣，故加以省略。 Since other structures, operations, and the like are the same as those of the first embodiment, they are omitted.

其次，針對從顯影液的複數個特性值，藉由多變量分析法算出溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值之手法進行說明。 Next, a method of calculating the measured value of the dissolved photoresist concentration and the measured value of the absorbed carbon dioxide concentration by a multivariate analysis method from a plurality of characteristic values of the developer will be described.

本案發明人發現只要運算手法是使用多變量分析法(例如，多元回歸分析法)，便可比使用習知方法的情況更高精確度地算出顯影液各成分的濃度，以及能夠測定以往難以測定的吸收二氧化碳濃度。只要使用藉由多變量分析法(例如，多元回歸分析法)所算出的顯影液的成分濃度(溶解光阻劑濃度及吸收二氧化碳濃度)，便可從具有已預先確認過顯影性能之溶解光阻劑濃度、及吸收二氧化碳濃度與導電率值的導電率數據，容易地獲得目標的導電率值。 The inventors of the present invention found that as long as the calculation method is a multivariate analysis method (for example, multiple regression analysis method), the concentration of each component of the developing solution can be calculated with higher accuracy than in the case of using a conventional method, and it is possible to measure conventionally difficult measurement Absorption of carbon dioxide concentration. By using the component concentration (dissolved photoresist concentration and absorbed carbon dioxide concentration) of the developing solution calculated by a multivariate analysis method (e.g., multiple regression analysis method), it is possible to dissolve the photoresist from a developer having previously confirmed development performance. The conductivity data of the agent concentration and the carbon dioxide concentration and the conductivity value can easily obtain the target conductivity value.

本案發明人設想一進行2.38%TMAH水溶液的管理的情況，調製出使鹼成分濃度、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。本案發明人進行如下的實驗：從針對這些模擬顯影液試樣所測得的各種特性值，藉由多元回歸分析法求取其成分濃度。以下，先說明採用多元回歸分析法之一般的運算手法，然後再說明根據發明人所進行的實驗，使用多元回歸分析法之顯影液成分濃度的運算手法。 The inventor of the present case imagines a case where a 2.38% TMAH aqueous solution is managed, and a TMAH aqueous solution prepared by making various changes in the concentration of the alkali component, the concentration of the dissolved photoresist, and the concentration of absorbed carbon dioxide is used as a mock developer sample. The inventors of the present invention conducted the following experiments: from the various characteristic values measured for these simulated developer samples, the component concentrations were determined by a multiple regression analysis method. In the following, a general calculation method using a multiple regression analysis method will be described first, and then a calculation method using a multiple regression analysis method for the concentration of the developer component according to an experiment performed by the inventor will be described.

多元回歸分析係由校正與預測等二階段組成。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個溶液中之第j個成分的濃度表示為C_ij。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，某波長的吸光度或導電率等的特性值)A_ik(k=1至p)。濃度數據與特性數據可分別彙整表示成矩陣的形式(C,A)。 Multiple regression analysis is composed of two stages: 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 as C _ij . Here, i = 1 to m and j = 1 to n. For m standard solutions, p characteristic values (for example, characteristic values such as absorbance or conductivity of a certain wavelength) A _ik (k = 1 to p) are measured. Concentration data and characteristic data can be aggregated and expressed in the form of a matrix (C, A).

將賦予該等矩陣關聯的矩陣係稱為校正矩陣，此處係以記號S(S_kj；k=1至p，j=1至n)表示。 The matrixes associated with such matrices are referred to as correction matrices, and are represented here with symbols S (S _kj ; k = 1 to p, j = 1 to n).

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

藉由矩陣運算從已知的C與A(A的內容係即使非純為同質的測定值而混有異質的測定值亦無妨。例如，導電率與吸光度與密度。)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較佳，在此情況中，係以下述方式進行最小平方運算。 A matrix calculation is performed from known C and A (the content of A is a mixture of heterogeneous measurement values even if they are not purely homogeneous measurement values. For example, conductivity and absorbance and density.) S is calculated as Calibration phase. At this time, it must be p ≧ n and m ≧ np. Since each element of S is unknown, m> np is preferred. In this case, the least square operation is performed in the following manner.

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 is the inverse matrix.

針對未知濃度的試料液測定p個特性值，若設這些特性值為Au(Au_k；k=1至p)，對這些特性值乘以S即可獲得應求取的濃度Cu(Cu_j；j=1至n)。 For p samples with unknown concentrations, determine p characteristic values. If these characteristic values are set to Au (Au _k ; k = 1 to p), multiply these characteristic values by S to obtain the required concentration Cu (Cu _j) . j = 1 to n).

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

這是預測階段。 This is the prediction phase.

發明人係進行了如下的實驗：將已使用的鹼性顯影液(2.38%TMAH水溶液)視為由鹼成分、溶解光阻劑、吸收二氧化碳等3成分所組成的多成分系(n=3)，從作為該顯影液的特性值之三個特性值(p=3)、亦即從顯影液的導電率值、特定波長的吸光度值及密度值，藉由上述多元回歸分析法算出各成分濃度。發明人係以2.38%TMAH水溶液作為顯影液的基本組成，調製出使鹼成分濃度(TMAH濃度)、溶解光阻劑濃度、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 inventors conducted the following experiment: The used alkaline developer (2.38% TMAH aqueous solution) was regarded as a multi-component system (n = 3) composed of 3 components, such as an alkali component, a dissolved photoresist, and carbon dioxide absorption. From the three characteristic values (p = 3) which are the characteristic values of the developing solution, that is, from the conductivity value of the developing solution, the absorbance value at a specific wavelength, and the density value, the concentration of each component is calculated by the above-mentioned multiple regression analysis method. . The inventor used a 2.38% TMAH aqueous solution as the basic composition of the developer, and prepared 11 calibration standard solutions (m = 11, which have various changes in the concentration of the alkali component (TMAH concentration), the concentration of the dissolved photoresist, and the concentration of absorbed carbon dioxide. 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。 The experiment is based on 11 calibration standard solutions. The conductivity value, the absorbance value at the wavelength λ = 560nm, and the density value are used as the characteristics of the developing solution. Multiple linear 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。溫度調整方式如下：先將裝入有校正標準溶液的瓶子(bottle)長時間浸漬於溫度管理在25℃附近的恆溫水槽，由此取樣，在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的導電率計。使用施行過鉑黑處理之本公司製的導電率流通槽來進行測定。於導電率計輸入另外藉校正作業確認過之導電率流通槽的槽常數(cell constant)。吸光光度計亦採用本公司製的吸光光度計。吸光光度計乃係具備波長λ=560nm的光源部和測光部和玻璃流通槽(glass flow cell)。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。所測得的導電率值、吸光度值、密度值的單位分別為mS/cm、Abs.(Absorbance)、g/cm³。 Regarding the measurement method, the temperature of the calibration standard solution was adjusted to 25.0 ° C, and then performed. The temperature adjustment method is as follows: first immerse the bottle filled with the calibration standard solution in a thermostatic water tank with a temperature management near 25 ° C for a long time, take a sample, and use the temperature controller to set it to 25.0 ° C immediately before the measurement. . The conductivity meter is a conductivity meter manufactured by our company. The measurement was performed using a conductivity flow cell made by our company that had been subjected to platinum black treatment. Enter the cell constant of the conductivity flow cell that has been confirmed by the calibration operation in the conductivity meter. The absorbance photometer is also made by our company. The absorbance photometer is provided with a light source section, a photometric section, and a glass flow cell having a wavelength of λ = 560 nm. The density measurement uses a densitometer. The density meter uses a natural vibration method for obtaining density from a natural vibration frequency measured by exciting a U-shaped tube through a flow channel. 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(留一交叉驗證法；Leave-One-Out法)，係選擇11個校正標準溶液當中的一個作為未知試料，以其餘10個標準求取校正矩陣，算出所假定之未知試料的濃度，再與既知的值(藉由其他的正確分析手法所測得的濃度值和重量調製值)進行比較。 Regarding the method used in the calculation (Leave-One-Out method; Leave-One-Out method), one of the 11 calibration standard solutions is selected as the unknown sample, and the calibration matrix is calculated based on the remaining 10 standards to calculate the assumed unknown. The concentration of the sample was compared with known values (concentration values and weight modulation values measured by other correct analysis methods).

將進行了MLR-ILS計算之結果顯示於表1。 Table 1 shows the results of the MLR-ILS calculation.

有鑑於TMAH水溶液為強鹼性，容易因吸收二氧化碳而劣化，在進行MLR-ILS計算時，使用於運算的濃度矩陣，係使用另以能夠正確地分析鹼成分濃度和吸收二氧化碳濃度的滴定分析法測定校正標準溶液而得的值。惟，關於溶解光阻劑濃度，係採用重量調製值。 Since the TMAH aqueous solution is strongly alkaline and easily deteriorates due to absorption of carbon dioxide, the concentration matrix used in the calculation when performing MLR-ILS calculations uses a titration analysis method that can accurately analyze the concentration of alkali components and the concentration of absorbed carbon dioxide. Measure the value obtained by calibrating the standard solution. However, regarding the dissolved photoresist concentration, a weight modulation value is used.

關於滴定方式，係以鹽酸作為滴定試藥的中和滴定。滴定裝置係使用三菱化學Analytech公司製的自動滴定裝置GT-200。 The titration method is a neutralization titration using hydrochloric acid as a titration reagent. The titration device used was an automatic titration device GT-200 made by Mitsubishi Chemical Analytech.

以下，將濃度矩陣顯示於表2。 The density matrix is shown in Table 2 below.

將此時之校正標準溶液的特性值的測定結果顯示於表3。吸光度的欄為波長λ=560nm之吸光度值(光路長d=10mm)。 Table 3 shows the measurement results of the characteristic values of the calibration standard solution at this time. The column of absorbance is the absorbance value (wavelength d = 10mm) at the wavelength λ = 560nm.

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

表5係顯示表2的濃度測定值與表1的MLR-ILS計算值之比較。 Table 5 shows a comparison between the concentration measurement values in Table 2 and the calculated MLR-ILS values in Table 1.

如表5所示，藉由多元回歸分析法所求得的TMAH濃度、溶解光阻劑濃度、吸收二氧化碳濃度皆成為與藉由滴定分析所測定之TMAH濃度、吸收二氧化碳濃度、及從調製重量所求得的溶解光阻劑濃度相當近似的值。 As shown in Table 5, the TMAH concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration obtained by the multiple regression analysis method are all the same as the TMAH concentration, the absorbed carbon dioxide concentration, and the adjusted weight obtained from the titration analysis. The obtained dissolved photoresist concentration was a fairly similar value.

如此，理解到藉由測定鹼性顯影液的導電率、特定波長的吸光度及密度，並使用多變量分析法(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 was understood that by measuring the conductivity of an alkaline developing solution, the absorbance and density at a specific wavelength, and using a multivariate analysis method (for example, multiple regression analysis method), it is possible to measure the alkali component concentration and dissolving photoresist of the developing solution. Agent concentration and carbon dioxide absorption.

多變量分析法(例如，多元回歸分析法)在運算並求出複數種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、…，可從該等測定值藉由多變量分析法(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，至少與該成分濃度有關的特性值係必須有至少一個經測定並使用在運算。 Multivariate analysis (for example, multiple regression analysis) has a good effect in calculating and determining the concentration of a plurality of components. A plurality of characteristic values a, b, c, ... of the developer are measured, and the component concentrations A, B, C, ... can be obtained from the measured values 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.

再者，成分濃度係表示該成分相對於整體的相對量之尺度。像重複使用的顯影液這種成分會隨時間而增減的混合液的成分濃度，無法由其成分單獨決定，通常係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，常常難以以平面圖表(graph)表示。在這種情況下，以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, a component concentration is a scale which shows the relative amount of the component with respect to the whole. The component concentration of a mixed solution, such as a repeatedly used developing solution, which may increase or decrease with 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 developing solution and the component concentration is often difficult to represent in a flat graph. In this case, it is not possible to calculate the component concentration from the characteristic value of the developer using an algorithm or the like using a calibration curve.

然而，若利用多變量分析法(例如，多元回歸分析法)，則只要收集到一組與欲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，便可算出一組成分濃度。即使是以習知見解中乍看之下難以測定的成分濃度，以多變量分析法(例如，多元回歸分析法) 進行的成分濃度測定，亦能夠獲得藉由測定特性值可測定成分濃度之顯著效果。 However, if a multivariate analysis method (for example, multiple regression analysis method) is used, as long as a set of measurement values of a plurality of characteristic values related to the concentration of the component to be calculated is collected, and these measurement values are used in the calculation, Calculate a set of component concentrations. Even if the component concentration is measured by a multivariate analysis method (for example, a multiple regression analysis method) based on a component concentration which is difficult to measure at a glance in the conventional knowledge, it is possible to obtain a significant component concentration that can be measured by measuring characteristic values. effect.

如以上所述，根據本發明的運算手法，可根據顯影液的特性值(例如，導電率、特定波長的吸光度、及密度)的測定值來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。根據本發明的運算手法，相較於習知法，能夠更高精確度地計算出各成分濃度。 As described above, according to the calculation method of the present invention, the alkali component concentration and the dissolved photoresist concentration of the developing solution can be calculated from the measured values of the characteristic values of the developing solution (for example, electrical conductivity, absorbance at a specific wavelength, and density). , And absorption of carbon dioxide concentration. According to the calculation method of the present invention, the concentration of each component can be calculated with higher accuracy than the conventional method.

此外，因本發明中使用了多變量分析法(例如，多元回歸分析法)，所以也可在算出顯影液之成分濃度的運算中，採用與顯影液的特定成分濃度無線性關係的顯影液特性值。 In addition, since a multivariate analysis method (for example, a multiple regression analysis method) is used in the present invention, in the calculation of the component concentration of the developer, a developer characteristic that is wirelessly related to the specific component concentration of the developer can be used. value.

又，若根據本發明，即可不需專利文獻2的發明中所必要之用於實現高精度測定用之非常多的試樣的準備與預備測定。(如同前述的實驗例，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，準備滿足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，則試樣數可更少。) In addition, according to the present invention, the preparation and preliminary measurement of a very large number of samples for realizing high-precision measurement, which is necessary in the invention of Patent Document 2, can be eliminated. (As in the previous experimental example, if it is a developing solution with the number of components n = 3, let the number of characteristic values for measurement be p = 3, and prepare the number of samples p that satisfy m ≧ np (for example, p = 11 samples) ) Is sufficient for the measurement. If the number of components is n = 2, the number of samples can be smaller.)

此外，本發明係使用多變量分析法(例如，多元回歸分析法)，所以能高精確度地算出習知難以測定之顯影液的吸收二氧化碳濃度。 In addition, since the present invention uses a multivariate analysis method (for example, a multiple regression analysis method), it is possible to calculate the absorbed carbon dioxide concentration of a developer which is conventionally difficult to measure with high accuracy.

本實施形態中，就與顯影液的溶解光阻劑濃度有相關之顯影液的特性值而言，係例示λ=560nm的吸光度，但不以此為限。亦可利用其他特定波長之吸光度作為特性值，亦即利用可視區域的特定波長的吸光度、更佳為360~600nm波長區域的特定波長的吸光度、更佳為波長λ=480nm的吸光度作為特性值。此乃因這些波長區域所含的特定波長的吸光度係與溶解阻劑濃度存在比較良好的對應關係之故。 In this embodiment, the characteristic value of the developing solution that is related to the dissolved photoresist concentration of the developing solution is exemplified by an absorbance of λ = 560 nm, but is not limited thereto. It is also possible to use the absorbance of other specific wavelengths as the characteristic value, that is, use the absorbance of the specific wavelength in the visible region, more preferably the specific wavelength of the 360-600 nm wavelength region, and more preferably the absorbance of the wavelength λ = 480 nm as the characteristic value. This is because there is a relatively good correspondence between the absorbance of specific wavelengths contained in these wavelength regions and the concentration of the dissolution resist.

又，就與顯影液的吸收二氧化碳濃度有相關之顯影液的特性值而言，雖例示有密度，但不限定於此。就與顯影液的溶解光阻劑濃度和吸收二氧化碳濃度有相關之顯影液的特性值而言，配合顯影液的導電率而進行測定的特性值所能夠採用的特性值係例如除了前述特定波長之吸光度和密度之外，還可舉出超音波傳播速度、折射率、滴定終點、pH等。 Moreover, although the characteristic value of the developing solution related to the carbon dioxide absorption concentration of the developing solution is exemplified by density, it is not limited thereto. As for the characteristic value of the developing solution which is related to the dissolved photoresist concentration and the carbon dioxide absorption concentration of the developing solution, the characteristic value that can be measured in accordance with the conductivity of the developing solution can be, for example, a characteristic value other than the aforementioned specific wavelength. In addition to the absorbance and density, ultrasonic propagation speed, refractive index, titration end point, pH, and the like can be mentioned.

[第三實施形態] [Third embodiment]

圖3係用以說明顯影裝置的示意圖。此外，有在與第一實施形態及第二實施形態的構成同樣的構成附上相同符號以省略說明之情況。 FIG. 3 is a schematic diagram for explaining a developing device. In addition, the same configurations as those of the first embodiment and the second embodiment may be assigned the same reference numerals, and descriptions thereof may be omitted.

本實施形態的顯影液管理裝置D具備有測定部1、控制手段21、及運算手段36。不同於第二實施形態，本實施形態中，控制手段21與進行運算的運算手段36係以分開設置的裝置構成。 The developer management apparatus D according to the present embodiment includes a measurement unit 1, a control unit 21, and a calculation unit 36. Different from the second embodiment, in this embodiment, the control means 21 and the arithmetic means 36 for performing calculations are configured as separate devices.

測定部1具備有導電率計11、第1特性值測定手段12A及第2特性值測定手段13A。運算手段36係從藉由第1特性值測定手段12A及第2特性值測定手段13A所測得的吸光度及密度，藉由多變量分析法算出顯影液之溶解光阻劑濃度的測定值及吸收二氧化碳濃度之測定值。此時，可從導電率、吸光度及密度，藉由多變量分析法算出溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。 The measurement unit 1 includes a conductivity meter 11, a first characteristic value measuring means 12A, and a second characteristic value measuring means 13A. The calculation means 36 is a method for calculating the measured value and absorption of the dissolved photoresist concentration in the developing solution by multivariate analysis from the absorbance and density measured by the first characteristic value measuring means 12A and the second characteristic value measuring means 13A. Measurement of carbon dioxide concentration. At this time, the measured value of the dissolved photoresist concentration and the measured value of the absorbed carbon dioxide concentration can be calculated from the conductivity, absorbance, and density by a multivariate analysis method.

控制部31係根據以運算手段所算出之溶解光阻劑濃度與吸收二氧化碳濃度，求取記憶在數據記憶部23的導電率數據中之藉由所測得的溶解光阻劑濃度及所測得的吸收二氧化碳濃度而特定的濃度區域之導電率值。將所求得的導電率值設定為顯影液導電率的控制目標值。 The control unit 31 obtains the measured dissolved photoresist concentration and the measured dissolved photoresist concentration stored in the conductivity data of the data storage unit 23 based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration calculated by the calculation means. The absorption of carbon dioxide concentration and the conductivity value in a specific concentration range. The obtained conductivity value is set as a control target value of the developer conductivity.

其他的構成、動作等係與第二實施形態同樣，故加以省略。 The other configurations, operations, and the like are the same as those of the second embodiment, and are omitted.

[第四實施形態] [Fourth embodiment]

圖4係用以說明顯影裝置的示意圖。此外，有在與第一實施形態、第二實施形態及第三實施形態的構成同樣的構成附上同一符號以省略說明之情況。 FIG. 4 is a schematic diagram for explaining a developing device. In addition, the same configurations as those of the first embodiment, the second embodiment, and the third embodiment may be assigned the same reference numerals, and descriptions thereof may be omitted.

本實施形態的測定部1具備導電率計11、第1濃度測定手段12及密度計13B。控制手段21具備數據記憶部23和運算部33。運算部33係依據顯影液的吸收二氧化碳濃度與密度之間的對應關係，從藉由密度計13B所測得的顯影液的密度，算出顯影液的吸收二氧化碳濃度。 The measurement unit 1 of this embodiment includes a conductivity meter 11, a first concentration measuring means 12, and a density meter 13B. The control means 21 includes a data storage unit 23 and a calculation unit 33. The calculation unit 33 calculates the absorbed carbon dioxide concentration of the developing solution from the density of the developing solution measured by the density meter 13B based on the correspondence between the absorbed carbon dioxide concentration and the density of the developing solution.

控制部31係依據藉測定部1所測得的溶解光阻劑濃度和藉運算部33所算出的吸收二氧化碳濃度，求出數據記憶部23所記憶的導電率數據之中藉由所測得的溶解光阻劑濃度及所測得的吸收二氧化碳濃度而特定之濃度區域的導電率值。將所求出的導電率值設定作為顯影液導電率的控制目標值。 The control unit 31 obtains the measured conductivity of the conductivity data stored in the data storage unit 23 based on the dissolved photoresist concentration measured by the measurement unit 1 and the absorbed carbon dioxide concentration calculated by the calculation unit 33. Dissolves the photoresist concentration and the measured value of the absorbed carbon dioxide concentration to determine the conductivity value in a specific concentration range. The obtained conductivity value is set as a control target value of the developer conductivity.

針對顯影液的密度值與吸收二氧化碳濃度值的關係進行說明。發明人持續致力研究的結果，獲得如下的見解。亦即，無關乎顯影液的鹼成分濃度和溶解光阻劑濃度，顯影液的密度值與吸收二氧化碳濃度值之間可獲得較良好的對應關係(線性關係)。此外，只要使用此對應關係(線性關係)，便能夠藉由以密度計測定顯影液的密度，而測定過往難以測定之吸收二氧化碳濃度。 The relationship between the density value of the developer and the carbon dioxide absorption value will be described. As a result of continuous research, the inventors obtained the following findings. That is, regardless of the concentration of the alkali component of the developing solution and the concentration of the dissolved photoresist, a relatively good correspondence relationship (linear relationship) can be obtained between the density value of the developing solution and the value of the absorbed carbon dioxide concentration. In addition, by using this correspondence relationship (linear relationship), by measuring the density of the developing solution with a density meter, it is possible to measure the absorbed carbon dioxide concentration which was difficult to measure in the past.

發明人進行了如下的實驗：係以採用了多變量分析法之顯影液的成分濃度的運算所使用之11個校正標準溶液作為模擬顯影液試樣，針對該些試樣測定鹼成分濃度(TMAH濃度)、溶解光阻劑濃度、吸收二氧化碳濃度及密度，確認成分濃度與密度的相關性。 The inventor conducted the following experiment: 11 calibration standard solutions used in the calculation of the component concentration of the developer using the multivariate analysis method were used as simulated developer samples, and the alkali component concentration (TMAH) was measured for these samples. Concentration), dissolved photoresist concentration, absorbed carbon dioxide concentration and density, and confirmed the correlation between the component concentration and density.

下表6係顯示各試樣的成分濃度與密度的測定結果。表6乃係表5的濃度測定值(wt%)與表3的密度(g/cm³)之對照表。 Table 6 below shows the measurement results of the component concentration and density of each sample. Table 6 is a comparison table between the concentration measurement values (wt%) in Table 5 and the density (g / cm ³ ) in Table ³ .

圖5係顯示表6所示之各試樣的吸收二氧化碳濃度與密度之圖表(graph)。此圖表係以吸收二氧化碳濃度(wt%)為橫軸，以密度(g/cm³)為縱軸，描繪(plot)出各試樣的值而成之圖表。從所描繪的各點，利用最小平方法求出迴歸線(regression line)。 FIG. 5 is a graph showing the carbon dioxide absorption concentration and density of each sample shown in Table 6. FIG. This graph plots the values of each sample with the absorption carbon dioxide concentration (wt%) as the horizontal axis and the density (g / cm ³ ) as the vertical axis. From each of the points drawn, a regression line is obtained by a least square method.

從圖5可理解到儘管顯影液的鹼成分濃度、溶解光阻劑濃度有各種不同變化，吸收二氧化碳濃度與顯影液的密度之間仍有良好的線性關係。本發明人依據此實驗結果而發現到：只要使用此顯影液的吸收二氧化碳濃度與密度之間的對應關係(線性關係)，便能夠藉由測定顯影液的密度，來算出顯影液的吸收二氧化碳濃度。 It can be understood from FIG. 5 that although there are various changes in the concentration of the alkali component of the developing solution and the concentration of the dissolved photoresist, there is still a good linear relationship between the concentration of the absorbed carbon dioxide and the density of the developing solution. Based on the results of this experiment, the inventors have discovered that as long as the correspondence relationship (linear relationship) between the concentration of carbon dioxide absorbed by the developer and the density is used, the concentration of carbon dioxide absorbed by the developer can be calculated by measuring the density of the developer .

因此，可無關乎鹼成分濃度(TMAH濃度)、溶解阻劑濃度，藉由利用此對應關係(線性關係)，使用密度計即可測定顯影液的吸收二氧化碳濃度。 Therefore, regardless of the alkali component concentration (TMAH concentration) and the dissolution inhibitor concentration, by using this correspondence (linear relationship), the density of the absorbed carbon dioxide of the developing solution can be measured using a density meter.

在運算部33中，利用顯影液的密度與吸收二氧化碳濃度的關係，便可容易地測定顯影液的吸收二氧化碳濃度。 In the calculation unit 33, the relationship between the density of the developing solution and the absorbed carbon dioxide concentration can be used to easily measure the absorbed carbon dioxide concentration of the developing solution.

[第五實施形態] [Fifth embodiment]

圖6係用以說明顯影裝置的示意圖。此外，有在與第一實施形態及第二實施形態的構成同樣的構成附上相同符號以省略說明之情況。 FIG. 6 is a schematic diagram for explaining a developing device. In addition, the same configurations as those of the first embodiment and the second embodiment may be assigned the same reference numerals, and descriptions thereof may be omitted.

本實施形態的顯影液管理裝置D具備有測定部1、控制手段21及運算手段37。本實施形態中，與第四實施形態不同，控制手段21與進行運算的運算手段37係以分開設置的裝置構成。本實施形態的測定部1具備導電率計11、第1濃度測定手段12及密度計13B。運算手段37係根據顯影液的吸收二氧化碳濃度與密度之間的對應關係，從藉由密度計13B所測得的顯影液的密度，算出顯影液的吸收二氧化碳濃度。 The developer management apparatus D according to the present embodiment includes a measurement unit 1, a control means 21, and a calculation means 37. In this embodiment, unlike the fourth embodiment, the control means 21 and the arithmetic means 37 for performing calculations are configured as separate devices. The measurement unit 1 of this embodiment includes a conductivity meter 11, a first concentration measuring means 12, and a density meter 13B. The calculation means 37 calculates the absorbed carbon dioxide concentration of the developing solution from the density of the developing solution measured by the density meter 13B based on the correspondence between the absorbed carbon dioxide concentration and the density of the developing solution.

控制部31係依據以測定部1所測得的溶解光阻劑濃度和以運算手段37所算出的吸收二氧化碳濃度，求出數據記憶部23所記憶的導電率數據中之藉由所測得的溶解光阻劑濃度及所測得的吸收二氧化碳濃度而特定之濃度區域的導電率值。將所求得的導電率值設定作為顯影液導電率的控制目標值。 The control unit 31 calculates the measured conductivity of the conductivity data stored in the data storage unit 23 based on the dissolved photoresist concentration measured by the measurement unit 1 and the absorbed carbon dioxide concentration calculated by the calculation means 37. Dissolves the photoresist concentration and the measured value of the absorbed carbon dioxide concentration to determine the conductivity value in a specific concentration range. The obtained conductivity value is set as a control target value of the developer conductivity.

其他的構成、動作等係與第四實施形態同樣，故加以省略。 The other configurations, operations, and the like are the same as those of the fourth embodiment, and are omitted.

如以上所述，根據本實施形態的顯影液管理裝置D，因不論顯影液會變成了怎樣的溶解光阻劑濃度及吸收二氧化碳濃度，顯影液中對顯影作用具活性的成分仍可維持一定，所以能夠維持所期望的顯影性能，能夠實現可維持形成於基板上之配線圖案的所期望之線寬及殘膜厚度的顯影處理。 As described above, according to the developing solution management device D of this embodiment, no matter what the concentration of the developing solution is to dissolve the photoresist concentration and absorb the carbon dioxide concentration, the active components in the developing solution that are active for the development can be maintained constant. Therefore, a desired development performance can be maintained, and a development process capable of maintaining a desired line width and a residual film thickness of a wiring pattern formed on a substrate can be realized.

其次，針對構成本實施形態的顯影裝置之顯影液管理裝置D的變形例進行說明。 Next, a modification of the developer management device D constituting the developing device of the present embodiment will be described.

雖然在圖1~4、6中係描繪出顯影液管理裝置D的測定部1與控制手段21和運算手段36、37一體構成的顯影液管理裝置D，但本實施形態的顯影液管理裝置D不限定於此。亦可將測定部1分開設置地構成。 Although FIGS. 1 to 4 and 6 show the developer management device D in which the measurement unit 1 of the developer management device D is integrated with the control means 21 and the calculation means 36 and 37, the developer management device D of this embodiment is shown. Not limited to this. The measurement unit 1 may be configured separately.

在測定部1中，具有因應於各自採用的測定原理之最佳設置方法，所以亦可設置成例如將測定部1以線內(inline)的方式連接於顯影液管路80、或將測定探針(measuring probe)浸漬於顯影液貯留槽61。導電率計11、第1濃度測定手段12、第1特性值測定手段12A、第2濃度測定手段13、第2特性值測定手段13A及密度計13B的各測定手段亦可個別地設置。本實施形態的顯影液管理裝置D只要構成為以使各測定手段可與控制手段21和運算手段36、37進行測定數據的收送之方式相互聯絡的態樣便能夠實現。 The measurement unit 1 has an optimal setting method according to the measurement principle adopted, so it may be provided, for example, to connect the measurement unit 1 to the developer line 80 inline, or to connect the measurement probe A developing probe is immersed in the developer storage tank 61. Each of the conductivity meters 11, the first concentration measuring means 12, the first characteristic value measuring means 12A, the second concentration measuring means 13, the second characteristic value measuring means 13A, and the density meter 13B may be individually provided. The developer management device D of the present embodiment can be realized as long as it is configured so that each measurement means can communicate with the control means 21 and the calculation means 36 and 37 to send and receive measurement data.

配合各測定手段所採用的測定原理，若需要進行試藥的添加，則各測定手段亦可具備供添加試藥用的配管，若一定會有廢液，各測定手段亦可具備供廢液用的管路。即便各測定手段沒有以串列連接時，本實施形態的顯影液管理裝置D仍可實現。 In accordance with the measurement principle adopted by each measurement method, if it is necessary to add a test drug, each measurement method may also have a pipe for adding a test drug. If there is a waste liquid, each measurement method may also be provided for waste liquid. Of the pipeline. Even when the measurement means are not connected in series, the developer management device D of this embodiment can be implemented.

雖然圖1~4、6中係描繪出以使設置在輸送補給至顯影液的補充液之管路的控制閥41~43成為顯影液管理裝置D的內部零件之方式，顯影液管理裝置D與顯影原液用管路81、顯影新液用管路82及純水用管路83連接之態樣，但本實施形態的顯影液管理裝置D並不限定於此。顯影液管理裝置亦可不以內部零件的形式具備控制閥41~43，亦可不與用於補給補充液至顯影液的顯影原液用管路81、顯影新液用管路82及純水用管路83連接。 Although FIGS. 1 to 4 and 6 depict the method in which the control valves 41 to 43 provided in the pipeline for supplying the replenishing liquid to the developer are made as internal parts of the developer management device D, the developer management device D and The development original solution pipe 81, the new development solution pipe 82, and the pure water pipe 83 are connected, but the developing solution management apparatus D of this embodiment is not limited to this. The developer management device may not include the control valves 41 to 43 as internal components, and may not be connected to the developer original solution pipeline 81, the developer new solution pipeline 82, and the pure water pipeline for replenishing the developer to the developer solution. 83 connections.

本實施形態的顯影液管理裝置D的控制手段21、與設置於用於補給補充液的管路之控制閥41~43只要構成為以使控制閥41~43接收到由顯影液管理裝置D的控制手段21所發出的控制信號而受到控制之方式可相互聯絡的態樣即可。即便控制閥不構成為顯影液管理裝置D的內部零件，本實施形態的顯影液管理裝置D仍可實現。 The control means 21 of the developer management device D of this embodiment and the control valves 41 to 43 provided in the pipeline for replenishing the liquid need only be configured so that the control valves 41 to 43 receive the signals from the developer management device D. The control signals sent by the control means 21 may be controlled in a manner in which the control methods can communicate with each other. Even if the control valve is not configured as an internal part of the developer management device D, the developer management device D of this embodiment can be implemented.

本發明的顯影液管理裝置不論上述的各種變形例是否被容許，皆具備導電率數據，該導電率數係按以顯影液之溶解光阻劑濃度及吸收二氧化碳濃度為指標而特定的每個濃度區域具有已預先確認能成為預定顯影性能之前述顯影液的導電率值；並且，以藉由顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值而特定之濃度區域的導電率數據的導電率值作為控制目標值，以顯影液的導電率成為前述控制目標值的方式輸送補給至前述顯影液的補充液。 The developer management device of the present invention has conductivity data regardless of whether the above-mentioned various modifications are allowed or not. The conductivity number is specified for each concentration based on the concentration of the dissolved photoresist in the developer and the concentration of absorbed carbon dioxide. The area has the conductivity value of the aforementioned developer solution, which has been confirmed to have predetermined development performance in advance; and the conductivity of the specific concentration area is determined by the measurement value of the dissolved photoresist concentration of the developer solution and the measurement value of the absorbed carbon dioxide concentration. The conductivity value of the data is used as the control target value, and the replenisher liquid supplied to the developer solution is transported so that the conductivity of the developer solution becomes the control target value.

如上所述，根據本發明的顯影液管理方法及顯影液管理裝置，不論顯影液成為了怎樣的溶解光阻劑濃度及吸收二氧化碳濃度，顯影液中對顯影作用具有活性的成分都可維持一定，所以能夠維持所期望的顯影性能，而能夠實現可維持基板上之配線圖案之所期望的線寬及殘膜厚度的顯影處理。 As described above, according to the developing solution management method and the developing solution management device of the present invention, regardless of the concentration of the dissolved photoresist and the concentration of carbon dioxide absorbed by the developing solution, the active components in the developing solution that are active for the development can be maintained constant. Therefore, a desired development performance can be maintained, and a development process capable of maintaining a desired line width and a residual film thickness of the wiring pattern on the substrate can be realized.

以顯影液管理裝置的較佳態樣而言，由於係藉由多變量分析法算出溶解光阻劑濃度、吸收二氧化碳濃度，故可以良好精確度求取溶解光阻劑濃度、吸收二氧化碳濃度。可根據這些溶解光阻劑濃度及吸收二氧化碳濃度，從導電率數據求取作為目標的導電率值。 In a preferred aspect of the developer management device, since the dissolved photoresist concentration and carbon dioxide absorption concentration are calculated by a multivariate analysis method, the dissolved photoresist concentration and carbon dioxide absorption concentration can be obtained with good accuracy. The target conductivity value can be obtained from the conductivity data based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration.

再者，以顯影液管理裝置的較佳態樣而言，係依據顯影液的吸收二氧化碳濃度與密度之間的對應關係，從藉由密度計所測得的顯影液的密度算出顯影液的吸收二氧化碳濃度。藉此，可更簡單地求取顯影液的吸收二氧化碳濃度。可根據此吸收二氧化碳濃度及另外求取的溶解光阻劑濃度，從導電率數據求取作為目標的導電率值。 Furthermore, in a preferred aspect of the developing solution management device, the absorption of the developing solution is calculated from the density of the developing solution measured by the density meter according to the correspondence between the concentration of the absorbed carbon dioxide and the density of the developing solution. CO2 concentration. This makes it easier to obtain the concentration of carbon dioxide absorbed by the developer. Based on the absorbed carbon dioxide concentration and the dissolved photoresist concentration obtained separately, the target conductivity value can be obtained from the conductivity data.

Claims

一種顯影裝置，係具備：顯影液調製裝置，將含有呈現鹼性之顯影液的主成分之顯影原液與純水混合，將所設定之濃度的前述顯影液調製作為顯影新液；顯影新液用管路，供補給自前述顯影液調製裝置的前述顯影新液輸送至重複使用的前述顯影液；顯影原液用管路，輸送會被補給到前述重複使用的前述顯影液之前述顯影原液；純水用管路，輸送會被補給至前述重複使用的前述顯影液的純水；及顯影液管理裝置，以前述重複使用之前述顯影液的鹼成分濃度或前述顯影液的導電率成為預定的管理值或管理範圍之方式進行管理。 A developing device is provided with a developing solution preparing device that mixes a developing raw solution containing a main component of a developing solution exhibiting alkalinity with pure water, and prepares the aforementioned developing solution at a set concentration as a new developing solution; A pipeline for supplying the developing fresh solution from the developing solution preparing device to the reused developing solution; a pipeline for developing a raw solution to transport the developing solution to be replenished to the reused developing solution; pure water Deliver pure water that will be replenished to the developer that is reused; and a developer management device that sets the alkali component concentration of the developer that is reused or the conductivity of the developer to a predetermined management value. Or scope of management.

如請求項1之顯影裝置，其中前述顯影液管理裝置進一步具備控制手段，該控制手段具備：數據記憶部，係儲存有導電率數據，該導電率數據係按以前述重複使用之前述顯影液的溶解光阻劑濃度及吸收二氧化碳濃度為指標而特定的每個濃度區域，具有已預先確認會成為預定的顯影性能之前述重複使用之前述顯影液的導電率值；及控制部，以藉由前述重複使用之前述顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值而特定的濃度區域之儲存於前述數據記憶部的前述導電率值作為控制目標值，以前述重複使用之前述顯影液的導電率成為前述控制目標值的方式，對設置於前述顯影新液用管路的控制閥、設置於前述顯影原液用管路的控制閥及設置於前述純水用管路的控制閥中的至少任一者發出控制信號。 For example, the developing device of claim 1, wherein the developer management device further includes a control means, the control means includes: a data memory section that stores conductivity data, and the conductivity data is based on the developer used repeatedly as described above. Each concentration region specified by the dissolved photoresist concentration and the absorbed carbon dioxide concentration as indicators has the conductivity value of the aforementioned developer solution that has been previously confirmed to be used for predetermined development performance; and a control unit to pass the aforementioned The measured value of the dissolved photoresist concentration and the measured value of the absorbed carbon dioxide concentration of the developer used repeatedly are used, and the conductivity value of the specific concentration region stored in the data memory section is used as a control target value. In a manner that the conductivity of the developing solution becomes the aforementioned control target value, a control valve provided in the pipeline for the new developing solution, a control valve provided in the pipeline for the developing original solution, and a control valve provided in the pipeline for pure water At least any one of them sends a control signal.

如請求項1之顯影裝置，其中前述顯影液管理裝置進一步具備控制手段，該控制手段具備：數據記憶部，係儲存有鹼成分濃度數據，該鹼成分濃度數據係以與前述重複使用之前述顯影液的溶解光阻劑濃度有相關的吸光度及吸收二氧化碳濃度為指標而特定的每個濃度區域，具有已預先確認會成為預定的顯影性能之前述重複使用的前述顯影液的鹼成分濃度值；以及控制部，以藉由前述重複使用之前述顯影液的吸光度及吸收二氧化碳濃度的測定值而特定的濃度區域之儲存於前述數據記憶部的前述鹼成分濃度值作為控制目標值，以前述重複使用的前述顯影液的鹼成分濃度成為前述控制目標值的方式，對設置於前述顯影新液用管路的控制閥、設置於前述顯影原液用管路的控制閥及設置於前述純水用管路的控制閥中的至少任一者發出控制信號。 For example, the developing device according to claim 1, wherein the developer management device further includes control means, the control means includes: a data memory section that stores alkali component concentration data, and the alkali component concentration data is based on the aforementioned development that is reused with the aforementioned The concentration of the dissolved photoresist in the liquid has specific absorbance and carbon dioxide absorption concentrations as indicators, and each concentration region has an alkali component concentration value of the aforementioned developing solution that has been previously confirmed to be used repeatedly for predetermined developing performance; and The control unit uses the alkali component concentration value stored in the data storage unit in a specific concentration region specified by the absorbance and carbon dioxide concentration measurement values of the developer used repeatedly as the control target value, and uses the reused In the manner in which the concentration of the alkali component of the developing solution becomes the control target value, the control valve provided in the pipeline for the new developing solution, the control valve provided in the pipeline for the original developing solution, and the control valve provided in the pipeline for pure water At least one of the control valves issues a control signal.

如請求項2之顯影裝置，其中前述顯影液管理裝置進一步具備複數個測定裝置，該複數個測定裝置係測定前述重複使用之前述顯影液的複數個特性值，該複數個特性值係包含與前述重複使用之前述顯影液的溶解光阻劑濃度有相關之前述重複使用之前述顯影液的特性值、和與前述重複使用之前述顯影液的吸收二氧化碳濃度有相關之前述重複使用之前述顯影液的特性值；前述顯影液管理裝置的前述控制手段進一步具備運算部，該運算部係從藉由前述複數個測定裝置所測得之前述顯影液的複數個特性值，藉由多變量分析法，算出前述重複使用之前述顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。 For example, the developing device of claim 2, wherein the developer management device further includes a plurality of measuring devices, and the plurality of measuring devices measure a plurality of characteristic values of the developer that is repeatedly used, and the plurality of characteristic values include the same as the foregoing. The dissolved photoresist concentration of the reused developer is related to the characteristic values of the reused developer and the carbon dioxide absorption of the developer is related to the reused developer solution. Characteristic value; the control means of the developer management device further includes a calculation unit that calculates from a plurality of characteristic values of the developer measured by the plurality of measuring devices by a multivariate analysis method The measurement value of the dissolved photoresist concentration and the measurement value of the absorbed carbon dioxide concentration of the developer used repeatedly.

如請求項2之顯影裝置，其中前述顯影液管理裝置進一步具備：複數個測定裝置，其係測定前述重複使用之前述顯影液的複數個特性值，該複數個特性值包含與前述重複使用之前述顯影液的溶解光阻劑濃度有相關之前述重複使用的前述顯影液的特性值、和與前述重複使用之前述顯影液的吸收二氧化碳濃度有相關之前述重複使用的前述顯影液的特性值；以及運算手段，其係從藉由前述複數個測定裝置所測得之前述重複使用之前述顯影液的複數個特性值，使用多變量分析法，算出前述重複使用之前述顯影液的溶解光阻劑濃度的測定值及吸收二氧化碳濃度的測定值。 The developing device according to claim 2, wherein the developing solution management device further includes: a plurality of measuring devices for measuring a plurality of characteristic values of the reused developer solution, the plurality of characteristic values including the aforesaid repeated use of the aforesaid developer solution. The dissolved photoresist concentration of the developer is related to the characteristic value of the reused developer solution and the characteristic value of the reused developer solution is correlated to the carbon dioxide absorption concentration of the developer solution. The calculation means is to calculate the dissolved photoresist concentration of the reused developing solution from the plurality of characteristic values of the reused developing solution measured by the plurality of measuring devices using a multivariate analysis method. Measured value and measured value of absorbed carbon dioxide concentration.

如請求項2之顯影裝置，其中前述顯影液管理裝置進一步具備密度計；前述顯影液管理裝置的前述控制手段進一步具備運算部，該運算部係依據前述重複使用之前述顯影液的吸收二氧化碳濃度與密度之間的對應關係，從藉前述密度計所測得之前述重複使用之前述顯影液的密度值，算出前述重複使用之前述顯影液的吸收二氧化碳濃度的測定值。 For example, the developing device according to claim 2, wherein the developer management device further includes a density meter; the control means of the developer management device further includes a computing unit, which is based on the carbon dioxide concentration and The correspondence between the densities is calculated from the density values of the repeatedly used developer solutions measured by the densitometer, and the measured values of the absorbed carbon dioxide concentration of the reused developer solutions are calculated.

如請求項2之顯影裝置，其中前述顯影液管理裝置進一步具備：密度計；及運算手段，係依據前述重複使用之前述顯影液的吸收二氧化碳濃度與密度之間的對應關係，從藉前述密度計所測得之前述重複使用之前述顯影液的密度值，算出前述重複使用之前述顯影液的吸收二氧化碳濃度的測定值。 For example, the developing device of claim 2, wherein the developer management device further includes: a density meter; and a calculation method based on the correspondence between the density of the absorbed carbon dioxide and the density of the developer used repeatedly, and borrowing the density meter. The density value of the developer used repeatedly is measured, and the measurement value of the carbon dioxide absorption concentration of the developer reused is calculated.