JP2018120893A - Device for measuring component concentration of developer, and developer management device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a component concentration measuring device that accurately calculates concentrations of components such as an alkali component, a dissolved photoresist and absorbed carbon dioxide in a developer showing alkalinity from characteristic values of the developer, and a developer management device that maintains and manages the development performance of a developer in an optimal condition.SOLUTION: A device for measuring a component concentration of a developer includes: a measuring part 1 for measuring a plurality of characteristic values of a developer that is repeatedly used and exhibits alkalinity, the characteristic values having correlation with component concentrations of the developer; a computing part 2 for calculating the component concentrations of the developer by multivariate analysis based on the plurality of characteristic values measured by the measuring part; and a display part DP for displaying at least either the characteristic value measured by the measuring part 1 or the component concentration calculated by the computing part 2.SELECTED DRAWING: Figure 4

Description

  The present invention relates to an alkali concentration developer concentration measuring apparatus and a developer management apparatus that are repeatedly used to develop a photoresist film in a development process of a circuit board in a semiconductor or a liquid crystal panel.

  In the development process of photolithography that realizes fine wiring processing in a semiconductor, a liquid crystal panel, etc., as a chemical solution that dissolves the photoresist formed on the substrate, an alkaline developer (hereinafter referred to as “alkaline developer”) is used. .) Is used.

  In the manufacturing process of semiconductors and liquid crystal panel substrates, in recent years, the enlargement of wafers and glass substrates and the miniaturization and high integration of wiring processing have been promoted. Under these circumstances, it is necessary to measure and maintain the developer by measuring the concentration of the main component of the alkaline developer with higher accuracy in order to realize finer wiring processing and higher integration of large substrates. It has become.

  As described in Patent Document 1, the measurement of the conventional alkaline developer component concentration is good between the alkali component concentration (hereinafter referred to as “alkaline component concentration”) and the electrical conductivity of the alkaline developer. A linear relationship is obtained, and a good linear relationship is obtained between the concentration of the photoresist dissolved in the alkaline developer (hereinafter referred to as “dissolved photoresist concentration”) and the absorbance. It was a thing.

  However, alkaline developers tend to deteriorate by absorbing carbon dioxide in the air and producing carbonates. Further, the alkaline developer produces a photoresist salt by dissolving the photoresist, and an alkaline component effective for the development processing is consumed. Therefore, the alkaline developer repeatedly used is a multi-component system including not only the alkali component but also a photoresist and carbon dioxide. Each of these components affects development performance with different contributions. Therefore, in order to maintain and manage the developing performance of the developing solution with high accuracy, it is necessary to manage the developing solution in consideration of the influence of these components on the developing performance.

  In order to solve such a problem, Patent Document 2 discloses the ultrasonic propagation velocity, conductivity and conductivity at alkali concentration, carbonate concentration and dissolved resin concentration by measuring the ultrasonic propagation velocity, conductivity and absorbance of the developer. The alkali concentration, carbonate concentration and dissolved resin concentration of the developer are detected based on a previously created relationship (matrix) between the absorbance and the absorbance, and the measured alkali concentration, carbonate concentration and dissolved resin concentration of the developer, Control the supply of the developer stock solution based on the pre-created relationship between the alkali concentration, carbonate concentration and dissolved resin concentration that can exhibit the dissolving ability so that the CD value (line width) becomes a constant value. A developer preparation device for adjusting the alkali concentration is disclosed.

  Patent Document 3 discloses a carbonate-based salt concentration measuring device that measures the refractive index, conductivity, and absorbance of a developer, and obtains the carbonate-based salt concentration in the developer from the measured values, and the carbonic acid salt. An alkaline developer management system including a system salt concentration measuring device and a control unit that controls a carbonate salt concentration in a developer is disclosed.

Japanese Patent No. 2561578 JP 2008-283162 A JP 2011-128455 A

  However, the ultrasonic wave propagation velocity value and refractive index value of the alkaline developer are characteristic values indicating the properties of the whole of the multi-component alkaline developer. Such characteristic values indicating the properties of the entire liquid generally do not correlate only with the concentration of a specific component contained in the liquid. Such characteristic values indicating the properties of the entire liquid generally have a correlation with each of the concentrations of various components contained in the liquid. Therefore, when the component concentration of the developer is calculated from the measured value of the characteristic value indicating the properties of the entire liquid, it is assumed that a certain characteristic value correlates with only a specific component concentration (for example, has a linear relationship). If the influence of the component on the characteristic value is ignored, the concentration of the specific component cannot be calculated with sufficient accuracy.

  On the other hand, when calculating the concentration of each component from the measured value of the characteristic value of the developer assuming that the characteristic value of the developer is a function of the concentration of various components contained in the developer, a plurality of characteristic values must be measured. Therefore, it is necessary to employ an appropriate calculation method for calculating the concentration of each component from the measured values of these characteristic values. However, it is very difficult to appropriately select a characteristic value to be measured and find an appropriate calculation method that can accurately calculate the concentration of each component from the measured value of the characteristic value. For this reason, there is a problem that the concentration of each component cannot be calculated with sufficient accuracy unless the measured characteristic value and calculation method are appropriate.

  Furthermore, in multicomponent liquids, the concentration of one component is generally not independent of the concentration of another component. In a multi-component liquid, there is a correlation that when the concentration of a certain component changes, the concentration of other components also changes at the same time. This makes it more difficult to calculate the component concentration with high accuracy and to manage the developer with high accuracy.

  In addition, with respect to the concentration of carbon dioxide absorbed in the developer (hereinafter referred to as “absorbed carbon dioxide concentration”), an appropriate characteristic value of the developer showing a good correlation with this is not known. It was difficult to accurately measure the absorbed carbon dioxide concentration.

  Further, in Patent Document 2, in order to detect the component concentration of the developer, it is necessary to obtain a correlation (matrix) between the component concentration of the developer and a characteristic value such as an ultrasonic propagation velocity in advance. . However, in this case, if the mutual relationship (matrix) is rough, the component concentration cannot be calculated with high accuracy. In order to calculate the component concentration with high accuracy, the correlation (matrix) between the characteristic value of the developer used for the calculation and the component concentration must be sufficiently dense. Therefore, as the calculation accuracy of the component concentration is increased, more samples must be prepared in advance, and the correlation between the component concentration and the characteristic value of the developer must be measured. Preparing such a close correlation (matrix) in advance is an enormous amount of work, and has been a problem in realizing high-precision measurement of the developer component concentration. In particular, it is important in managing the developing solution that the user can confirm the component concentration of the developing solution.

  The present invention has been made to solve the above-described problems. The present invention can measure the component concentration of the developer with high accuracy from the characteristic values of the developer which is a multi-component system, and can analyze the component concentration of the developer without preparing a large number of samples and preliminary measurement. An object of the present invention is to provide a developer component concentration measuring device capable of displaying the component concentration and a developer managing device capable of managing the component concentration of the developer more precisely.

  To achieve the above object, the present invention is as follows.

  (1) Based on the measurement unit that measures a plurality of characteristic values of the developer that is used repeatedly and has a correlation with the component concentration of the developer that exhibits alkalinity, and the plurality of characteristic values measured by the measurement unit , At least one of a calculation unit that calculates the component concentration of the developer by the multivariate analysis method, the characteristic value measured by the measurement unit, and the component concentration calculated by the calculation unit And a display unit for displaying the component concentration measuring device of the developer.

  (2) A measuring unit that repeatedly measures a plurality of characteristic values of the developing solution that are repeatedly used and correlates with a component concentration of the developing solution that exhibits alkalinity, and each time the measuring unit measures the plurality of characteristic values A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit, and the component concentration calculated by the calculation unit as a time and A measurement data storage unit that stores together with at least one of the elapsed time from the start of measurement, and the component concentration data stored in the measurement data storage unit from the time stored in the measurement data storage unit or the measurement start And a display unit that displays the graph using the elapsed time of the index as an index.

  (3) A measurement unit that repeatedly measures a plurality of characteristic values of the developer that correlates with a component concentration of a developer that exhibits alkalinity, and each time the measurement unit measures the plurality of characteristic values. A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit, and the characteristic value and the calculation unit that are measured by the measurement unit A measurement data storage unit that stores the concentration of the component calculated by the above together with at least one of time and elapsed time from the start of measurement, and at least one of a characteristic value and a component concentration stored in the measurement data storage unit And a display unit that displays a graph using the time stored in the measurement data storage unit or the elapsed time from the start of measurement as an index.

  (4) The development according to (3), further comprising display switching means for switching whether the graph displayed on the display unit is a graph of the characteristic value of the developer or a component concentration of the developer. Liquid component concentration measuring device.

  (5) Based on the measurement unit that measures a plurality of characteristic values of the developer that are used repeatedly and has a correlation with the component concentration of the developer that exhibits alkalinity, and the plurality of characteristic values measured by the measurement unit , At least one of a calculation unit that calculates the component concentration of the developer by the multivariate analysis method, the characteristic value measured by the measurement unit, and the component concentration calculated by the calculation unit , And a measured value of a management target item selected from a plurality of characteristic values of the developer measured by the measuring unit and a component concentration of the developer calculated by the calculating unit, or And a control unit that issues a control signal to a control valve provided in a conduit for supplying a replenisher to be replenished to the developer based on the calculated value.

  (6) A measuring unit that repeatedly measures a plurality of characteristic values of the developing solution that are repeatedly used and correlates with a component concentration of the developing solution that exhibits alkalinity, and each time the measuring unit measures the plurality of characteristic values A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit, and the component concentration calculated by the calculation unit as a time and A measurement data storage unit that stores together with at least one of the elapsed time from the start of measurement, and the component concentration data stored in the measurement data storage unit from the time stored in the measurement data storage unit or the measurement start A display section that displays a graph using the elapsed time of the index as an index, a plurality of characteristic values of the developer measured by the measurement section, and a component concentration of the developer calculated by the calculation section And a control unit that issues a control signal to a control valve provided in a conduit for supplying a replenisher to be replenished to the developer based on a measured value or a calculated value of a management target item selected from Liquid management device.

  (7) A measurement unit that repeatedly measures a plurality of characteristic values of the developer that correlates with a component concentration of a developer that exhibits alkalinity, and each time the measurement unit measures the plurality of characteristic values. A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit, and the characteristic value and the calculation unit that are measured by the measurement unit A measurement data storage unit that stores the concentration of the component calculated by the above together with at least one of time and elapsed time from the start of measurement, and at least one of a characteristic value and a component concentration stored in the measurement data storage unit One of the display unit displays a graph using the time stored in the measurement data storage unit or the elapsed time from the start of measurement as an index, and the developer measured by the measurement unit Based on a measured value or a calculated value of a management target item selected from a plurality of characteristic values and a component concentration of the developer calculated by the calculation unit, a replenisher to be replenished to the developer is sent. And a control unit that issues a control signal to a control valve provided in the pipeline.

  (8) The development according to (7), further comprising display switching means for switching whether the graph displayed on the display unit is a graph of the characteristic value of the developer or a component concentration of the developer. Liquid management device.

  (9) The measurement unit includes a first measurement unit that measures a characteristic value of the developer that is correlated with a concentration of at least an alkali component among the components of the developer, and at least the component concentration of the developer. The developer management apparatus according to any one of (5) to (8), further comprising: a second measuring unit that measures a characteristic value of the developer having a correlation with a concentration of the photoresist dissolved in the developer.

  (10) The calculation unit includes a calculation block for calculating the alkali component concentration and the photoresist concentration of the developer, and the control unit calculates the alkali component concentration calculated by the calculation block to a predetermined management value. A control block that issues a control signal to the control valve, and a control block that issues a control signal to the control valve so that the concentration of the photoresist calculated by the calculation block is a predetermined management value or less. The developing solution management apparatus according to (9).

  (11) The measurement unit further includes third measurement means for measuring a characteristic value of the developer having a correlation with at least a concentration of carbon dioxide absorbed in the developer among the components of the developer. The developer management apparatus according to (9).

  (12) The calculation unit includes a calculation block for calculating the concentration of carbon dioxide in the developer, and the control unit has a characteristic value of the developer measured by the first measuring unit as a predetermined management value. A control block that issues a control signal to the control valve, and a control signal to the control valve so that the characteristic value of the developer measured by the second measuring means falls within a predetermined management region. And a control block that issues a control signal to the control valve so that the concentration of carbon dioxide calculated by the calculation block is equal to or lower than a predetermined management value. apparatus.

  (13) The calculation unit includes a calculation block for calculating a concentration of an alkali component and a concentration of carbon dioxide in the developer, and the control unit has a predetermined management value for the concentration of the alkali component calculated in the calculation block. A control block that issues a control signal to the control valve, and a control signal to the control valve so that the characteristic value of the developer measured by the second measuring means falls within a predetermined management region. And a control block that issues a control signal to the control valve so that the concentration of carbon dioxide calculated by the calculation block is equal to or lower than a predetermined management value. apparatus.

  (14) The calculation unit includes a calculation block that calculates an alkali component concentration, a photoresist concentration, and a carbon dioxide concentration of the developer, and the control unit calculates an alkali component concentration calculated by the calculation block. A control block that issues a control signal to the control valve, and a control signal to the control valve so that the photoresist concentration calculated by the calculation block is equal to or lower than a predetermined management value. And a control block that issues a control signal to the control valve so that the concentration of carbon dioxide calculated by the calculation block is equal to or less than a predetermined management value. Management device.

  According to the present invention, the component concentration of a multi-component alkaline developer is calculated by a calculation means using a multivariate analysis method (for example, multiple regression analysis method). Compared to the conventional method of calculating the component concentration assuming that the component concentration has a predetermined correlation (for example, a linear relationship), the component concentration of the developer can be accurately determined from the characteristic values affected by the plurality of developer components. It is possible to calculate. In particular, according to the present invention, it is possible to measure the absorbed carbon dioxide concentration of a developer, which has been difficult to measure conventionally. Compared to a method in which a correlation (matrix) between a plurality of measurement characteristic values and a plurality of component concentrations is prepared in advance and used for calculation of the component concentration, the present invention prepares a huge amount of samples and performs preliminary measurement. There is no need to implement it. In the present invention, the measurement result can be easily confirmed.

  According to the present invention, since the concentration of each component of a multi-component alkaline developer can be measured with higher accuracy than before, the alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration are more accurate than the conventional ones. It is possible to control well. Further, according to the present invention, it is possible to select management for controlling the conductivity value of the developer to be constant and management for controlling the absorbance value of the developer to be equal to or less than the certain absorbance value.

It is a flowchart of the component density | concentration measuring method which shows the flow of a signal in the case of measuring the component density | concentration of two components from two characteristic values. It is a flowchart of the component density | concentration measuring method which shows the flow of a signal in the case of measuring the component density | concentration of three or more components from three or more characteristic values. It is a flowchart of the component density | concentration measuring method which shows the flow of a signal in case the calculation method different from a multivariate analysis method is included. It is a schematic diagram of the component density | concentration measuring apparatus which measures two components of a developing solution. It is a schematic diagram of the component density | concentration measuring apparatus which measures three components of a developing solution. It is a schematic diagram of the component density | concentration measuring apparatus which has a calculation block by the calculation method different from a multivariate analysis method in a calculating part. It is a schematic diagram of the component concentration measuring apparatus when a measurement part and a calculating part are separate bodies and in-line measurement is performed. It is a schematic diagram of the component concentration measuring apparatus when a measuring means consists of a main body and a probe part. It is a schematic diagram of the component density | concentration measuring apparatus provided with a measurement means in parallel. It is a schematic diagram of a component concentration measuring device when a measuring device requiring chemical addition is provided. It is the model which applied the component density | concentration measuring apparatus to the developing solution management apparatus. It is a schematic diagram for showing the application example of a component concentration measuring apparatus. It is a flowchart of the developing solution management method which manages two components of a developing solution by component concentration. FIG. 5 is a flowchart of a developer management method in which one of two components of a developer is managed by component concentration and the other is managed by a characteristic value. It is a flowchart of the developing solution management method which manages three components of a developing solution by component concentration. FIG. 5 is a flowchart of a developer management method in which one of three components of a developer is managed by a characteristic value and the other two are managed by a component concentration. FIG. 5 is a flowchart of a developer management method in which two of three components of a developer are managed by characteristic values and the other is managed by component concentration. It is a schematic diagram of the image development process for demonstrating the developing solution management apparatus of this invention. It is a schematic diagram of the developing solution management apparatus which controls the control valve outside an apparatus. It is a schematic diagram of a developer management apparatus provided with a calculation control unit having both a calculation function and a control function. It is a schematic diagram of the developing solution management apparatus which manages two components of a developing solution. It is a schematic diagram of the developing solution management apparatus which manages two components of a developing solution by component concentration. FIG. 4 is a schematic diagram of a developer management apparatus that manages two of the three components of the developer based on characteristic values and the other based on the component concentration. FIG. 3 is a schematic diagram of a developer management apparatus that manages one of three components of a developer by a characteristic value and the other two by a component concentration. It is a schematic diagram of the developing solution management apparatus which manages three components of a developing solution by component concentration.

  Hereinafter, preferred embodiments of the present invention will be described in detail with appropriate reference to the drawings. However, the shapes, sizes, dimensional ratios, relative arrangements, etc. of the devices described in these embodiments are only those shown within the scope of the present invention unless otherwise specified. It is not limited. It is only schematically shown as an example for explanation.

  In the following description, as a specific example of the developer, a 2.38% tetramethylammonium hydroxide aqueous solution (hereinafter, tetramethylammonium hydroxide is referred to as TMAH) that is mainly used in the manufacturing process of semiconductors and liquid crystal panel substrates. Will be described as appropriate. However, the developer to which the present invention is applied is not limited to this. Examples of other developing solutions to which the component concentration measuring device or developing solution management device of the developing solution of the present invention can be applied, an aqueous solution of an inorganic compound such as potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, An aqueous solution of an organic compound such as trimethylmonoethanolammonium hydroxide (choline) can be mentioned.

  In addition, the multivariate analysis method (for example, multiple regression analysis method) does not depend on the unit concentration of the component concentration when calculating the component concentration. However, in the following explanation, the alkali component concentration, dissolved photoresist is used. The component concentration such as the concentration and the absorbed carbon dioxide concentration is a concentration by weight percentage concentration (wt%). “Dissolved photoresist concentration” refers to the concentration when the dissolved photoresist is converted as the amount of photoresist, and “absorbed carbon dioxide concentration” refers to when the absorbed carbon dioxide is converted as the amount of carbon dioxide. The concentration of

  In the development process, development is performed by the developer dissolving unnecessary portions of the photoresist film after the exposure process. The photoresist dissolved in the developer generates a photoresist salt with the alkali component of the developer. For this reason, unless the developer is appropriately managed, as the development process proceeds, the developer deteriorates due to consumption of an alkaline component having development activity, and the development performance deteriorates. At the same time, the dissolved photoresist is accumulated in the developer as a photoresist salt with an alkali component.

  The photoresist dissolved in the developer exhibits a surface activity in the developer. For this reason, the photoresist dissolved in the developer improves the wettability of the photoresist film subjected to the development process with respect to the developer and improves the familiarity between the developer and the photoresist film. Therefore, with a developer containing a moderate amount of photoresist, the developer spreads well in fine concave portions of the photoresist film, and the development processing of the photoresist film having fine irregularities can be performed satisfactorily.

  Further, in recent development processing, with the increase in the size of the substrate, a large amount of the developer has been repeatedly used, so that the opportunity for the developer to be exposed to air is increasing. However, alkaline developers absorb carbon dioxide in the air when exposed to air. The absorbed carbon dioxide forms carbonate with the alkali component of the developer. For this reason, if the developer is not properly managed, the developer is consumed and reduced by the carbon dioxide in which the alkali component having development activity is absorbed. At the same time, the absorbed carbon dioxide is accumulated in the developer as a carbonate with an alkali component.

  The carbonate in the developer has a developing action because it shows alkalinity in the developer. For example, in the case of a 2.38% TMAH aqueous solution, development is possible if the carbon dioxide in the developer is about 0.4 wt% or less.

  Thus, unlike the conventional recognition that the photoresist dissolved in the developer and the absorbed carbon dioxide are unnecessary for the development process, the photoresist actually contributes to the developing performance of the developer. Therefore, it is not a developer management that completely eliminates dissolved photoresist and absorbed carbon dioxide, but a developer that maintains these at an optimum concentration while allowing them to be slightly dissolved in the developer. Management is required.

  Further, a part of the photoresist salt or carbonate generated in the developer is dissociated to generate various free ions such as photoresist ion, carbonate ion, hydrogen carbonate ion. These free ions affect the conductivity of the developer with various contributions.

  According to the conventional component concentration analysis of an alkaline developer, the alkali component concentration of the developer has a good linear relationship with the conductivity value of the developer, and the dissolved photoresist concentration of the developer is good with the absorbance value of the developer. (Hereinafter, this is referred to as “conventional method”). The developer management accuracy required in the conventional development process has been sufficiently realized by this analysis method because the carbon dioxide absorption amount has not yet been large.

  The conductivity value of the developer is a physical property value that depends on the number of charged particles such as ions contained in the developer and the amount of charges. In the developer, as described above, not only the alkali component but also various free ions derived from the photoresist dissolved in the developer and carbon dioxide absorbed in the developer. Therefore, in order to increase the analysis accuracy of the component concentration, it is necessary to use a calculation method that takes into account the influence of these free ions on the conductivity value of the developer.

  The absorbance value of the developer is a physical property value that has a linear relationship with the concentration of a specific component that selectively absorbs light of the measurement wavelength (Lambert-Beer law). However, in a multi-component system, although the degree varies depending on the measurement wavelength, the absorption spectrum of other components usually overlaps the absorption spectrum of the target component. Therefore, in order to improve the analysis accuracy of the component concentration, it is necessary to use a calculation method that takes into consideration not only the photoresist dissolved in the developer but also the influence of other components on the absorbance value of the developer. .

  With regard to these points, the inventor has conducted intensive research, and as a result, when a multivariate analysis method (for example, multiple regression analysis method) is used as the calculation method, each component of the developer is more accurately obtained than when using the conventional method. It was found that the concentration of carbon dioxide can be calculated, and that the absorbed carbon dioxide concentration, which has been difficult in the past, can be measured. In addition, the inventor can maintain and manage the dissolved photoresist concentration and absorbed carbon dioxide concentration in a good state by using the developer component concentration calculated by a multivariate analysis method (for example, multiple regression analysis method). I found.

  The inventor prepared a TMAH aqueous solution in which the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration were variously changed as a simulated developer sample on the assumption that the 2.38% TMAH aqueous solution was managed. The inventor conducted an experiment for determining the component concentration by a multiple regression analysis method from various characteristic values measured for these simulated developer samples. Hereinafter, a general calculation method based on the multiple regression analysis method will be described, and thereafter, a calculation method of the developer component concentration using the multiple regression analysis method will be described based on experiments conducted by the inventors.

Multiple regression analysis consists of two stages: calibration and prediction. Assume that m calibration standard solutions are prepared in an n-component multiple regression analysis. 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. With respect to m standard solutions, p characteristic values (for example, physical properties such as absorbance or conductivity at a certain wavelength) A _ik (k = 1 to p) are measured. The density data and the characteristic data can be collectively represented in matrix form (C, A).

A matrix relating these matrices is referred to as a calibration matrix, and here a symbol S (S _kj ; k = 1
~ P, j = 1 to n).

  It is possible to calculate S by matrix calculation from known C and A (the contents of A may include not only the same measurement value but also different measurement values. For example, conductivity, absorbance and density). Calibration stage. At this time, p> = n and m> = np must be satisfied. Since all elements of S are unknown, it is desirable that m> np. In this case, the least squares operation is performed as follows.

  Here, the superscript T means a transposed matrix, and the superscript -1 means an inverse matrix.

If p characteristic values are measured for a sample solution of unknown concentration and these are set to Au (Au _k ; k = 1 to p), the concentration Cu (Cu _j ; j = 1 to n) to be obtained by multiplying it by S ) Can be obtained.

  This is the prediction stage.

  The inventor regards the used alkaline developer (2.38% TMAH aqueous solution) as a multi-component system (n = 3) composed of three components of an alkali component, a dissolved photoresist, and absorbed carbon dioxide, and the developer. An experiment was conducted to calculate the concentration of each component by the multiple regression analysis method from three physical property values (p = 3), that is, the conductivity value of the developer, the absorbance value at a specific wavelength, and the density value. It was. The inventor prepared 11 calibration standard solutions in which the alkali component concentration (TMAH concentration), dissolved photoresist concentration, and absorbed carbon dioxide concentration were variously changed with a 2.38% TMAH aqueous solution as the basic composition of the developer. (When m = 11, p> = n and m> np are satisfied).

  In the experiment, for 11 calibration standard solutions, the conductivity value, the absorbance value at a wavelength λ = 560 nm, and the density value were measured as the characteristic values of the developer, and the concentration of each component was determined by linear multiple regression analysis (Multiple Linear Regression − Inverse Least Squares (MLR-ILS).

The measurement was performed by adjusting the temperature of the calibration standard solution to 25.0 ° C. To adjust the temperature, immerse the bottle containing the calibration standard solution in a constant temperature water bath whose temperature is controlled at around 25 ° C. for a long time, sample from here, and set the temperature controller to 25.0 ° C. again immediately before the measurement. This is the method. A conductivity meter made in-house was adopted as the conductivity meter. It measured using the conductivity flow cell made in-house which gave the platinum black process. The conductivity meter is inputted with the cell constant of the conductivity flow cell confirmed by a separate calibration operation. An in-house manufactured absorptiometer was also used. It is an absorptiometer including a light source unit having a wavelength λ = 560 nm, a photometric unit, and a glass flow cell. For the density measurement, a density meter employing a natural vibration method for obtaining a density from a natural frequency measured by exciting a U-shaped flow cell was used. The measured conductivity value, absorbance value, and density value are in units of mS / cm, Abs. (Absorbance), g / cm ³ .

  The calculation is based on the assumption that one of the 11 calibration standard solutions is an unknown sample, a calibration matrix is obtained with the remaining 10 standards, the concentration of the assumed unknown sample is calculated, and a known value (by other accurate analysis method) is calculated. This is based on a method (a single cross check method; Leave-One-Out method) compared with a measured concentration value or weight adjustment value.

  The results of MLR-ILS calculation are shown in Table 1.

  In the MLR-ILS calculation, in view of the fact that the TMAH aqueous solution is strongly alkaline and easily deteriorates by absorbing carbon dioxide, the concentration matrix used for the calculation includes a titration analysis method capable of accurately analyzing the concentration of alkali components and absorbed carbon dioxide. A value obtained by separately measuring the calibration standard solution was used. However, the weight preparation value was used for the dissolved photoresist concentration.

  Titration is neutralization titration using hydrochloric acid as a titration reagent. As a titration apparatus, an automatic titration apparatus GT-200 manufactured by Mitsubishi Chemical Analytech Co., Ltd. was used.

  Table 2 below shows the concentration matrix.

  Table 3 shows the measurement results of the physical property values of the calibration standard solution at this time. The column for absorbance is the absorbance value at the wavelength λ = 560 nm (optical path length d = 10 mm).

  Table 4 shows the calibration matrix.

  Table 5 shows a comparison between the measured concentration values in Table 2 and the calculated MLR-ILS values in Table 1.

  As shown in Table 5, the TMAH concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration determined by multiple regression analysis were all determined from the TMAH concentration and absorbed carbon dioxide concentration measured by titration analysis, and the adjusted weight. Both values are very close to the photoresist concentration.

  Thus, by measuring the conductivity, the absorbance at a specific wavelength, and the density of an alkaline developer, and using a multivariate analysis method (for example, multiple regression analysis), the alkali component concentration of the developer, dissolved photo It is understood that the resist concentration and the absorbed carbon dioxide concentration can be measured.

  A multivariate analysis method (for example, multiple regression analysis method) is effective for calculating and obtaining concentrations of a plurality of components. A plurality of characteristic values a, b, c,... Of the developer are measured, and component concentrations A, B, C,... Are obtained from the measured values by a multivariate analysis method (for example, multiple regression analysis method). it can. At this time, it is necessary that at least one characteristic value correlated with the component concentration is measured and used for calculation for the component concentration to be obtained.

  Here, the characteristic value of the developer that is “correlated” with the component concentration is that the characteristic value is related to the component concentration, and the characteristic value changes according to the change in the component concentration. Say. For example, the developer characteristic value a having a correlation with at least the component concentration A among the component concentrations of the developer is obtained when the characteristic value a is obtained by a function having the component concentration as a variable. The concentration A is included. The characteristic value a may be a function of only the component concentration A. Usually, when the characteristic value a is a multivariable function having the component concentrations B and C as variables in addition to the component concentration A, the multivariate analysis is performed. The significance of using a method (for example, multiple regression analysis) is great.

  The component concentration is a scale indicating the relative amount of the component with respect to the whole. The component concentration of a mixed solution whose components increase or decrease over time, such as a developer that is used repeatedly, is not determined by the component alone, but is usually a function of the concentration of other components. Therefore, it is often difficult to display the relationship between the characteristic value of the developer and the component concentration in a planar graph. In such a case, the component concentration cannot be calculated from the characteristic value of the developer by a calculation method using a calibration curve.

  However, according to the multivariate analysis method (for example, multiple regression analysis method), if a set of measured values of a plurality of characteristic values correlated with the component concentration to be calculated is prepared, this is used for the calculation. Is calculated as a set. The component concentration by the multivariate analysis method (for example, multiple regression analysis method) has the remarkable effect that the component concentration can be measured by measuring the characteristic value even if the component concentration is difficult to measure at first glance. It can be obtained by measurement.

  As described above, according to the calculation method of the present invention, the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration of the developer are determined based on the characteristic values of the developer (for example, conductivity, absorbance at a specific wavelength, and , Density) can be calculated based on the measured value. According to the calculation method of the present invention, the concentration of each component can be calculated with higher accuracy than in the conventional method.

  Further, since a multivariate analysis method (for example, multiple regression analysis method) is used in the present invention, the characteristics of the developer not having a linear relationship with a specific component concentration of the developer are used in the calculation of the component concentration of the developer. Values can also be adopted.

In addition, according to the present invention, it is not necessary to prepare a large number of samples and perform preliminary measurement to enable high-precision measurement, which is necessary in the invention of Patent Document 2. (As in the above experimental example, if the developer has n = 3 components, the number of characteristic values to be measured is p = 3, and the number of samples p satisfying m> = np (for example, p = 11 samples) is set. It is sufficient to prepare and measure.If the number of components is n = 2, the number of samples may be smaller.)
Furthermore, since the present invention uses a multivariate analysis method (for example, multiple regression analysis method), it is possible to accurately calculate the absorbed carbon dioxide concentration of the developer, which has been difficult to measure conventionally.

  Next, specific examples will be described with reference to the drawings. In the following examples, characteristic values a, b, c,... And component concentrations A, B, C,. For more specific understanding, the characteristic values a, b, c,... Are the conductivity, the absorbance at a specific wavelength (for example, λ = 560 nm), the density,. ,... May be re-read as alkali component concentration, dissolved photoresist concentration, absorbed carbon dioxide concentration,.

  However, the characteristic values a, b, c are the conductivity, the absorbance at a specific wavelength (for example, λ = 560 nm), the density, etc. This is merely an example of an optimal combination of characteristic values for calculating density and the like, and the present invention is not limited to this. Various combinations of the characteristic values a, b, c,... Can be selected according to the component concentrations A, B, C,. Examples of characteristic values that can be employed include developer conductivity, absorbance, ultrasonic wave propagation speed, refractive index, density, titration end point, pH, and the like. Since the developer may contain various additives, the component concentration may include the additive concentration in addition to the above three components.

  When managing the developer by measuring the alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration of the developer, a combination of conductivity, absorbance at a specific wavelength, and density is preferable as the characteristic value. The specific wavelength for measuring the absorbance is preferably a specific wavelength in the visible region, more preferably in the wavelength region of 360 to 600 nm, and even more preferably the wavelength λ = 480 nm or 560 nm. When the absorbed carbon dioxide concentration of the developer is relatively small and the change with time is gradual, the conductivity of the developer is in a relatively good linear relationship with the alkali component concentration, and the specific wavelength of the developer (for example, λ = 560 nm). This is because the absorbance in (1) has a relatively good linear relationship with the dissolved photoresist concentration. In addition, a combination of conductivity, absorbance at a specific wavelength, and ultrasonic wave propagation speed, and a combination of conductivity, absorbance at a specific wavelength, and refractive index can be preferably employed.

  The first to third embodiments described below relate to a method for measuring a component concentration of a developer according to the present invention.

  FIG. 1 is a flowchart of a component concentration measuring method of the present embodiment showing a signal flow when measuring component concentrations of two components of a developer from two characteristic values of the developer.

In the component concentration calculation method of this embodiment, first, in the step of measuring the characteristic values a and b of the developer, the respective measured values a _m and b _m are acquired. The acquired measurement values a _m and b _m are sent to the calculation step. Next, operation step receives the measured value a _m and b _m, using these, multivariate analysis (e.g., multiple regression analysis) by, calculating the component concentrations A, B. In this way, the component concentrations A and B are measured. If this flow is repeated, the component concentrations A and B of the developer can be measured continuously.

  FIG. 2 is a flowchart of the component concentration measurement method of this embodiment showing the signal flow when measuring the component concentrations of three or more components of the developer from the three or more characteristic values of the developer. It is.

In the component concentration calculation method of the present embodiment, first, in the step of measuring the developer characteristic values a, b, c,..., The respective measured values a _m , b _m , _cm ,. The acquired measurement values a _m , b _m , c _m ,... Are sent to the calculation step. Next, the calculation step receives the measurement values a _m , b _m , c _m ,..., And uses them to determine the component concentrations A, B, C,... By multivariate analysis (for example, multiple regression analysis). Is calculated. In this way, the component concentrations A, B, C,... Are measured. Moreover, if this flow is repeated, the component concentrations A, B, C,... Of the developer can be continuously measured.

  FIG. 3 shows the signal flow in the case where the calculation step in the case of measuring a plurality of component concentrations from the characteristic values of a plurality of developers also includes a step by a calculation method different from the multivariate analysis method. It is a flowchart of the component concentration measuring method of form.

  This embodiment is suitably employed when, for example, the developer characteristic value p, which is related only to the concentration P of a certain component of the developer, is employed as the measurement target. More specifically, the alkali component concentration and the absorbed carbon dioxide concentration of the developer are calculated from the conductivity value and density value of the developer by a multivariate analysis method, and the dissolved photoresist concentration of the developer is determined at a specific wavelength (for example, Examples include a case where a linear relationship with absorbance at λ = 560 nm) is calculated and measured using a calibration curve.

In the developer concentration measurement method of this embodiment, in the measurement step, the developer characteristic values a, b,... With a plurality of component concentrations as variables, and the developer characteristic values with only the component concentration P as variables. ,... are measured, and the measured values a _m , b _m ,... and pm _,.

  The calculation step includes a step of calculating a component concentration by a multivariate analysis method (for example, multiple regression analysis method), and a step of calculating a component concentration by a calculation method (for example, a calibration curve method) different from the multivariate analysis method; ,including. There is no limitation on the order of the calculation in these steps. It may be simultaneous.

  The step of calculating the component concentration by the multivariate analysis method (for example, multiple regression analysis method) is based on the measured values of the developer characteristic values a, b,... The component concentrations A, B,... Are calculated by a regression analysis method.

  In the step of calculating the component concentration by a calculation method different from the multivariate analysis method (for example, the calibration curve method), the linear relationship between the characteristic value p and the component concentration P obtained in advance is used as a calibration curve. The component concentration P,... Is calculated from the measured values of the developer characteristic values p,.

  As described above, the developer concentration measurement method includes a measurement step for measuring a plurality of characteristic values of a developer having a correlation with the component concentration of the developer, and a multivariate analysis method based on the measured plurality of characteristic values. And calculating a component concentration.

  The measurement step further includes a measurement step for measuring the characteristic value a, a measurement step for measuring the characteristic value b, a measurement step for measuring the characteristic value c, and so on. However, the order of these steps does not matter. It may be measured simultaneously. In addition, the temperature adjustment step, the reagent addition step, the waste liquid step, and the like may include steps necessary as appropriate according to the measurement technique.

  The calculation step only needs to include a calculation step for calculating the component concentration by the multivariate analysis method. A step of calculating a component concentration by a calculation method (for example, a calibration curve method) different from the multivariate analysis method may be included.

  Hereinafter, embodiments relate to a developer component concentration measuring apparatus of the present invention.

[First embodiment]
FIG. 4 is a schematic diagram of a component concentration measuring apparatus that measures two components of a developing solution. For convenience of explanation, the developer concentration measuring apparatus A is shown together with the developing process equipment B in a form connected to the developing process equipment B.

  First, the development process facility B will be briefly described.

  The development process facility B mainly includes a developer storage tank 61, an overflow tank 62, a development chamber hood 64, a roller conveyor 65, a developer shower nozzle 67, and the like. A developer is stored in the developer storage tank 61. The composition of the developing solution is replenished with the replenishing solution and is omitted in FIG. The developer storage tank 61 includes a level gauge 63 and an overflow tank 62, and manages an increase in the amount of liquid due to replenishment of the replenisher. The developer storage tank 61 and the developer shower nozzle 67 are connected by a developer conduit 80, and the developer stored in the developer reservoir 61 is filtered by a circulation pump 72 provided in the developer conduit 80. The liquid is fed to the developer shower nozzle 67 through 73. The roller conveyor 65 is provided above the developer storage tank 61 and conveys a substrate 66 on which a photoresist film is formed. The developer is dropped from the developer shower nozzle 67, and the substrate 66 conveyed by the roller conveyor 65 passes through the dropped developer and is immersed in the developer. Thereafter, the developer is collected in the developer storage tank 61 and stored again. As described above, the developer is circulated and used repeatedly in the development process. Note that the developing chamber in a small glass substrate may be subjected to a treatment that does not absorb carbon dioxide in the air, for example, by being filled with nitrogen gas. The deteriorated developer is drained (drained) by operating the waste liquid pump 71.

  Next, the developer concentration measuring apparatus A of the present embodiment will be described. The component concentration measuring apparatus of the present embodiment is a component concentration measuring apparatus that measures a characteristic value by sampling a developer.

  The developer component concentration measuring apparatus A includes a measurement unit 1 and a calculation unit 2, and is connected to a developer storage tank 61 by a sampling pipe 15 and a return pipe 16. The measurement unit 1 and the calculation unit 2 are connected by measurement data signal lines 51 and 52.

  The measuring unit 1 includes a sampling pump 14, a first measuring unit 11 and a second measuring unit 12 (the first measuring unit 11 and the second measuring unit 12 may be referred to as measuring units). is there). The measuring means 11 and 12 are connected in series downstream of the sampling pump 14. The measurement unit 1 preferably further includes a temperature adjusting means (not shown) that stabilizes the sampled developer at a predetermined temperature in order to increase the measurement accuracy. At this time, the temperature adjusting means is preferably provided immediately before the measuring means. The sampling pipe 15 is connected to the sampling pump 14 of the measuring unit 1, and the return pipe 16 is connected to a pipe at the end of the measuring means.

  The calculation unit 2 includes a calculation block 21 based on a multivariate analysis method. The calculation block 21 based on the multivariate analysis method includes a first measurement unit 11 provided in the measurement unit 1 by a measurement data signal line 51 and a second measurement provided in the measurement unit 1 by a measurement data signal line 52. It is connected to the means 12.

  Next, the measurement operation and calculation operation of the component concentration measuring apparatus A will be described.

  The developer collected from the developer storage tank 61 by the sampling pump 14 is guided into the measuring unit 1 of the component concentration measuring apparatus A through the sampling pipe 15. Thereafter, when the temperature adjusting means is provided, the sampled developer is sent to the temperature adjusting means, maintained at a predetermined measurement temperature (for example, 25 ° C.), and sent to the measuring means 11 and 12. . The first measuring means measures the characteristic value a of the developer, and the second measuring means measures the characteristic value b of the developer. The measured developer is returned to the developer storage tank 61 through the return pipe 16.

The measured value a _{m of} the developer characteristic value a measured by the first measuring unit 11 and the measured value b _m of the developer characteristic value b measured by the second measuring unit 12 are respectively measured. Via the data signal lines 51 and 52, it is sent to the calculation block 21 by the multivariate analysis method. Receiving the measurement values a _m and b _m , the calculation block 21 calculates these measurement values by the multivariate analysis method to calculate the component concentrations A and B of the developer. In this way, the component concentration measuring apparatus A measures the component concentrations A and B of the developer.

  The component concentration measuring apparatus A according to the embodiment includes a display unit DP. On the display unit DP, at least one of the characteristic value measured by the measurement unit 1 and the component concentration calculated by the calculation unit 2 is displayed. As shown in FIG. 4, the component concentrations A and B calculated by the calculation unit 2 may be displayed on the display unit DP, or the developer characteristic values (not shown) measured by the measurement unit 1. May be displayed. Both may be displayed. Also, any one of the characteristic value and the component concentration corresponding to each component of the developer may be selected and displayed.

  The display unit DP may be a display monitor electrically connected to the component concentration measuring device A, or a touch panel computer incorporated in the component concentration measuring device A. In the case of a touch panel computer, the calculation unit 2 can be included.

[Second Embodiment]
FIG. 5 is a schematic diagram of a component concentration measuring apparatus that measures three components of the developer. The developer component concentration measuring apparatus A includes a measuring unit 1 and a calculating unit 2, and is connected to a developing process facility B (developer storage tank 61) by a sampling pipe 15 and a return pipe 16. The measuring unit 1 includes a first measuring unit 11, a second measuring unit 12, and a third measuring unit 13, and these measure three characteristic values of the developer. The measured values of the three characteristic values are sent to the calculation unit 2 via the measurement data signal lines 51, 52 and 53, and the component concentrations of the three components of the developer are determined by the multivariate analysis method. Calculated. The description of the measurement operation, the calculation operation, and the members overlapping with those in FIG. 4 is the same as in the fourth embodiment, and will be omitted.

  The component concentration measuring apparatus A of the embodiment includes a display unit DP. The display unit DP can display the characteristic values (for example, a, b, c) measured by the measurement unit 1 and the component concentrations (for example, A, B, C) calculated by the calculation unit 2. In the embodiment, the display unit DP can switch the display of the characteristic value and the component concentration by a switching button BT which is a display switching unit set on the screen of the display unit DP. In the embodiment, the display is switched and displayed on the display unit DP. However, the characteristic values (a, b, c) and the component concentrations (A, B, C) are simultaneously displayed on the display unit DP. May be.

  As the display switching means, a switch for switching whether the display target displayed on the display unit DP is a characteristic value or a component concentration may be mounted on the outer surface of the apparatus, or operated on the display unit It may be displayed and implemented as a simple GUI (graphical user interface). Further, the display switching means may switch whether to display the characteristic value or the component concentration for all the components at once, or may be able to switch individually for each component.

[Third embodiment]
FIG. 6 is a schematic diagram of a component concentration measuring apparatus in which the calculation unit 2 has a calculation block using a calculation method different from the multivariate analysis method. For example, it is applied when there is a set of developer characteristic value and component concentration capable of measuring the developer component concentration from the measured developer physical property value by a calibration curve method or the like.

  The component concentration measuring apparatus A of the present embodiment includes a measuring unit 1 that measures a plurality of characteristic values of a developing solution, and an arithmetic unit 2 that calculates the component concentration of the developing solution from the measured values. The calculation unit 2 includes a calculation block 21 based on a multivariate analysis method and a calculation block 22 based on a calculation method other than the multivariate analysis method (for example, a calibration curve method).

  The measured value of the characteristic value of the developer used for calculation in the multivariate analysis method is measured by the measurement unit 1 and then sent to the calculation block 21 by the multivariate analysis method of the calculation unit 2. The measured values of the characteristic values of the developer used for calculation methods other than the multivariate analysis method (for example, the calibration curve method) are sent to the calculation block 22. By calculating the calculation blocks 21 and 22, the component concentration of the developer is calculated.

  Note that there may be a plurality of calculation blocks 22 by a calculation method other than the multivariate analysis method (for example, a calibration curve method). There is no limitation on the order of the calculation by the multivariate analysis method and the calculation by other methods (for example, the calibration curve method). In addition, description of the member etc. which overlap with the above-mentioned embodiment is abbreviate | omitted.

  The component concentration measuring apparatus A of the embodiment includes a display unit DP. Further, the component concentration measuring apparatus A includes a measurement data storage unit 10 having a storage block 101. The measurement data storage unit 10 stores the component concentration calculated by the calculation unit 2 together with at least one of time and elapsed time from the start of measurement. The storage block 101 may be composed of a plurality of storage blocks.

  As shown in FIG. 6, the display unit DP displays the data of the component concentrations (for example, A, B, C) stored in the measurement data storage unit 10 at the time stored in the measurement data storage unit 10 or the measurement start. The graph can be displayed using the elapsed time from as an index.

[Fourth embodiment]
FIG. 7 is a schematic diagram of a component concentration measuring apparatus in which the measurement unit 1 and the calculation unit 2 are configured separately. In the component concentration measuring apparatus A of the present embodiment, the measurement unit 1 is provided in a pipeline bypassed from the developer pipeline 80 of the development process equipment B, and is connected to the calculation unit 2 by measurement data signal lines 51 to 53. Has been. It may be directly connected to the developer pipe 80 or other pipe. Instead of the sampling pump 14, a flow rate adjusting valve (not shown) or the like may be used in combination.

  The component concentration measuring apparatus A of the embodiment includes a display unit DP. Further, the component concentration measuring apparatus A includes a measurement data storage unit 10 having a storage block 101. The measurement data storage unit 10 measures the characteristic values (for example, a, b, c) measured by the measurement unit 1 and the component concentrations (for example, A, B, C) calculated by the calculation unit 2, the time and measurement. It is stored together with at least one of the elapsed time from the start.

  The display unit DP stores at least one of the characteristic values (a, b, c) and component concentrations (A, B, C) stored in the measurement data storage unit 10 at the time stored in the measurement data storage unit 10. Alternatively, the graph can be displayed using the elapsed time from the start of measurement as an index. In the embodiment, the display unit DP can switch the graph display of the characteristic value and the component concentration by a switching button BT that is a display switching unit set on the screen of the display unit DP. In the embodiment, the graph display is switched and displayed on the display unit DP. However, the graph display of the characteristic values (a, b, c) and the component concentrations (A, B, C) is simultaneously performed on the display unit DP. May be displayed.

  As the display switching means, a switch for switching whether the display target displayed on the display unit is a graph of characteristic values or a graph of component concentration may be mounted on the outer surface of the apparatus, It may be displayed and implemented as an operable GUI (graphical user interface). Further, the display switching means may switch whether to display the characteristic value or the component concentration for all the components at once, or may be able to switch individually for each component.

[Fifth embodiment]
FIG. 8 shows a component concentration measuring apparatus when measuring means 11 to 13 for measuring characteristic values of a developing solution are constituted by measuring apparatus main bodies 11a, 12a and 13a and measuring probes 11b, 12b and 13b, respectively. FIG. The component concentration measuring apparatus of the embodiment includes a display unit DP. The same display as in the first to fourth embodiments can be performed by the display unit DP.

  In the present embodiment, the measurement probes 11b to 13b of the measuring units 11 to 13 are immersed in the developer stored in the developer storage tank 61, whereby the characteristic value of the developer is measured. The measured characteristic value of the developing solution is sent to the calculation unit 2 via the measurement data signal lines 51 to 53. The component concentration of the developer is measured by calculating the component concentration by the multivariate analysis method in the calculation unit 2.

  Although FIG. 8 shows a case where the measurement unit 1 and the calculation unit 2 are configured separately, a component concentration measurement device configured integrally may be used. In this case, the measurement probe immersed in the developer and the measurement device main body arranged in the measurement unit 1 of the component concentration measurement device are connected by a cable or the like.

[Sixth embodiment]
FIG. 9 is a schematic diagram of a component concentration measuring apparatus when measuring means in the measuring unit 1 are arranged in parallel. The component concentration measuring apparatus of the embodiment includes a display unit DP. The same display as in the first to fourth embodiments can be performed by the display unit DP.

  Each measuring means constituting the measuring unit 1 is not limited to being connected in series, and may be connected in parallel. As shown in FIG. 9, the measuring means 11 to 13 may include sampling pipes 15 a to 15 c, sampling pumps 14 a to 14 c, return pipes 16 a to 16 c, etc., or pipes branched in the middle. May be connected in parallel. The characteristic values of the developer measured by the measuring units 11 to 13 are sent to the calculation unit 2. The calculation unit 2 calculates the developer component concentration by a multivariate analysis method.

[Seventh embodiment]
FIG. 10 is a schematic diagram of a component concentration measuring apparatus having a measuring apparatus that requires chemical addition, such as an automatic titration apparatus. In FIG. 10, the third measuring means 13 is a measuring device that requires drug addition. The component concentration measuring apparatus of the embodiment includes a display unit DP. The same display as in the first to fourth embodiments can be performed by the display unit DP.

  In this case, the third measuring means 13 is connected to the sampling pipe 15 and the sampling pump 14 and is connected to the additive reagent 93 through the liquid feeding pipe 18. The added reagent is collected by a liquid feed pump and used for measurement. The developer after the measurement is drained (drained) through the waste liquid pipe 19. In addition, the measurement operation, the calculation operation, and the like are the same as those in the other embodiments, and are omitted.

  As described above, as shown in the first to seventh embodiments, the component concentration measuring apparatus of the present invention includes the measuring unit 1 that measures a plurality of characteristic values of the developer having a correlation with the component concentration of the developer, and the measurement. A calculation unit 2 that measures the component concentration of the developer by a multivariate analysis method based on a plurality of characteristic values of the developer measured by the unit 1 and a display unit DP are provided.

  The measuring unit 1 of the component concentration measuring apparatus A of the present embodiment can take various embodiments. Since the measuring device used for the measuring means has a method of installation and connection suitable for the measuring method employed by the measuring device, the measuring unit 1 of the component concentration measuring device of the present invention is optimal for the measuring means. What is necessary is just to make it a structure.

  The measuring unit 1 only needs to be provided with measuring means necessary for measuring a plurality of characteristic values of the developer. It is desirable to provide temperature adjusting means (not shown). It is desirable that the sampling pump 14, the liquid feed pump 17, the waste liquid pipe 19, and the like are appropriately provided as necessary, but they are not necessarily indispensable as internal components of the measurement unit 1.

  Further, the measurement unit 1 and the calculation unit 2 may be integrated or separated. The measurement unit 1 and the calculation unit 2 only need to communicate with each other so that the calculation unit 2 can receive measurement data of the developer characteristic value measured by the measurement unit 1. The measurement unit 1 and the calculation unit 2 are not limited to being connected by a signal line, but may be configured to be able to transmit and receive data wirelessly. There is no need for a plurality of measuring means to be integrated into one place to form the measuring unit 1, and only one specific measuring means may be provided separately.

  Each measuring means may be not only a method of sampling and measuring, but also a method of directly attaching to a pipe or a method of immersing a probe in a liquid. Each measuring means may be connected in series or may be connected in parallel. The measurement unit 1 may be configured by these various combinations.

  Note that the order of the measurement of the plurality of characteristic values of the developer in the measurement unit 1 of the present embodiment is not limited. The arrangement of each measuring means in the measuring unit 1 in the drawings from FIG. 4 to FIG. 10, and “first”, “first measuring means”, “second measuring means”,. Words such as “second”,... Do not limit the order of measurement in the present invention. Words such as “first”, “second”,... Are merely conveniences for distinguishing a plurality of measuring means.

  Moreover, if the calculating part 2 of the component concentration measuring apparatus of this embodiment includes the calculation block 21 by the multivariate analysis method, it has the calculation block by methods (for example, calibration curve method) other than the multivariate analysis method separately. It may be. At this time, the order of operations does not matter.

  In the component concentration measuring apparatus of the present embodiment, each measuring means constituting the measuring unit 1 is installed and connected in an arrangement suitable for the measuring method, measures a plurality of characteristic values of the developer, and the calculating unit 2 By receiving the measured value of the characteristic value of the developer measured by the measurement unit 1, the component concentration of the developer is calculated by a multivariate analysis method (including a calculation method).

  Hereinafter, in the eighth embodiment and the ninth embodiment, application examples of the component concentration measuring apparatus of the present embodiment will be described. The component concentration measuring apparatus of the present embodiment can be applied to various apparatuses and systems as one component.

[Eighth embodiment]
FIG. 11 is a schematic diagram of a developer management apparatus using the component concentration measuring apparatus of the present embodiment.

  In the present embodiment, the component concentration measuring apparatus A is connected to the control unit 3 (control apparatus) that controls the control valves 41 to 43 by the calculation data signal line 54. The control unit 3 (control device) is connected to the control valves 41 to 43 through control signal signal lines 55 to 57. The control valves 41 to 43 are respectively supplied with replenisher lines 81 and 82 for supplying replenisher from the replenisher reservoirs 91 and 92 and a pure water line 83 for supplying pure water. , Is provided. The component concentration measuring apparatus A includes a display unit DP.

  The replenisher storage tanks 91 and 92 are pressurized with nitrogen gas, and the controller 3 (control device) opens and closes the control valves 41 to 43 so that the replenisher passes through the merging conduit 84 and becomes developer. To be replenished. The replenisher to be replenished is returned to the developer storage tank 61 by the circulation pump 74 via the circulation line 85 and stirred. The method and mechanism of the replenisher replenishment operation will be described in the embodiments of the developer management method and developer management apparatus described later.

  As described above, the component concentration measuring apparatus of the present embodiment is developed by combining with a control valve provided in a conduit for supplying a replenisher to be replenished to the developer and a controller for controlling them. It can be used as a component of the liquid management device.

Note that the replenisher refers to, for example, a stock solution of a developing solution, a new solution, and a regenerating solution. May contain pure water. The stock solution is an unused developer having a high alkali component concentration (for example, 20 to 2).
5% TMAH aqueous solution). The new solution is an unused developer (for example, 2.38% TMAH aqueous solution) having the same alkali component concentration as the concentration used in the development step. The regenerated solution is a developer that can be reused by removing unnecessary substances from the used developer. These have different uses and effects as replenishers. For example, the stock solution is a replenisher for increasing the alkali component concentration, and lowers the dissolved photoresist concentration and the absorbed carbon dioxide concentration. The new solution is a replenisher for maintaining or slowly increasing / decreasing the alkali component concentration to lower the dissolved photoresist concentration and absorbed carbon dioxide concentration. Pure water is a replenisher for lowering the concentration of each component. The same applies to the description of the following embodiments.

  Further, FIG. 11 illustrates a case where the replenisher is supplied from the replenisher reservoirs 91 and 92 via the replenisher conduits 81 and 82 and the pure water is supplied via the pure water conduit 83. However, it is not limited to this. The replenisher may be sent from a replenisher reservoir 91 or 92 to a preparation tank (not shown), adjusted to a predetermined concentration therein, and then sent to the developer reservoir 61. In this case, the control valve is provided in the middle of a pipeline that is fed from the preparation tank to the developer storage tank 61. In some cases, pure water is not directly supplied to the developer storage tank 61. At this time, the pure water conduit 83 and the control valve 43 are not present. The same applies to the description of the following embodiments and the following drawings.

  The replenisher is stored in the replenisher reservoirs 91 and 92 of the replenisher reservoir C. The replenisher storage tanks 91 and 92 are connected to a nitrogen gas pipe 86 provided with pressurized gas valves 46 and 47, and are pressurized by nitrogen gas supplied through the pipes. Also, replenisher reservoirs 91 and 92 are connected to replenisher conduits 81 and 82, respectively, and replenisher is fed through valves 44 and 45 that are normally open. The replenisher lines 81 and 82 and the pure water line 83 are provided with control valves 41 to 43, and the control valves 41 to 43 are controlled to be opened and closed by the control unit 3. By operating the control valve, the replenisher stored in the replenisher reservoirs 91 and 92 is pumped and pure water is transported. Thereafter, the replenisher is joined to the circulation stirring mechanism D via the joining conduit 84, and is supplied to the developer storage tank 61 and stirred.

  When the replenisher stored in the replenisher reservoirs 91 and 92 decreases due to replenishment, the internal pressure decreases and the supply amount becomes unstable. Nitrogen gas is supplied by opening as appropriate, and the internal pressure of the replenisher storage tanks 91 and 92 is maintained. When the replenisher reservoirs 91 and 92 are emptied, the valves 44 and 45 are closed and replaced with a new replenisher reservoir filled with the replenisher, or the separately procured replenisher is emptied. The replenisher storage tanks 91 and 92 are filled again.

[Ninth embodiment]
The component concentration measuring apparatus according to the present embodiment can be applied to a developer concentration abnormality alarm device in combination with a warning lamp WL or an alarm device WT. FIG. 12 is a schematic diagram for showing an application example of the component concentration measuring apparatus of the present invention. Thus, the component concentration measuring apparatus of the present invention can be applied to various apparatuses and systems as parts.

  Hereinafter, FIGS. 13 to 17 relate to the developer management method of the embodiment.

  The developer management method of the present invention includes a measurement step for measuring a plurality of characteristic values of a developer having a correlation with a component concentration of an alkaline developer, and a developer component by a multivariate analysis method from the measured plurality of characteristic values. And a replenishment step of replenishing the developer with the replenisher based on either the measured developer characteristic value or the calculated developer component concentration. Since the measurement step and the calculation step are the same as the measurement step and the calculation step in the developer component concentration measurement method described above, redundant description thereof will be omitted in the following embodiments from FIG. 13 to FIG.

  Further, in the following description, the “predetermined control value” is previously known experimentally or experimentally as a characteristic value or component concentration value when the developer exhibits optimum liquid performance. Characteristic value or component concentration value. That is, for example, a numerical value that is an index of the developing performance of the developer, such as a line width and a residual film thickness formed on the substrate after development, is known in advance as a characteristic value or a component concentration value that makes the most preferable state. It means a certain value. The “predetermined management area” is also a range of such management values. The same applies to the description of the developer management apparatus.

  FIG. 13 is a flowchart of a developer management method for managing two components of a developer based on component concentrations. In the developer management method of this embodiment, in an alkaline developer that is managed so as to absorb less carbon dioxide, the alkali component concentration of the developer becomes a predetermined management value, and the dissolved photoresist concentration is It is preferably applied when managing the developer so as to be below a predetermined control value.

In the present embodiment, it is assumed that the component concentration A is managed to a predetermined management value A ₀ and the component concentration B is managed to be a predetermined management value B ₀ or less. The component concentration A is, for example, an alkali component concentration, and the component concentration B is, for example, a dissolved photoresist concentration.

In the measuring step, the characteristic values a and b of the developer are measured, and the measured values a _m and b _m are sent to the calculation step. In the calculation step, the component concentrations A and B of the developer are measured from the measured values a _m and b _m by a multivariate analysis method. The component concentrations A and B calculated by the calculation step are sent to the replenishment step.

  The replenishment step includes a step of adjusting the component concentration A and a step of adjusting the component concentration B.

First, in the step of adjusting the component concentration A, component concentration A is the management value A ₀ or greater than or to determine whether small. When it is larger, a replenisher (such as a new developer or pure water) that reduces the component concentration A is replenished to the developer. When it is small, a replenisher (such as a developing solution stock solution or a new solution) that works to increase the component concentration A is replenished to the developing solution. When component concentration A is the same as the management value A ₀ does nothing.

In the step of adjusting the component concentration B, component concentration B to determine whether the management value B ₀ is greater than. When it is larger, a replenisher that works to reduce the component concentration B (for example, a new developer is preferable because it does not change the alkali component concentration) is replenished to the developer. When it is small, nothing is done.

  FIG. 14 is a flowchart of a developer management method in the case where one of the two components of the developer is managed by the component concentration and the other is managed by the characteristic value. In the developing solution management method of the present embodiment, in an alkaline developing solution managed so as to absorb less carbon dioxide, the alkali component concentration of the developing solution becomes a predetermined management value, and the specific wavelength of the developing solution This is preferably applied to the case where the developer is managed so that the absorbance at (for example, λ = 560 nm) is not more than a predetermined management value.

In the present embodiment, the component concentration A to a predetermined control value A _0, and manages the measured values b _m for characteristic values b of the developer to a predetermined control value b ₀ or less. The component concentration A is, for example, the alkali component concentration, and the characteristic value b is, for example, the absorbance at a specific wavelength (for example, λ = 560 nm).

In the measuring step, the characteristic values a and b of the developer are measured, and the measured values a _m and b _m are sent to the calculation step. In the calculation step, the component concentrations A and B of the developer are measured from the measured values a _m and b _m by a multivariate analysis method. The component concentration A calculated by the calculation step and the measurement value b _m of the characteristic value b measured by the measurement step are sent to the replenishment step.

  The replenishment step includes a step of adjusting the component concentration A and a step of adjusting the characteristic value b. The step of adjusting the component concentration A is the same as that in the case of FIG.

In the step of adjusting the characteristic value b, it is determined whether or not the measured value b _m is larger than the management value b ₀ . When it is larger, a replenisher that works to reduce the component concentration B (for example, a new developer is preferable because it does not change the alkali component concentration) is replenished to the developer. When it is small, nothing is done.

When the the characteristic value b and component concentration B has a correlation of monotonically increasing, by characteristic value b is managed below the management value b0, is managed as the component concentration B is the management value B ₀ following Will be. When the characteristic value b and the component concentration B have a monotonously decreasing correlation, the component concentration B can be managed to be equal to or less than the management value B ₀ by operating the judgment with the magnitude relationship reversed. .

  FIG. 15 is a flowchart of a developer management method for managing the three components of the developer based on the component concentrations. In the developer management method of the present embodiment, for example, the alkali component concentration of the developer is set to a predetermined control value, the dissolved photoresist concentration is set to a predetermined control value or less, and the absorbed carbon dioxide concentration is set to a predetermined control value or less. It is preferably applied when managing.

In the replenishment step, the component concentration A is managed to a predetermined management value A ₀ , the component concentration B is managed to a predetermined management value B ₀ or less, and the component concentration C is managed to a predetermined management value C ₀ or less. The component concentration A is, for example, an alkali component concentration, the component concentration B is, for example, a dissolved photoresist concentration, and the component concentration C is, for example, an absorbed carbon dioxide concentration.

In the measurement step, the characteristic values a, b, c,... Of the developer are measured, and the measured values a _m , b _m , _cm ,. In the calculation step, the developer component concentrations A, B, C,... Are measured from the measured values a _m , b _m , _cm ,. The component concentrations A, B, C,... Calculated by the calculation step are sent to the replenishment step.

  The replenishment step includes a step of adjusting the component concentration A, a step of adjusting the component concentration B, and a step of adjusting the component concentration C.

First, in the step of adjusting the component concentration A, component concentration A is the management value A ₀ or greater than or to determine whether small. When it is larger, a replenisher (such as a new developer or pure water) that reduces the component concentration A is replenished to the developer. When it is small, a replenisher (such as a developing solution stock or a new solution) that works to increase the component concentration A is replenished to the developer. When component concentration A is the same as the management value A ₀ does nothing.

In the step of adjusting the component concentration B, component concentration B to determine whether the management value B ₀ is greater than. When it is large, a replenisher that works to reduce the component concentration B (for example, a new developer is preferable because it does not change the alkali component concentration) is replenished to the developer. When it is small, nothing is done.

In the step of adjusting the component concentration C, component concentration C is determined whether the larger control value C _0. When it is large, a replenisher that works to reduce the component concentration C (for example, a new developer is preferable because it does not change the alkali component concentration) is replenished to the developer. When it is small, nothing is done.

  FIG. 16 is a flowchart of a developer management method in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration. In the developer management method of the present embodiment, the absorbance at a specific wavelength (for example, λ = 560 nm) of the developer is equal to or less than the predetermined management value so that the alkali component concentration of the developer becomes a predetermined management value. And it is preferably applied when managing the developer so that the absorbed carbon dioxide concentration of the developer is not more than a predetermined control value.

In this embodiment, the component concentration A is set to a predetermined management value A ₀ , the measured value b _m of the developer characteristic value b is set to a predetermined management value b ₀ or less, and the component concentration C is set to a predetermined management value C ₀ or less. Shall be managed. The component concentration A is, for example, the alkali component concentration, the characteristic value b is, for example, the absorbance at a specific wavelength (for example, λ = 560 nm), and the component concentration C is, for example, the absorbed carbon dioxide concentration.

In the measurement step, the characteristic values a, b, and c of the developer are measured, and the measured values a _m , b _m , and _cm are sent to the calculation step. In the calculation step, the component concentrations A, B, and C of the developer are measured from the measured values a _m , b _m , and _cm by a multivariate analysis method. The component concentrations A and C calculated in the calculation step and the measurement value b _m of the characteristic value b measured in the measurement step are sent to the replenishment step.

  The replenishment step includes a step of adjusting the component concentration A, a step of adjusting the characteristic value b, and a step of adjusting the component concentration C. The step of adjusting the component concentration A and the step of adjusting the component concentration C are the same as those in FIG.

In the step of adjusting the characteristic value b, it is determined whether or not the measured value b _m is larger than the management value b ₀ . When it is larger, a replenisher that works to reduce the component concentration B (for example, a new developer is preferable because it does not change the alkali component concentration) is replenished to the developer. When it is small, nothing is done.

When the characteristic value b and the component concentration B have a monotonically increasing correlation, the characteristic value b is managed to be less than or equal to the management value b ₀ , so that the component concentration B is managed to be less than or equal to the management value B _0. Will be. When the characteristic value b and the component concentration B have a monotonously decreasing correlation, if the magnitude relationship of the judgment is reversed (that is, b _m <b ₀ ) and the operation is performed, the component concentration B similarly has its management value B _It can be managed to be ₀ or less.

  FIG. 17 is a flowchart of a developer management method in which two of the three components of the developer are managed by the characteristic value and the other is managed by the component concentration. The developer management method of the present embodiment is such that the absorbance at a specific wavelength (for example, λ = 560 nm) of the developer is equal to or less than a predetermined management value so that the conductivity of the developer has a predetermined management value, and It is preferably applied when managing the developing solution so that the absorbed carbon dioxide concentration of the developing solution is not more than a predetermined control value.

In the present embodiment, the characteristic value measurement a _m a predetermined control value a ₀ of a developer, the measured values bm characteristic value b of the developer to a predetermined control value b0 below, the component concentration C given Management value C shall be managed below ₀ . The characteristic value a is, for example, conductivity, the characteristic value b is, for example, absorbance at a specific wavelength (for example, λ = 560 nm), and the component concentration C is, for example, absorbed carbon dioxide concentration.

In the measurement step, the characteristic values a, b, and c of the developer are measured, and the measured values a _m , b _m , and _cm are sent to the calculation step. In the calculation step, the component concentrations A, B, and C of the developer are measured from the measured values a _m , b _m , and _cm by a multivariate analysis method. The measurement value a _m of the characteristic value a measured in the measurement step, the measurement value b _m of b, and the component concentration C calculated in the calculation step are sent to the replenishment step.

  The replenishment step includes a step of adjusting the characteristic value a, a step of adjusting the characteristic value b, and a step of adjusting the component concentration C. The step of adjusting the characteristic value b and the step of adjusting the component concentration C are the same as in FIG.

In the step of adjusting the characteristic value a, the measured value a _m to determine whether large or small compared to its control value a _0. When it is larger, a replenisher (such as a developing solution stock solution or a new solution) that works to reduce the component concentration A is replenished to the developer. When it is small, a replenisher (such as a new developer or pure water) that works to increase the component concentration A is replenished to the developer. If they are the same, do nothing.

When the characteristic value a and the component concentration A have a monotonically increasing correlation, the characteristic value a is maintained at the management value a ₀ so that the component concentration A is managed to be the management value A _0. It will be. When the characteristic value a and component concentration A has correlation monotonic decrease, be operated by inverting the magnitude relationship between the determination, similarly, can be managed as the component concentration A becomes the management value A _0.

  As described above, the developer management method shown in FIGS. 13 to 17 is based on the measurement step for measuring a plurality of characteristic values of the developer having a correlation with the component concentration of the developer, and based on the measured plurality of characteristic values. A calculation step for calculating the component concentration of the developer by the variable analysis method, and a measured value or a calculated value of the management target item selected from the plurality of characteristic values of the measured developer and the calculated component concentration of the developer And a replenishment step of replenishing the developer with the replenisher based on the above.

  The measurement step further includes a measurement step for measuring the characteristic value a, a measurement step for measuring the characteristic value b, a measurement step for measuring the characteristic value c, and so on. However, the order of these steps does not matter. It may be measured simultaneously. In addition, the temperature adjustment step, the reagent addition step, the waste liquid step, and the like may include steps necessary as appropriate according to the measurement technique.

  The calculation step only needs to include a calculation step for calculating the component concentration by the multivariate analysis method. A step of calculating a component concentration by a calculation method (for example, a calibration curve method) different from the multivariate analysis method may be included.

  In the replenishment step, the management target item (either the developer characteristic value or the component concentration) is used as a control amount so that it becomes a predetermined management value, or less than the predetermined management value or within the management area. In addition, a step of replenishing the developer with a replenisher, a step of adjusting the component concentration A, a step of adjusting the component concentration B, a step of adjusting the component concentration C, and the like are included. The order is not limited to the order shown in the drawings.

  As a control method, various control methods used for control for adjusting a control amount to a target value can be adopted. In particular, proportional control (P control), integral control (I control), differential control (D control), and a combination of these (PI control, etc.) are preferable. More preferably, PID control is suitable.

In the embodiment shown in FIGS. 13 to 17, by repeating the measurement step, the calculation step, and the replenishment step, the developer component concentration A is maintained at its control value _A0 , and the developer component concentration B is the control value. Below B ₀ , the component concentration C is managed below its control value C ₀ . Therefore, the developing solution management method of the embodiment can maintain optimum developing performance, and can realize a desired line width and remaining film thickness.

  Hereinafter, tenth to seventeenth embodiments relate to the developer management apparatus of the present invention.

  The developer management apparatus according to the present embodiment includes a measurement unit 1 that measures a plurality of characteristic values of a developer having a correlation with a component concentration of an alkaline developer, and multivariate analysis from the plurality of characteristic values measured by the measurement unit 1. And a replenishment replenished to the developer based on the characteristic value of the developer measured by the measuring unit 1 or the component concentration of the developer calculated by the calculator 2. And a control unit 3 that emits a control signal to control valves 41 to 43 provided in pipes for feeding the liquid. Since the measurement unit 1 and the calculation unit 2 of the developer management apparatus of the present invention are the same as the measurement unit 1 and the calculation unit 2 in the developer component concentration measurement apparatus described above, the following eighteenth to twenty-fifth. In the above embodiments, the overlapping description is omitted.

[Tenth embodiment]
FIG. 18 is a schematic diagram of a developing process for explaining the developer management apparatus of the present invention. A developing solution management apparatus E of the present invention is shown together with a developing process facility B, a replenisher storing portion C, a circulation stirring mechanism D, and the like.

  The developing solution management apparatus E of the present embodiment includes a measuring unit 1 including a plurality of measuring units 11 to 13 that measure a plurality of characteristic values of the developing solution, a calculating unit 2 including a calculating block 21 based on a multivariate analysis method, And a control unit 3 for controlling either one of the developer characteristic value or the component concentration as a control amount so as to be within a predetermined management value or management region. Further, the developer management apparatus of the present embodiment includes control valves 41 to 43 that are connected to the control unit 3 and controlled.

  The developer management apparatus E is connected to the developer storage tank 61 by the sampling pipe 15. The developer sampled by the sampling pump 14 is guided into the measuring unit 1 through the sampling pipe 15. In the measuring unit 1, each measuring means 11-13 measures the characteristic value of the developer. The measured developer is returned to the developer storage tank 61 through the return pipe 16.

  The computing unit 2 receives a set of measured values of a plurality of characteristic values of the developer measured by the measuring unit 1. The computing unit 2 calculates the component concentration of the developer from the received set of measured values by a multivariate analysis method.

  The details of the measurement operation and the calculation operation are the same as those of the developer concentration measuring apparatus described above, and will be omitted. Hereinafter, the control operation will be described.

  The developer management apparatus E is connected to pipe lines 81 to 83 for supplying a replenisher to be replenished to the developer (including pure water as a replenisher). The pipes 81 to 83 are connected to control valves 41 to 43 whose operations are controlled by the control unit 3 in the developer management apparatus E.

  The control unit 3 receives the measured value of the developer characteristic value from the measurement unit 1 and the calculated component concentration from the calculation unit 2. The control unit 3 uses the received characteristic value or component concentration of the developer as a control amount, and issues a control signal to the control valves 41 to 43 based on the control amount. The control is performed, for example, so that the control amount becomes a predetermined management value or within a predetermined management area.

  The control unit 3 includes a control block. For example, if the developer management device E manages three component concentrations A, B, and C of the developer, the control unit 3 controls the control block 31 for controlling the component concentration A, and the component concentration B. And a control block 33 for controlling the component concentration C. If the component concentration to be managed is two, the number of control blocks may be two, and if the component concentration to be managed is more than three, the same control block is further provided accordingly. Thus, the control part 3 can issue a control signal required for the control valves 41 to 43.

  When the control valves 41 to 43 are, for example, control valves that are opened while receiving an “open” signal, and are open / close control valves that have been adjusted in advance so that a predetermined flow rate can be supplied when the valve is open. The control unit 3 needs a replenisher necessary for developing solution management by sending an “open” signal over a predetermined time to a control valve provided in a conduit for supplying a replenisher to be replenished. The developer is replenished by the amount.

  The control operation of the control valve is not limited to this example. When the control valve switches between an open state and a closed state of the valve by an open / close switching signal, the control unit 3 sends a pulsed open / close switching signal to the control valve at a predetermined time interval to provide the necessary replenishment. The developer is replenished to the developer in the required amount.

  Further, the control valves 41 to 43 may be capable of controlling the opening degree of the valve, or may be a combination of a simple flow rate adjustment valve (needle valve) and an open / close control valve. The control valves 41 to 43 may be electromagnetic valves or pneumatically operated valves (air operated valves).

  When the control valves 41 to 43 operate based on the control signal issued by the control unit 3, the replenisher in an amount necessary for developer management is replenished to the developer. The control unit 3 performs control so that the necessary replenishment amount is fed based on the type of replenisher obtained from the received control amount (characteristic value or component concentration of the developer) and the required replenishment amount. A control signal is issued to the control valve to be operated.

  In this way, the developer management apparatus according to the present embodiment uses the measured developer characteristic value or the calculated developer component concentration so that these become a predetermined management value, or a predetermined value. The developer can be maintained and managed so as to be within the management area.

  More specifically, the following developer management is possible. However, the developer management described below is merely an example, and the present invention is not limited to this.

  First, development in which a replenisher is replenished so that the alkaline component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration of an alkaline developer that is repeatedly used have predetermined control values. Liquid management. For example, according to the developer management apparatus of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution is preferably a predetermined management value within the range of 2.375 to 2.390 (wt%), more preferably 2. The dissolved photoresist concentration is preferably 380 (wt%), preferably a predetermined control value of 0.40 (wt%) or less, more preferably 0.15 (wt%), and the absorbed carbon dioxide concentration is preferably Can be managed to a predetermined management value of 0.40 (wt%) or less, more preferably 0.25 (wt%).

  Secondly, the developer so that the dissolved photoresist concentration and the absorbed carbon dioxide concentration are not more than the predetermined control values for each so that the alkali component concentration of the alkaline developer repeatedly used becomes a predetermined control value. This is developer management for supplying a replenisher. For example, according to the developer management apparatus of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution is preferably a predetermined management value within the range of 2.375 to 2.390 (wt%), more preferably 2. 380 (wt%) so that the dissolved photoresist concentration is preferably 0.40 (wt%) or less, and the absorbed carbon dioxide concentration is preferably 0.40 (wt%) or less. Can be managed.

  Third, development in which a replenisher is supplied to the developer so that the alkaline component concentration, the absorbance at a specific wavelength, and the absorbed carbon dioxide concentration of the alkaline developer to be used repeatedly become predetermined control values for each. Liquid management. For example, according to the developer management apparatus of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution is preferably a predetermined management value within the range of 2.375 to 2.390 (wt%), more preferably 2. Absorbance at a wavelength λ = 560 nm (cell optical path length d = 10 mm) at 2.380 (wt%), preferably a predetermined control value of 1.30 (Abs.) Or less, more preferably 0.50 (Abs. ), The absorbed carbon dioxide concentration can be managed preferably at a predetermined control value of 0.40 (wt%) or less, more preferably at 0.25 (wt%).

  Fourth, the absorbed carbon dioxide concentration is less than or equal to a predetermined management value so that the absorbance at a specific wavelength is within a predetermined management region so that the alkali component concentration of the alkaline developer repeatedly used is within the predetermined management. In this way, the developer management is to replenish the developer with the replenisher. For example, according to the developer management apparatus of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution is preferably a predetermined management value within the range of 2.375 to 2.390 (wt%), more preferably 2. Absorbance (cell optical path length d = 10 mm) at a wavelength λ = 560 nm at 2.380 (wt%), preferably 1.30 (Abs.) Or less, more preferably 0.65 (Abs.) Or less. In addition, the absorbed carbon dioxide concentration can be controlled so as to be preferably 0.40 (wt%) or less.

  Fifth, developer management that replenishes the developer with a replenisher so that the conductivity of the alkaline developer that is used repeatedly, the absorbance at a specific wavelength, and the absorbed carbon dioxide concentration are the predetermined control values for each. It is. For example, according to the developer management apparatus of the present invention, the conductivity of the 2.38% TMAH aqueous solution is preferably a predetermined management value within the range of 54.47 to 54.75 (mS / cm), more preferably Absorbance (cell optical path length d = 10 mm) at a wavelength λ = 560 nm at 54.58 (mS / cm), preferably a predetermined control value of 1.3 (Abs.) Or less, more preferably 0.50 (Abs) .), The absorbed carbon dioxide concentration can be controlled to a predetermined control value of preferably 0.40 (wt%) or less, more preferably 0.25 (wt%).

  Sixth, the absorbed carbon dioxide concentration is less than or equal to a predetermined management value so that the absorbance at a specific wavelength is within a predetermined management region so that the conductivity of the alkaline developer repeatedly used has a predetermined management value. In this way, the developer management is to replenish the developer with the replenisher. For example, according to the developer management apparatus of the present invention, the conductivity of the 2.38% TMAH aqueous solution is preferably a predetermined management value within the range of 54.47 to 54.75 (mS / cm), more preferably At 54.58 (mS / cm), the absorbance (cell optical path length d = 10 mm) at a wavelength λ = 560 nm is preferably 1.30 (Abs.) Or less, more preferably 0.65 (Abs.) Or less. Thus, it is possible to manage the absorbed carbon dioxide concentration so as to be preferably 0.40 (wt%) or less.

  Therefore, according to the developer management apparatus of the present embodiment, each component concentration or each characteristic value of the developer can be accurately managed within a predetermined management value or management area as compared with the conventional one. Optimum development performance can be maintained, and a desired line width and remaining film thickness can be realized. Various data and graphs can be displayed on the display unit DP.

[Eleventh embodiment]
FIG. 19 illustrates the developer management apparatus according to the embodiment in which the control valves 41 to 43 provided in the pipelines for supplying the replenisher supplied to the developer are outside the developer management apparatus according to the present embodiment. It is a schematic diagram for doing.

  The developer management apparatus E according to the present embodiment includes a measurement unit 1 including a plurality of measurement units that measure a plurality of characteristic values of the developer, a calculation unit 2 including a calculation block 21 based on a multivariate analysis method, and a developer. A control unit which issues a control signal to the control valves 41 to 43 provided in the replenishment liquid supply line so that either one of the characteristic value or the component concentration is a control amount, and this is within a predetermined management value or management region 3 is provided.

  In the present embodiment, the control valves 41 to 43 controlled by the control unit 3 are not internal components of the developer management apparatus E. As a separate body from the developer management device E, it is provided in a conduit through which the replenisher is fed. The developer management apparatus E is not connected to these pipelines through which the replenisher is fed. Other configurations and operations are the same as those in the tenth embodiment, and are omitted.

[Twelfth embodiment]
FIG. 20 is a schematic diagram of a developer management apparatus E including an arithmetic control unit 23 having both an arithmetic function and a control function.

  The developing solution management apparatus E of the present invention is not limited to the case where the calculation unit 2 and the control unit 3 are configured as separate devices. You may be comprised as the integral calculation control part 23 which has a calculation function and a control function together. An example of the arithmetic control unit 23 is a multifunction device such as a computer.

  Computers have a great variety of functions such as input / output functions, transmission / reception functions, arithmetic functions, control functions, and display functions. Therefore, the calculation function and control function of the developer management apparatus E of the present invention can be realized by a computer. The calculation control part 23 should just be connected with the measurement part 1 and the control valves 41-43. At this time, an arithmetic processing program for calculating the component concentration from the characteristic value of the developer measured by the multivariate analysis method and the control amount (the characteristic value or component concentration of the developer) become a predetermined management value, or If the control program that issues a control signal to the control valves 41 to 43 is mounted on the computer so as to be in the predetermined management area, the developer can be maintained in a predetermined state.

  Other configurations and operations are the same as those in the tenth embodiment, and are omitted.

[13th embodiment]
FIG. 21 is a schematic diagram of a developer management apparatus that manages two components of the developer. The developer management apparatus E of the present embodiment is preferably applied when managing the alkali component concentration and the dissolved photoresist concentration of an alkaline developer that is managed so as to absorb less carbon dioxide.

  The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of the developer having a correlation with at least the alkali component concentration among the components of the developer. It is assumed that the measuring unit 12 is a measuring unit (for example, an absorptiometer that measures absorbance at a wavelength λ = 560 nm) that measures at least the characteristic value of the developer that correlates with the dissolved photoresist concentration among the components of the developer. For example, since the calculation unit 2 includes the calculation block 21 based on the multivariate analysis method, the alkali component concentration and the dissolved photoresist concentration of the developer can be calculated from the characteristic values of the developer measured by the multivariate analysis method.

Then, the control block 31 is a control block that issues a control signal to the control valve so that the conductivity or alkali component concentration of the developer becomes a predetermined control value, and the control block 32 has a specific wavelength (for example, λ = 560 nm) of the developer. ) Is a control block that issues a control signal to the control valve so that the absorbance or dissolved photoresist concentration in the control region is within a predetermined control value or control region, the control unit 3 calculates the measured developer characteristic value. Since it is connected to the measurement unit 1 and the calculation unit 2 so that the component concentration of the developer can be received, the developer management device E of the present embodiment causes the alkali component concentration of the developer to become a predetermined management value. In addition, the developer can be maintained and managed so that the dissolved photoresist concentration falls within a predetermined management value or management area.

  The other details are the same as those of the other embodiments, and will be omitted.

[14th embodiment]
FIG. 22 is a schematic diagram of a developer management apparatus that manages two components of a developer based on component concentrations. The developer management apparatus of the present embodiment is preferably applied when managing the alkali component concentration and dissolved photoresist concentration of an alkaline developer managed so as not to absorb carbon dioxide to a management concentration value.

  The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring the characteristic value of the developer having a correlation with at least the alkali component concentration among the components of the developer. If the means 12 is a measuring means (for example, an absorptiometer that measures the absorbance at λ = 560 nm) that measures at least the characteristic value of the developer that correlates with the dissolved photoresist concentration among the components of the developer, an arithmetic operation is performed. Since the part 2 includes the calculation block 21 by the multivariate analysis method, the alkali component concentration and the dissolved photoresist concentration of the developer can be calculated from the characteristic values of the developer measured by the multivariate analysis method.

  Then, the control block 31 is a control block that issues a control signal to the control valve so that the alkali component concentration becomes a predetermined management value, and the control block 32 makes the dissolved photoresist concentration lower than the predetermined management value or the management value. If the control block is a control block that issues a control signal to the control valve, the control unit 3 is connected to the calculation unit 2 so as to receive the calculated component concentration of the developer. With the apparatus E, the developer can be maintained and managed so that the concentration of the alkali component of the developer becomes a predetermined management value, and the dissolved photoresist concentration becomes a predetermined management value or less than the management value.

  The other details are the same as those of the other embodiments, and will be omitted.

[Fifteenth embodiment]
FIG. 23 is a schematic diagram of a developer management apparatus that manages two of the three components of the developer based on characteristic values and the other based on the component concentration. The developer management apparatus of this embodiment manages the alkali component concentration of an alkaline developer by conductivity, the dissolved photoresist concentration by absorbance at a specific wavelength (for example, λ = 560 nm), and the absorbed carbon dioxide concentration by concentration. It is preferably applied to cases.

  The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of the developer having a correlation with at least the alkali component concentration among the components of the developer. The measuring unit 12 is a measuring unit (for example, an absorptiometer that measures absorbance at λ = 560 nm) that measures at least the characteristic value of the developer that correlates with the dissolved photoresist concentration among the components of the developer. If the measuring means is a measuring means (for example, a density meter for measuring the density) that measures at least the characteristic value of the developer that correlates with the absorbed carbon dioxide concentration among the components of the developer, Since the calculation block 21 by the multivariate analysis method is included, the alkali component concentration of the developer, the dissolved photoresist concentration, and the absorbed carbon dioxide are determined from the characteristic values of the developer measured by the multivariate analysis method. It is possible to calculate the degree.

  Then, the control block 31 is a control block that issues a control signal to the control valve so that the conductivity of the developer becomes a predetermined management value, and the control block 32 determines the absorbance at the characteristic wavelength of the developer (for example, λ = 560 nm). A control block that issues a control signal to the control valve so as to be within a predetermined management value or management area, and the control block 33 controls the control valve so that the absorbed carbon dioxide concentration is equal to or lower than the predetermined management value or management value. Control unit 3 is connected to measurement unit 1 so as to receive the measured characteristic value of the developer, and with calculation unit 2 so as to receive the calculated component concentration of the developer. Since it is connected, the concentration of dissolved photoresist is adjusted by the developer management apparatus E of this embodiment so that the alkali component concentration of the developer becomes a predetermined control value. As it will be less constant control value or the control value, and, as the absorption of carbon dioxide concentration equal to or less than a predetermined control value or control value, can maintain a developer.

  The other details are the same as those of the other embodiments, and will be omitted.

[Sixteenth embodiment]
FIG. 24 is a schematic diagram of a developer management apparatus that manages one of the three components of the developer based on the characteristic value and the other two based on the component concentration. The developer management apparatus of the present embodiment manages the alkaline component concentration and the absorbed carbon dioxide concentration of the alkaline developer by the concentration, and manages the dissolved photoresist concentration by the absorbance at a specific wavelength (for example, λ = 560 nm). , Preferably applied.

  The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of the developer having a correlation with at least the alkali component concentration among the components of the developer. The measuring unit 12 is a measuring unit (for example, an absorptiometer that measures absorbance at λ = 560 nm) that measures at least the characteristic value of the developer that correlates with the dissolved photoresist concentration among the components of the developer. If the measuring means is a measuring means (for example, a density meter for measuring the density) that measures at least the characteristic value of the developing solution that correlates with the absorbed carbon dioxide concentration among the components of the developing solution, there are many calculation units 2. Since the calculation block 21 by the variable analysis method is included, the alkali component concentration of the developer, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration are determined from the characteristic values of the developer measured by the multivariate analysis method. It can be calculated.

  Then, the control block 31 is a control block that issues a control signal to the control valve so that the alkali component concentration becomes a predetermined management value, and the control block 32 determines the absorbance at a characteristic wavelength (for example, λ = 560 nm) of the developer. Is a control block that issues a control signal to the control valve so that the control value falls within the management region, and the control block 33 sends a control signal to the control valve so that the absorbed carbon dioxide concentration becomes a predetermined management value or a management value or less. When the control block is issued, the control unit 3 is connected to the measurement unit 1 so as to receive the measured characteristic value of the developer, and is connected to the calculation unit 2 so as to receive the calculated component concentration of the developer. Therefore, the developer management device E of the present embodiment uses the dissolution photoresist so that the alkali component concentration of the developer becomes a predetermined control value. So that the concentration equal to or less than a predetermined control value or control value, and, as the absorption of carbon dioxide concentration equal to or less than a predetermined control value or control value, can maintain a developer.

  The other details are the same as those of the other embodiments, and will be omitted.

[17th embodiment]
FIG. 25 is a schematic diagram of a developer management apparatus that manages three components of a developer based on component concentrations. The developer management apparatus of the present embodiment is preferably applied to the case where the alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration of the alkaline developer are managed by the concentration.

  The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring the characteristic value of the developer having a correlation with at least the alkali component concentration among the components of the developer. The means 12 is a measuring means (for example, an absorptiometer for measuring the absorbance at λ = 560 nm) that measures at least the characteristic value of the developer having a correlation with the dissolved photoresist concentration among the components of the developer. If the means is a measuring means (for example, a density meter that measures the density) that measures at least the characteristic value of the developer that correlates with the absorbed carbon dioxide concentration among the components of the developer, the arithmetic unit 2 performs multivariate analysis. Since the calculation block 21 by the method is included, the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration of the developer are calculated from the characteristic values of the developer measured by the multivariate analysis method. It can be out.

  Then, the control block 31 is a control block that issues a control signal to the control valve so that the alkali component concentration becomes a predetermined management value, and the control block 32 makes the container photoresist concentration lower than the predetermined management value or the management value. When the control block 33 is a control block that issues a control signal to the control valve so that the absorbed carbon dioxide concentration becomes a predetermined management value or less than the management value. Is connected to the calculation unit 2 so as to receive the calculated component concentration of the developer, so that the developer management apparatus E according to the present embodiment causes the alkali component concentration of the developer to become a predetermined management value. The dissolved photoresist concentration is set to a predetermined control value or lower than the control value, and the absorbed carbon dioxide concentration is set to a predetermined control value or control. So that less can maintain the developing solution.

  The other details are the same as those of the other embodiments, and will be omitted.

  As described above, as shown in the tenth to seventeenth embodiments, the developer management apparatus according to the present embodiment includes the measurement unit 1 that measures a plurality of characteristic values of the developer having a correlation with the component concentration of the alkaline developer. The calculation unit 2 calculates the developer component concentration from the plurality of characteristic values measured by the measurement unit 1 by a multivariate analysis method, and the developer characteristic value measured by the measurement unit 1 or the calculation unit 2 And a control unit 3 that issues a control signal to control valves 41 to 43 provided in pipes for supplying a replenisher replenished to the developer based on the component concentration of the developer.

  The measurement unit 1 and the calculation unit 2 in the developer management apparatus according to the present embodiment can take various aspects, like the measurement unit 1 and the calculation unit 2 in the developer concentration measurement apparatus.

  The control unit 3 in the developer management apparatus of the present embodiment does not need to be provided as a separate device from the calculation unit 2, and may be implemented as a control function and a calculation function of an integrated device (for example, a computer). Good. In addition, as shown in FIG. 11, the control unit 3 may be configured separately from the measurement unit 1 and the calculation unit 2. The control unit 3 communicates with the measurement unit 1 and the calculation unit 2 so that the characteristic value measured by the measurement unit 1 serving as the control amount or the component concentration calculated by the calculation unit 2 can be received. It only has to be. Then, a necessary control signal can be issued based on the received characteristic value and component concentration.

  The conduit for feeding the replenisher may also be connected to the developer management apparatus E of the present embodiment, or may not be connected. The control valve may not be an internal component of the developer management apparatus E. As long as the control unit 3 communicates with the control unit 3 so as to be controlled by the control signal of the control unit 3, it may be provided outside the developer management apparatus E.

As described above, according to the developer management apparatus of the present invention, each component concentration or each characteristic value of the developer can be managed within a predetermined management value or management range. Therefore, with the developer management apparatus of the present invention, it is possible to maintain optimum developing performance and realize a desired line width and remaining film thickness.

  According to the developer management apparatus of the present invention, since the concentration of each component of the developer is accurately controlled to a predetermined state, the development performance of the developer can be maintained and managed so as to be more accurate and constant. Therefore, the development speed when developing the photoresist is stabilized, the line width and remaining film thickness by the development process are made constant, the product quality is improved, and further miniaturization and higher integration are realized. It is expected to contribute to

  According to the developer management apparatus of the present invention, since the developer is automatically maintained at the optimum development performance at all times, the yield of the product is improved, and the replacement work of the developer is not required, and the running cost and the waste liquid cost are reduced. It is expected to contribute to

A ... Component concentration measuring device, B ... Development process equipment, C ... Replenisher storage unit, D ... Circulating stirring mechanism, E ... Developer management device 1 ... Measuring unit 11 ... First measuring means, 12 ... Second measurement Means, 13 ... third measuring means,
11a, 12a, 13a ... measuring device main body, 11b, 12b, 13b ... measuring probe 14, 14a, 14b, 14c ... sampling pump, 15, 15a, 15b, 15c ... sampling pipe, 16, 16a, 16b, 16c ... return pipe DESCRIPTION OF SYMBOLS 17 ... Liquid feed pump, 18 ... Liquid feed piping, 19 ... Waste liquid piping 2 ... Calculation part 21 ... Calculation block by multivariate analysis method, 22 ... Calculation block 23 by calibration curve method ... Calculation control part (for example, computer)
3 ... Control unit 31, 32, 33 ... Control block 4 ... Valve 41-43 ... Control valve, 44, 45 ... Valve, 46, 47 ... Valve for pressurized gas 5 ... Signal line 51-53 ... Signal line for measurement data 54 ... Calculation data signal line 55-57 ... Control signal signal line 6 ... Development facility 61 ... Developer storage tank 62 ... Overflow tank 63 ... Liquid level gauge 64 ... Development chamber hood 65 ... Roller conveyor , 66 ... Substrate, 67 ... Developer shower nozzle 7 ... Development equipment 71 ... Waste liquid pump, 72, 74 ... Circulation pump, 73, 75 ... Filter 8 ... Fluid line 80 ... Developer line, 81, 82 ... Replenisher (Development stock solution and / or new solution) conduit, 83... Pure water conduit, 84. Confluence conduit, 85 .. circulation conduit, 86 .. nitrogen gas conduit 9 .. replenisher reservoir, and others 91 92 ... Replenisher (developer stock solution and / or new solution) Tomeso 93 ... adding reagent 10 ... measurement data storage section 101 ... storage block DP ... display unit

Claims (14)

A measurement unit that measures a plurality of characteristic values of the developer that are used repeatedly and correlates with a component concentration of the developer that exhibits alkalinity;
Based on the plurality of characteristic values measured by the measurement unit, a calculation unit that calculates a component concentration of the developer by a multivariate analysis method;
A display unit that displays at least one of the characteristic value measured by the measurement unit and the component concentration calculated by the calculation unit;
An apparatus for measuring a concentration of a component of a developer. A measurement unit that repeatedly measures a plurality of characteristic values of the developer that are correlated with the component concentration of the alkaline developer that is used repeatedly;
A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit each time the measurement unit measures the plurality of characteristic values;
A measurement data storage unit that stores the component concentration calculated by the calculation unit together with at least one of time and elapsed time from the start of measurement;
A display unit for displaying the data of the component concentration stored in the measurement data storage unit as a graph with the time stored in the measurement data storage unit or the elapsed time from the start of measurement as an index;
An apparatus for measuring a concentration of a component of a developer. A measurement unit that repeatedly measures a plurality of characteristic values of the developer that are correlated with the component concentration of the alkaline developer that is used repeatedly;
A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit each time the measurement unit measures the plurality of characteristic values;
A measurement data storage unit that stores the characteristic value measured by the measurement unit and the component concentration calculated by the calculation unit together with at least one of time and elapsed time from the start of measurement;
A display unit that displays at least one of the characteristic value and the component concentration stored in the measurement data storage unit as a graph with the time stored in the measurement data storage unit or the elapsed time from the start of measurement as an index;
An apparatus for measuring a concentration of a component of a developer.   4. The developer concentration measurement of a developer according to claim 3, further comprising display switching means for switching whether the graph displayed on the display unit is a graph of the characteristic value of the developer or a component concentration of the developer. apparatus. A measurement unit that measures a plurality of characteristic values of the developer that are used repeatedly and correlates with a component concentration of the developer that exhibits alkalinity;
Based on the plurality of characteristic values measured by the measurement unit, a calculation unit that calculates a component concentration of the developer by a multivariate analysis method;
A display unit that displays at least one of the characteristic value measured by the measurement unit and the component concentration calculated by the calculation unit;
Based on a measured value or calculated value of a management target item selected from a plurality of characteristic values of the developer measured by the measuring unit and a component concentration of the developer calculated by the calculating unit. A control unit that issues a control signal to a control valve provided in a conduit for supplying replenisher to be replenished to the liquid;
A developer management apparatus comprising: A measurement unit that repeatedly measures a plurality of characteristic values of the developer that are correlated with the component concentration of the alkaline developer that is used repeatedly;
A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit each time the measurement unit measures the plurality of characteristic values;
A measurement data storage unit that stores the component concentration calculated by the calculation unit together with at least one of time and elapsed time from the start of measurement;
A display unit for displaying the data of the component concentration stored in the measurement data storage unit as a graph with the time stored in the measurement data storage unit or the elapsed time from the start of measurement as an index;
Based on a measured value or calculated value of a management target item selected from a plurality of characteristic values of the developer measured by the measuring unit and a component concentration of the developer calculated by the calculating unit. A control unit that issues a control signal to a control valve provided in a conduit for supplying replenisher to be replenished to the liquid;
A developer management apparatus comprising: A measurement unit that repeatedly measures a plurality of characteristic values of the developer that are correlated with the component concentration of the alkaline developer that is used repeatedly;
A calculation unit that calculates a component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit each time the measurement unit measures the plurality of characteristic values;
A measurement data storage unit that stores the characteristic value measured by the measurement unit and the component concentration calculated by the calculation unit together with at least one of time and elapsed time from the start of measurement;
A display unit that displays at least one of the characteristic value and the component concentration stored in the measurement data storage unit as a graph with the time stored in the measurement data storage unit or the elapsed time from the start of measurement as an index;
Based on a measured value or calculated value of a management target item selected from a plurality of characteristic values of the developer measured by the measuring unit and a component concentration of the developer calculated by the calculating unit. A control unit that issues a control signal to a control valve provided in a conduit for supplying replenisher to be replenished to the liquid;
A developer management apparatus comprising:   The developer management apparatus according to claim 7, further comprising a display switching unit that switches a graph displayed on the display unit to be a graph of a characteristic value of the developer or a component concentration of the developer. . The measurement unit is
A first measuring means for measuring a characteristic value of the developer having a correlation with a concentration of at least an alkali component among the components of the developer;
A second measuring means for measuring a characteristic value of the developer having a correlation with at least a concentration of the photoresist dissolved in the developer among the component concentrations of the developer;
A developer management apparatus according to claim 5, comprising: The calculation unit includes a calculation block for calculating the concentration of alkali components and the concentration of photoresist in the developer,
The control unit is
A control block that issues a control signal to the control valve such that the concentration of the alkali component calculated by the calculation block becomes a predetermined management value;
A control block that issues a control signal to the control valve such that the concentration of the photoresist calculated by the calculation block is equal to or lower than a predetermined management value;
The developing solution management apparatus according to claim 9.   The measurement unit further includes third measurement means for measuring a characteristic value of the developer that is correlated with a concentration of carbon dioxide absorbed in at least the developer among the components of the developer. The developer management apparatus according to 1. The calculation unit includes a calculation block for calculating the concentration of carbon dioxide in the developer.
The control unit is
A control block for issuing a control signal to the control valve so that the characteristic value of the developer measured by the first measuring means becomes a predetermined management value;
A control block that issues a control signal to the control valve so that the characteristic value of the developer measured by the second measuring means enters a predetermined management region;
A control block that issues a control signal to the control valve such that the concentration of carbon dioxide calculated by the calculation block is equal to or lower than a predetermined management value;
The developing solution management apparatus according to claim 11. The calculation unit includes a calculation block for calculating a concentration of an alkali component and a concentration of carbon dioxide in the developer,
The control unit is
A control block that issues a control signal to the control valve so that the concentration of the alkali component calculated by the calculation block becomes a predetermined management value;
A control block that issues a control signal to the control valve so that the characteristic value of the developer measured by the second measuring means enters a predetermined management region;
A control block that issues a control signal to the control valve such that the concentration of carbon dioxide calculated by the calculation block is equal to or lower than a predetermined management value;
The developing solution management apparatus according to claim 11. The calculation unit includes a calculation block for calculating an alkali component concentration, a photoresist concentration, and a carbon dioxide concentration in the developer,
The control unit is
A control block that issues a control signal to the control valve so that the concentration of the alkali component calculated by the calculation block becomes a predetermined management value;
A control block that issues a control signal to the control valve such that the concentration of the photoresist calculated in the calculation block is equal to or lower than a predetermined management value;
A control block that issues a control signal to the control valve such that the concentration of carbon dioxide calculated by the calculation block is equal to or lower than a predetermined management value;
The developing solution management apparatus according to claim 11.

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