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

Abstract

To provide a concentration monitoring device that accurately calculates the concentration of each component such as the alkali component of the alkaline developer, the dissolved photoresist, and the absorbed carbon dioxide from the characteristic value of the developer, and develops the developer A developer management device that maintains and manages performance in the best state.

The developer concentration monitoring device A is equipped with: a measuring section 1, which measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and a computing section 2, based on the measurement by the measuring section 1. A plurality of characteristic values are calculated by the multivariate analysis method to calculate the component concentration of the developer; and the alarm unit WD, which generates an alarm when at least one of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

Description

Developer concentration monitoring device and developer management device

It relates to an alkaline developer concentration monitoring device and developer management device that are repeatedly used in the development process of semiconductor or liquid crystal panel circuit substrates in order to develop photoresist films.

In the development process of photolithography that realizes the processing of fine wiring in semiconductors, liquid crystal panels, etc., an alkaline developer (hereinafter referred to as "alkaline developer") is used as a film on the substrate The photoresist is dissolved in a liquid medicine.

In the manufacturing process of semiconductors, liquid crystal panel substrates, etc., in recent years, great progress has been made in the enlargement of wafers and glass substrates, and the miniaturization and high integration of wiring processing. Under such circumstances, in order to realize the miniaturization and high integration of the wiring processing of large-sized substrates, it is necessary to measure the concentration of the main components of the alkaline developer with higher accuracy to maintain and manage the developer.

As described in Patent Document 1, the conventional measurement of the component concentration of an alkaline developer is based on the difference between the concentration of the alkaline component of the alkaline developer (hereinafter referred to as "alkali component concentration") and the electrical conductivity. A good linear relationship and a good linear relationship can be obtained between the concentration of the photoresist dissolved in the alkaline developer (hereinafter referred to as "dissolved photoresist concentration") and the absorbance.

In addition, the alkaline developer absorbs carbon dioxide in the air, and tends to produce carbonate and deteriorate. In addition, the alkaline developer generates photoresist salt by dissolving the photoresist, and the alkaline components effective for the development process are consumed. Therefore, the repeatedly used alkaline developer becomes a multi-component system containing not only an alkali component but also a photoresist, carbon dioxide, and the like. Moreover, its components have different contributions to the development performance. Therefore, in order to maintain and manage the developing performance of the developer with high accuracy, the management of the developer in consideration of the influence of these components on the developing performance is necessary.

In order to solve this problem, Patent Document 2 discloses a developer preparation device, etc., which measure the ultrasonic propagation velocity, conductivity, and absorbance of the developer based on the ultrasonic propagation under the alkali concentration, carbonate concentration, and dissolved resin concentration. The relationship (matrix) between speed, conductivity and absorbance is pre-made to detect the alkali concentration, carbonate concentration and dissolved resin concentration of the developer, and based on the measured alkali concentration, carbonate concentration and dissolved resin concentration of the developer, and The pre-established relationship between alkali concentration and carbonate concentration and dissolved resin concentration can be used to exert the dissolving power of CD value (critical dimension value) (line width) to a fixed value, and control the supply of developer stock solution to adjust alkali concentration.

In addition, Patent Document 3 discloses: a carbonate-based salt concentration measuring device that measures the refractive index, conductivity, and absorbance of a developer and obtains the concentration of carbonate-based salts in the developer from the measured values, and a device provided with the carbonic acid It is the alkali developer management system of the control unit that controls the concentration of carbonate salts in the developer, etc.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent No. 2561578

Patent Document 2 JP 2008-283162 A

Patent Document 3 JP 2011-128455 A

However, the ultrasonic propagation velocity value and the refractive index value of the alkaline developer are characteristic values showing the properties of the entire liquid of the multi-component alkaline developer. The characteristic value showing the properties of such a liquid as a whole is generally not only related to the concentration of a specific component contained in the liquid. The characteristic values showing the properties of the entire liquid are generally related to the concentrations of various components contained in the liquid. Therefore, in the case of calculating the component concentration of the developer from the measured value of the characteristic value showing the properties of the liquid as a whole, when a certain characteristic value is only related to a specific component concentration (for example, in a linear relationship) and other components are ignored When the characteristic value is affected, there is a problem that the concentration of the specific component cannot be calculated with sufficient accuracy.

On the other hand, in the case of calculating the concentration of each component from the measured value of the characteristic value of the developer by taking the characteristic value of the developer as the correlation of the concentration of the various components contained in the developer, after measuring a plurality of characteristic values, there is It is necessary to adopt an appropriate calculation method to calculate the concentration of each component from the measured values of these characteristic values. However, it is very difficult to appropriately select the characteristic value to be measured and find an appropriate calculation method that can accurately calculate the concentration of each component from the measured value of the characteristic value. Therefore, there is a problem that if the measured characteristic value and calculation method are inappropriate, the concentration of each component cannot be calculated with sufficient accuracy.

Moreover, in a multi-component liquid, generally speaking, the concentration of a certain component is not independent of the concentration of other components. In a multi-component liquid, there is a so-called correlation that when the concentration of a certain component changes, the concentrations of other components also change at the same time. This makes the calculation of high-precision component concentration and high-precision developer management more difficult.

In addition, with regard to the concentration of carbon dioxide absorbed by the developer (hereinafter referred to as the "absorbed carbon dioxide concentration"), the appropriate characteristic value of the developer, which shows a good correlation with it, is not known, and it is difficult to measure the absorption with high accuracy in the conventional system. Carbon dioxide concentration.

In addition, in Patent Document 2, in order to detect the component concentration of the developer, it is necessary to obtain the correlation (matrix) between the component concentration of the developer and the characteristic values such as the ultrasonic wave propagation velocity in advance. However, in this case, when the correlation (matrix) is not detailed, the component concentration cannot be calculated with high accuracy. In order to calculate the component concentration with high accuracy, the correlation (matrix) between the characteristic value of the developer used in the calculation and the component concentration (matrix) must be sufficiently dense. Therefore, the more accurate the calculation of the component concentration is desired, the more samples must be prepared in advance, and the correlation between the component concentration and the characteristic value of the developer must be measured in advance. Preparing such a dense correlation (matrix) in advance is a huge workload, and becomes a problem in achieving high-precision measurement of the component concentration of the developer. In particular, monitoring changes in the concentration of the developer is important in managing the developer.

The present invention was accomplished to solve the above-mentioned problems. The object of the present invention is to provide a method that can measure the component concentration of a developer with high accuracy from the characteristic values of a multi-component developer, and can analyze the developer without preparing a large number of samples and without preliminary measurement, etc. Component concentration, a monitoring device that can monitor the concentration of the developer, and a developer management device that can more precisely manage the component concentration of the developer.

The present invention for achieving the aforementioned object is as follows.

(1) A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; the computing unit is based on the measurement unit The measured plurality of characteristic values are calculated by multivariate analysis to calculate the component concentration of the developer; and an alarm unit, which generates an alarm when at least one of the component concentrations calculated by the calculation unit deviates from the set management range .

(2) A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and a computing unit based on the measuring unit The measured plurality of characteristic values are calculated by multivariate analysis to calculate the component concentration of the developer. According to the component concentration, an alarm is issued when the component concentration calculated by the calculation unit deviates from the set management range. unit.

(3) The developer concentration monitoring device as in (1) or (2), which serves as an alarm unit at least one of the following: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, and a light spot The warning light that lights up or flashes, the display device that shows the warning, and the relay terminal that switches the contacts on and off.

(4) A developer management device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; an arithmetic unit based on the measurement by the measuring unit The plurality of characteristic values are calculated by the multivariate analysis method to calculate the component concentration of the developer; the alarm unit, when at least one of the component concentrations calculated by the calculation unit deviates from the set management range; and control The part is based on the measured value or calculated value of the management target item selected from the plurality of characteristic values of the developer measured by the measuring part and the component concentration of the developer calculated by the calculating part. The control valve on the pipeline for conveying the replenishing liquid to be replenished to the aforementioned developer sends a control signal.

(5) The developer management device as in (4), wherein as an alarm unit, at least one of the following is provided: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, and a warning lamp that lights or flashes light , The display device to display the warning, and the relay terminal to switch the opening and closing of the contact.

(6) A developer management device, comprising: a measuring unit that measures a plurality of characteristic values of the aforementioned developer related to the component concentration of the alkaline developer that is repeatedly used; The arithmetic unit calculates the component concentration of the developer by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit; and the control unit, based on the plural of the developer measured by the measurement unit The characteristic value and the measured value or calculated value of the management target item selected in the component concentration of the developer calculated by the arithmetic unit are set on the pipeline for conveying the replenishing liquid to be replenished to the developer The control valve emits a control signal, and is equipped with an alarm unit that issues an alarm when the concentration of the component calculated by the calculation unit deviates from the set management range according to the concentration.

(7) The developer management device according to (6), wherein as the aforementioned alarm unit, at least one of the following is provided: an external output that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes light, A display device that displays warnings, and a relay terminal that switches contacts on and off.

(8) The developer management device according to any one of (4) to (7), wherein the component concentration is the concentration of the alkali component of the developer and the concentration of the photoresist, and the measurement unit includes: A measuring means for measuring the characteristic value of the developer related to the concentration of at least the alkali component in the components of the developer; and a second measuring means for measuring the photoresist at least dissolved in the developer in the components of the developer Regarding the characteristic value of the developer with respect to the concentration, the arithmetic unit includes an arithmetic block for calculating the concentration of the alkali component of the developer and the concentration of the photoresist.

(9) The developer management device according to any one of (4) to (7), wherein the component concentration is the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide, and the measurement unit includes: The first measuring means measures the characteristic value of the developer with respect to the concentration of at least the alkali component in the components of the developer; the second measuring means measures the photoresist dissolved in the developer at least among the components of the developer The characteristic value of the developer related to the concentration of the developer; and a third measuring means for measuring the characteristic value of the developer related to the concentration of at least the carbon dioxide absorbed by the developer in the components of the developer, and the arithmetic unit is equipped to calculate the A calculation block for the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide.

According to the present invention, since the component concentration of the multi-component alkaline developer is calculated by the arithmetic means using the multivariate analysis method (for example, the multiple regression analysis method), it is the same as the measured characteristic value and the specific component concentration. Compared with the conventional method of calculating the component concentration in a predetermined correlation (for example, a linear relationship), the component concentration of the developer can be calculated with high accuracy from the characteristic value affected by a plurality of developer components. In particular, according to the present invention, it is possible to measure the absorbed carbon dioxide concentration of a developer which is difficult to measure in the prior art. In addition, compared with the method of preparing correlations (matrices) between a plurality of measured characteristic values and a plurality of component concentrations in advance and using them for calculating component concentrations, there is no need to prepare a huge number of samples and perform preliminary measurements in the present invention. And can easily monitor the concentration of the developer.

According to the present invention, since the concentration of each component of the multi-component alkaline developer can be measured with higher accuracy than the conventional one, the concentration of the alkali component, the concentration of the dissolved photoresist and the concentration of carbon dioxide absorption can be controlled more accurately than the conventional one. . Furthermore, according to the present invention, it is also possible to select management to control the conductivity value of the developer to a fixed value, and management to control the absorbance value of the developer to be below a fixed absorbance value.

A: Concentration monitoring device

B: Development process equipment

C: Replenishment liquid storage part

D: Circulating stirring mechanism

E: Developer management device

1: Measurement department

11: The first measurement component

12: The second measuring component

13: The third measuring component

11a, 12a, 13a: measuring device body

11b, 12b, 13b: measuring probe

14, 14a, 14b, 14c: sampling pump

15, 15a, 15b, 15c: sampling piping

16, 16a, 16b, 16c: return piping

17: Liquid delivery pump

18: Liquid delivery piping

19: Waste liquid piping

2: Computing Department

21: Operation block using multivariate analysis

22: Operation block using calibration curve method

23: Operation control unit (e.g. computer)

3: Control Department

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‧‧‧Operation data signal line

55~57‧‧‧Signal line for control signal

61‧‧‧Developer storage tank

62‧‧‧Overflow trough

63‧‧‧Level Gauge

64‧‧‧Development chamber cover

65‧‧‧Roller Conveyor

66‧‧‧Substrate

67‧‧‧Developer spray head

71‧‧‧Waste pump

72、74‧‧‧Circulating pump

73、75‧‧‧Filter

8‧‧‧Fluid pipeline

80‧‧‧Developing solution pipeline

81、82‧‧‧Supply solution (developing stock solution and/or new solution) pipeline

83‧‧‧Pure water pipeline

84‧‧‧Combined pipeline

85‧‧‧Circulation pipeline

86: Nitrogen pipeline

9: Replenishment liquid storage tank, others

91, 92: Replenisher (developing stock solution and/or new solution) storage tank

93: Add reagent

WD: Alarm Department

Fig. 1 is a flowchart showing a method of measuring the component concentration of a signal flow when the component concentration of two components is measured from two characteristic values.

Fig. 2 is a flowchart showing a component concentration measurement method of signal flow when the component concentration of three or more components is measured from three or more characteristic values.

Fig. 3 is a flowchart showing a method of measuring the component concentration of the signal flow when an operation method different from the multivariate analysis method is included.

Figure 4 is a schematic diagram of a monitoring device for measuring the concentration of two components of a developer.

Figure 5 is a schematic diagram of a monitoring device for measuring the concentration of three components of a developer.

Fig. 6 is a schematic diagram of a concentration monitoring device having an arithmetic block using an arithmetic method different from the multivariate analysis method in the arithmetic section.

Fig. 7 is a schematic diagram of a concentration monitoring device when the measurement unit and the calculation unit are separated and inline measurement is performed.

Fig. 8 is a schematic diagram of a concentration monitoring device when the measuring member is composed of a main body and a probe part.

Fig. 9 is a schematic diagram of a concentration monitoring device provided with measuring means in parallel.

Fig. 10 is a schematic diagram of a concentration monitoring device in a case where a measurement device that requires drug addition is provided.

Figure 11 is a schematic diagram of applying a concentration monitoring device to a developer management device.

Fig. 12 is a schematic diagram showing an application example of the concentration monitoring device.

FIG. 13 is a flowchart of a developer management method for managing two components of a developer by component concentration.

14 is a flowchart of a developer management method in which one of the two components of the developer is managed by the component concentration and the other is managed by the characteristic value.

FIG. 15 is a flowchart of a developer management method in which the three components of the developer are managed by the component concentration.

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.

FIG. 17 is a flowchart of a developer management method in which two of the three components of the developer are managed by characteristic values and the other is managed by the component concentration.

FIG. 18 is a schematic diagram for explaining the development process of the developer management device of the present invention.

Figure 19 is a schematic diagram of a developer management device that controls a control valve outside the device.

Fig. 20 is a schematic diagram of a developer management device provided with an arithmetic control unit having arithmetic and control functions.

Figure 21 is a schematic diagram of a developer management device that manages two components of a developer.

Fig. 22 is a schematic diagram of a developer management device in which two components of a developer are managed by component concentrations.

FIG. 23 is a schematic diagram of a developer management device in which two of the three components of the developer are managed by characteristic values and the other by the component concentration.

FIG. 24 is a schematic diagram of a developer management device in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration.

FIG. 25 is a schematic diagram of a developer management device in which three components of a developer are managed by component concentrations.

Hereinafter, the preferred embodiments of the present invention will be described in detail while referring to appropriate drawings. However, the shapes, sizes, size ratios, relative arrangements, etc. of the devices and the like described in these embodiments should not be limited to the content shown in the scope of the present invention as long as there is no specific description. It is a schematic illustration as a purely illustrative example.

In addition, in the following description, as a specific example of the developer, a 2.38% tetramethyl ammonium hydroxide aqueous solution (hereinafter referred to as hydrogen), which is mainly used in the manufacturing process of semiconductors and liquid crystal panel substrates, is suitably used. Tetramethylammonium oxide is called TMAH.) for illustration. However, the developer to which the present invention is applied is not limited by this. Examples of other developer solutions that can be applied to the developer concentration monitoring device and developer management device of the present invention include aqueous solutions of inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, and sodium silicate. An aqueous solution of an organic compound such as trimethyl monoethanol ammonium hydroxide (choline).

In addition, the multivariate analysis method (such as the multiple regression analysis method) does not depend on the concentration of the component when calculating the component concentration. However, in the following description, the alkali component concentration, dissolved photoresist concentration, absorption The concentration of the components such as carbon dioxide concentration is the concentration by weight percentage concentration (wt%). The "dissolved photoresist concentration" means the concentration when the dissolved photoresist is converted into the amount of the photoresist, and the "absorbed carbon dioxide concentration" means the concentration when the absorbed carbon dioxide is converted into the amount of carbon dioxide.

In the development process, the unnecessary part of the photoresist film after the exposure treatment is dissolved through the developer solution for development. The photoresist dissolved in the developer solution generates a photoresist salt with the alkali component of the developer solution. Therefore, if the developer is not properly managed, as the development process progresses, the developer will be degraded due to the consumption of alkali components having development activity, and the development performance will continue to deteriorate. At the same time, the photoresist dissolved in the developer is gradually accumulated in the form of a photoresist salt with the alkali component.

The photoresist dissolved in the developing solution exhibits interfacial activity in the developing solution. Therefore, the photoresist dissolved in the developing solution improves the wettability of the developing solution to the photoresist film used for development, and improves the affinity between the developing solution and the photoresist film. Therefore, in the developer containing a moderate amount of photoresist, the developer also spreads in the fine recesses of the photoresist film, and the photoresist film with fine irregularities can be well developed.

In addition, in recent development processes, along with the enlargement of the substrate, a large amount of the developer has been reused, so the chance of the developer being exposed to the air has increased. However, when the alkaline developer is exposed to the air, it absorbs carbon dioxide in the air. Carbonate is formed between the absorbed carbon dioxide and the alkali component of the developer. Therefore, if the developer is not properly managed, the alkali components with development activity in the developer will be consumed and reduced by the absorbed carbon dioxide. At the same time, the carbon dioxide absorbed in the developer is gradually accumulated in the form of carbonate formed with alkali components.

The carbonate in the developer has a developing effect because it is alkaline in the developer. For example, in the case of a 2.38% TMAH aqueous solution, if the carbon dioxide in the developer is about 0.4 wt% or less, the development can be performed.

As mentioned above, unlike the previous recognition that the development activity of the development process will be inactivated, the photoresist dissolved in the developer and the carbon dioxide absorbed actually contribute to the development performance of the developer. Therefore, what must be done is the developer management that allows the dissolved photoresist and carbon dioxide to be dissolved in the developer solution and the presence of dissolved photoresist and absorbs carbon dioxide, and maintains management of the dissolved photoresist and carbon dioxide absorption at the optimal concentration, rather than the management of the dissolved light. Developer management for complete removal of resist and carbon dioxide absorption.

Furthermore, part of the photoresist salt, carbonate, etc. generated in the developer is dissociated to generate various free ions such as photoresist ions, carbonate ions, and hydrogen carbonate ions. Moreover, these free ions will affect the conductivity of the developer with various contribution rates.

The analysis of the component concentration of the conventional alkaline developer is that the alkali component concentration of the developer and the conductivity value of the developer have a good linear relationship, and the dissolved photoresist concentration of the developer has a good absorbance value. (Hereinafter referred to as "the conventional method"). The developer management precision required in the conventional development process may also have a low carbon dioxide absorption, which can be fully realized by this analysis method.

The electrical conductivity value of the developer is a physical property value that depends on the number of charged particles such as ions contained in the developer and the amount of charge. As described above, there are not only alkali components in the developer, but also photoresist dissolved in the developer or various free ions derived from carbon dioxide absorbed by the developer. Therefore, in order to improve the analysis accuracy of the component concentration, it is necessary to use an algorithm that also includes the influence of such free ions on the conductivity value of the developer.

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

The inventors have continued to carefully study these points and found that if a multivariate analysis method (for example, multiple regression analysis) is used in the calculation method, the developer can be calculated with high accuracy based on the conventional method. The concentration of each component, and the concentration of carbon dioxide absorbed can be measured, which is difficult to measure conventionally. In addition, the inventor found that if the component concentration of the developer calculated by a multivariate analysis method (for example, a multiple regression analysis method) is used, the dissolved photoresist concentration and the absorbed carbon dioxide concentration of the developer can be maintained and managed in a good status.

The inventor assumed the management of a 2.38% TMAH aqueous solution, and prepared a TMAH aqueous solution obtained by varying the alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration as a simulated developer sample. The inventors conducted experiments to obtain the component concentrations of the various characteristic values measured for these simulated developer samples by multiple regression analysis. Hereinafter, the general calculation method using the multiple regression analysis method will be explained, and then, based on the experiment conducted by the inventor, the calculation method of the component concentration of the developer using the multiple regression analysis method will be explained.

The multiple regression analysis system consists of two stages of correction and prediction. In the multiple regression analysis of the n-component system, it is assumed that m calibration standard solutions are prepared. The concentration of the j-th component present in the i-th solution is represented by C _ij . Here, i=1 to m, j=1 to n. For m standard solutions, respectively measure p characteristic values (for example, physical property values such as absorbance or conductivity at a certain wavelength) A _ik (k=1 to p). Concentration data and characteristic data can be aggregated and displayed in matrix form (C, A).

The matrix that gives these matrices a relationship is called a correction matrix, and is represented by the notation S (S _kj ; k=1 to p, j=1 to n) here.

Mathematical formula 2 C=A. S

Matrix calculations are used to calculate S from the known C and A (even if the content of A is not a homogeneous measurement value but mixed with a heterogeneous measurement value. For example, conductivity, absorbance, and density.) The calculation of S is a correction stage. At this time, it must be p≧n and m≧np. Since each element of S is unknown, m>np is better. In this case, the least square operation is performed in the following manner.

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

Measure p characteristic values for a sample solution of unknown concentration. If these characteristic values are set to Au(Au _k ; k=1 to p), then these characteristic values can be multiplied by S to obtain the desired concentration Cu( Cu _j ; j=1 to n).

Mathematical formula 4 Cu=Au. S

This is the forecast stage.

The inventor considers the used alkaline developer (2.38% TMAH aqueous solution) as a multi-component system (n=3) composed of three components: alkali component, dissolved photoresist, and carbon dioxide absorption. Three physical property values (p=3) of the characteristic value of the liquid, that is, from the conductivity value of the developer, the absorbance value at a specific wavelength, and the density value, the experiment was performed to calculate the concentration of each component by the above-mentioned multiple regression analysis method . The inventors used 2.38% TMAH aqueous solution as the basic composition of the developer, and prepared 11 calibration standard solutions (m=11, satisfying various changes in alkali component concentration (TMAH concentration), dissolved photoresist concentration, and absorbed carbon dioxide concentration) p≧n and m>np).

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

Regarding the method of measurement, adjust the temperature of the calibration standard solution to 25.0°C before proceeding. The temperature adjustment system is to immerse a bottle containing a calibration standard solution for a long time in a constant temperature water tank whose temperature is controlled to be around 25°C, to sample, and then set it to 25.0°C with a temperature controller immediately before the measurement. . The conductivity meter is made by our company. The measurement was performed using a conductivity flow cell manufactured by our company that has been subjected to platinum black treatment. The conductivity meter is inputted with the cell constant of the conductivity flow cell that is additionally confirmed by calibration. The company's products are also used in the absorbance photometer. The absorbance photometer is equipped with a light source unit with a wavelength of λ=560nm, a photometric unit, and a glass flow cell. Density measurement uses a densitometer that uses the natural vibration method to obtain density from the natural vibration frequency measured by exciting the U-tube flow groove. The units of the measured conductivity value, absorbance value and density value are mS/cm, Abs. (Absorbance) and g/cm ^{3 respectively} .

Regarding the calculation method, one of the 11 calibration standard solutions is used as an unknown sample, and the remaining 10 standards are used to obtain the calibration matrix to calculate the assumed concentration of the unknown sample, and then compare it with the known value ( The method of comparison (Leave-One-Out method; Leave-One-Out method) is used to compare the concentration value and weight modulation value measured by other correct analysis methods.

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

When calculating MLR-ILS, considering that the TMAH aqueous solution is strongly alkaline and easily degraded by carbon dioxide absorption, the concentration matrix used in the calculation is based on another titration analysis method that can accurately analyze the concentration of alkali components and the concentration of carbon dioxide absorbed. The value obtained by measuring the calibration standard solution. However, regarding the dissolved photoresist concentration, the weight modulation value is used.

Regarding the titration method, the neutralization titration using hydrochloric acid as the titration reagent. As the titration device, an automatic titration device GT-200 manufactured by Mitsubishi Chemical Analytech was used.

Below, the concentration matrix is shown in Table 2.

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

The correction matrix is shown in Table 4.

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

As shown in Table 5, the TMAH concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration obtained by the multiple regression analysis method are all compared with the TMAH concentration, absorbed carbon dioxide concentration and adjusted weight determined by titration analysis. The obtained dissolved photoresist concentration is quite approximate.

In this way, it is understood that by measuring the conductivity of the alkaline developer, the absorbance at a specific wavelength, and the density, the use of multivariate analysis methods (for example, multiple regression analysis) can determine the alkali component concentration of the developer and the dissolved photoresist Concentration and absorption of carbon dioxide.

Multivariate analysis (for example, multiple regression analysis) has a good effect in calculating and calculating the concentration of multiple components. A plurality of characteristic values a, b, c, ... of the developer are measured, and from these measured values, the component concentrations A, B, C, ... can be obtained by a multivariate analysis method (for example, a multiple regression analysis method). At this time, for the required component concentration, at least one characteristic value related to the component concentration must be measured and used in the calculation.

Here, the so-called developer characteristic value "related" to the component concentration means that the characteristic value is related to the component concentration, and the characteristic value changes with the change of the component concentration. For example, in the component concentration of the developer, the so-called developer characteristic value a that is at least related to the component concentration A means that when the characteristic value a is to be obtained using a function with the component concentration as a variable, one of the variables must include at least the component concentration A . The characteristic value a can only be a function of the component concentration A, but usually in addition to the component concentration A, when it is also formed as a multivariate function with component concentration B or C as a variable, a multivariate analysis method (for example, multiple regression analysis Law) is of greater significance.

In addition, the component concentration means the degree of the relative amount of the component to the whole. The component concentration of the mixed solution whose components such as the repeatedly used developer increase or decrease over time cannot be determined by its components alone, and is usually a function of the concentration of other components. Therefore, the relationship between the characteristic value of the developer and the component concentration is difficult to display with a graph. In such a case, it is impossible to calculate the component concentration from the characteristic value of the developer using the calculation method of the calibration curve.

However, if it is based on a multivariate analysis method (for example, multiple regression analysis), you only need to collect a set of measured values of a plurality of characteristic values related to the component concentration you want to calculate, and use these measured values in the calculation, that is Can calculate the concentration of a group of ingredients. Even if the concentration of the component is difficult to be measured under the conventional knowledge, the measurement of the component concentration using a multivariate analysis method (for example, multiple regression analysis) can obtain a significant effect of measuring the component concentration by measuring the characteristic value. .

As mentioned above, according to the algorithm of the present invention, the alkali component concentration of the developer, the dissolved photoresist concentration, and the measured values of the characteristic values of the developer (for example, conductivity, absorbance at a specific wavelength, and density) can be calculated Absorb the concentration of carbon dioxide. According to the calculation method of the present invention, the concentration of each component can be calculated with higher accuracy than the conventional method.

In addition, in the present invention, since a multivariate analysis method (for example, a multiple regression analysis method) is used, it is also possible to use the characteristics of the developer that are wirelessly related to the specific component concentration of the developer in the calculation to calculate the component concentration of the developer. value.

In addition, according to the present invention, the preparation and preliminary measurement of a very large number of samples for high-precision measurement are not required in the invention of Patent Document 2. (As in the previous experimental example, if it is a developer with the number of components n=3, let the number of characteristic values to be measured p=3, and the number of samples p satisfying m≧np (for example, p=11 samples) It is sufficient to perform the measurement. If the number of components is n=2, the number of samples may be smaller.)

Furthermore, since the present invention uses a multivariate analysis method (for example, a multiple regression analysis method), it is possible to accurately calculate the absorbed carbon dioxide concentration of the developer, which is difficult to measure in the prior art.

Next, specific embodiments will be described with reference to the drawings. In the following examples, the characteristic values a, b, c,..., and the component concentrations A, B, C,..., etc., are described using letters as appropriate. In order to be more specific, the characteristic values a, b, c, ... are re-understood as conductivity, absorbance at a specific wavelength (for example, λ=560nm), density, ..., etc., and component concentrations A, B, C, …Are re-understood as alkali component concentration, dissolved photoresist concentration, carbon dioxide absorption concentration, etc.

Among them, setting the characteristic values a, b, and c as electrical conductivity, absorbance and density at a specific wavelength (for example, λ=560nm), etc., is nothing more than calculating the alkali component concentration of the developer, the dissolved photoresist concentration, etc. according to the present invention. The combination of optimal characteristic values in the case of absorbing carbon dioxide concentration etc. is only an example, but it is not limited to this. The characteristic values a, b, c,... can be selected in various combinations according to the component concentrations A, B, C,... Usable characteristic values include, for example, the conductivity, absorbance, ultrasonic propagation velocity, refractive index, density, titration end point, pH, etc. of the developer. Since there are cases where various additives are contained in the developer, the concentration of additives may be contained in addition to the above three components in the component concentration.

When measuring the alkali component concentration, dissolved photoresist concentration, and carbon dioxide absorption concentration of the developer to manage the developer, it is suitable to use the combination of conductivity, absorbance at a specific wavelength, and density as characteristic values. The specific wavelength for measuring absorbance is preferably in the visible region, preferably the specific wavelength in the wavelength region of 360 to 600 nm, and more preferably the wavelength λ=480 nm or 560 nm. This is when the concentration of carbon dioxide absorbed by the developer is small and its change over time is gentle, the conductivity of the developer and the concentration of the alkali component are in a good linear relationship, and the developer’s specific wavelength (for example, λ=560nm) The absorbance and the dissolved photoresist concentration are in a relatively good linear relationship. In addition, it is preferable that the combination of conductivity, absorbance at a specific wavelength and ultrasonic propagation velocity, conductivity, combination of absorbance at a specific wavelength and refractive index, etc. can also be used.

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

FIG. 1 is a flowchart showing the flow of a signal when the component concentration of two components of the developer is measured from two characteristic values of the developer.

In the component concentration calculation method of this embodiment, first, in the step of measuring the characteristic values a and b of the developer, the respective measured values a _m and b _{m are obtained} . The obtained measured values a _m and b _m are sent to the calculation step. Next, the calculation step is to receive the measured values a _m and b _m , and use these to calculate the component concentrations A and B by a multivariate analysis method (for example, a multiple regression analysis method). In this way, the component concentrations A and B are measured. Moreover, if this process is repeated, the component concentrations A and B of the developer can be continuously measured.

Figure 2 is a flow chart of the component concentration measurement method of the present embodiment showing the flow of signals when the component concentration of three or more components of the developer is measured from three or more characteristic values of the developer .

The method of calculating the concentration step according to the present embodiment, first, the characteristics of the developer measured values a, b, c, ..., the respective measurement values to obtain _{a m, b m, c m} , .... The measurement value obtained _{a m, b m, c m} , ... is sent to the system operation step. Next, the step of calculating the measured value based receiving _{a m, b m, c m} , ..., by use of such a multivariate analysis (e.g., multiple regression analysis) was calculated concentration of the component A, B, C, .... In this way, the component concentrations A, B, C, ... are measured. In addition, if this process is repeated, the component concentrations A, B, C,... of the developer can be continuously measured.

Figure 3 shows the measurement of the component concentration in the present embodiment of the signal flow when the concentration of a plurality of components is measured from the characteristic values of a plurality of developers, and the calculation step also includes a step using a calculation method different from the multivariate analysis method Flow chart of the method.

This embodiment can be appropriately selected and used when the characteristic value p of the developer only related to the concentration P of a certain component of the developer is used as the measurement target. More specifically, a multivariate analysis method can be used to calculate the alkali component concentration and carbon dioxide absorption concentration of the developer from the conductivity value and density value of the developer, and the dissolved photoresist concentration of the developer can be used and specified. The linear relationship of absorbance in wavelength (for example, λ=560nm) is calculated and measured as a calibration curve.

In the method for measuring the component concentration of the developer of this embodiment, in the measuring step, the characteristic values a, b, ... of the developer with a plurality of component concentrations as variables are measured, and the developer with only the component concentration P as the variable is measured The characteristic values p,..., and the measured values a _m , b _m ,..., and p _m ,... are sent to the calculation step.

The calculation step includes a step of calculating the component concentration by a multivariate analysis method (for example, multiple regression analysis method); and a step of calculating the component concentration by a calculation method different from the multivariate analysis method (for example, a calibration curve method, etc.). The order of these steps is not limited. Can also be at the same time.

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

The step of calculating the component concentration by a calculation method different from the multivariate analysis method (for example, the calibration curve method) is to use the linear relationship between the characteristic value p and the component concentration P obtained in advance as a calibration curve, etc., by the measurement step Calculate the component concentration P,... from the measured value of the measured characteristic value p of the developer.

Above, the method for measuring the component concentration of the developer includes: a measuring step, measuring multiple characteristic values of the developer related to the component concentration of the developer; and an arithmetic step, based on the measured plural characteristic values, by a multivariate analysis method Calculate the component concentration of the developer.

The measuring step further includes: the measuring step of measuring the characteristic value a; the measuring step of measuring the characteristic value b; the measuring step of measuring the characteristic value c, etc. However, the order of these steps is not limited. It can also be measured at the same time. In addition, the temperature adjustment step, the reagent addition step, the waste solution step, and the like may include steps appropriately required in accordance with the measurement method.

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

Hereinafter, the first to seventh embodiments relate to the developer concentration monitoring device of the present invention.

[First Embodiment]

Figure 4 is a schematic diagram of a monitoring device for measuring the concentration of two components of a developer. For the convenience of description, the developer concentration monitoring device A is shown together with the development process equipment B in a state of being connected to the development process equipment B.

First, a brief description of the development process equipment B will be given.

The developing process equipment B is mainly composed of a developer storage tank 61, an overflow tank 62, a developing room hood 64, a roller conveyor 65, a developer nozzle 67 and the like. The developer liquid is stored in the developer liquid storage tank 61. The developer system is replenished with replenisher for composition management, but this is omitted in FIG. 4. The developer storage tank 61 is equipped with a level gauge 63 and an overflow tank 62 to manage the increase in the liquid volume caused by the replenishment of the replenishing liquid. The developer storage tank 61 and the developer spray head 67 are connected by the developer pipeline 80, and the developer stored in the developer storage tank 61 is passed through the filter 73 by the circulating pump 72 provided in the developer pipeline 80. Transported to the developer spray head 67. The roller conveyor 65 is installed above the developer storage tank 61 to transport the substrate 66 on which the photoresist film is formed. The developer is dropped from the developer spray head 67, and the substrate 66 conveyed by the roller conveyor 65 is immersed in the developer through the dropped developer. After that, the developer is recovered by the developer storage tank 61 and stored again. In this way, the developer is repeatedly used in the development process. In addition, the developing chamber in the small glass substrate may be filled with nitrogen gas to prevent the carbon dioxide in the air from being absorbed. In addition, the deteriorated developer is drained (drain) by operating the waste pump 71.

Next, the developer concentration monitoring device A of this embodiment will be described. The concentration monitoring device of this embodiment is a concentration monitoring device that samples the developer to measure the characteristic value.

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

The measurement unit 1 includes a sampling pump 14, a first measurement member 11, and a second measurement member 12 (the first measurement member 11 and the second measurement member 12 may be referred to as measurement members). The measuring members 11 and 12 are connected in series to the rear stage of the sampling pump 14. It is more preferable that the measurement unit 1 is provided with a temperature adjustment member (not shown) that stabilizes the sampled developer to a predetermined temperature in order to improve the measurement accuracy. In this case, the temperature adjusting member is preferably provided in front of the measuring member. The sampling pipe 15 is connected to the sampling pump 14 of the measurement unit 1, and the return pipe 16 is connected to the pipe at the end of the measurement member.

The calculation unit 2 includes a calculation block 21 using a multivariate analysis method. The arithmetic block 21 using the multivariate analysis method is connected to the first measurement member 11 provided in the measurement section 1 via the measurement data signal line 51 and the second measurement member 11 provided in the measurement section 1 via the measurement data signal line 52. Measuring member 12.

Next, the measurement operation and calculation operation of the concentration monitoring device A will be described.

The developer collected from the developer storage tank 61 by the sampling pump 14 is introduced into the measuring section 1 of the concentration monitoring device A through the sampling pipe 15. After that, in the case where the temperature adjustment member is provided, the sampled developer is sent to the temperature adjustment member to maintain a predetermined measurement temperature (for example, 25° C.), and is then sent to the measurement members 11 and 12. The characteristic value a of the developer is measured by the first measuring member, and the characteristic value b of the developer is measured by the second measuring member. The developer after the measurement is returned to the developer storage tank 61 through the return pipe 16.

The measured value a _m of the characteristic value a of the developer measured by the first measuring member 11 and the measured value b _m of the characteristic value b of the developer measured by the second measuring member 12 are respectively measured through the measurement data The signal lines 51 and 52 are sent to the arithmetic block 21 using the multivariate analysis method. The arithmetic block 21 that has received the measured values a _m and b _m calculates the component concentrations A and B of the developer by calculating the measured values thereof by a multivariate analysis method. In this way, the concentration monitoring device A measures the component concentrations A and B of the developer.

The concentration monitoring device A of the embodiment includes an alarm unit WD. The alarm unit WD can issue an alarm when at least any one of the component concentrations (for example, A or B) calculated by the calculation unit 2 deviates from the set management range.

For example, the management range can be stored in the calculation unit 2 in advance, and the calculation unit 2 can determine whether the component concentration is outside the management range. The information is sent from the computing unit 2 to the alarm unit, and the alarm unit WD can issue an alarm based on the information.

In addition, the management range is stored in the alarm unit WD in advance, and information on the component concentration is received from the computing unit 2, and the alarm unit WD determines whether the component concentration is within the management range. Based on this judgment, the alarm unit WD can issue an alarm.

As long as the alarm unit WD can issue an alarm, the memory means and judgment means in the management range are not particularly limited.

As for the alarm unit WD, it is preferable to include an external output signal terminal for transmitting an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, a display device that displays a warning, and a switch contact opening and closing At least any one of the relay terminals.

When the alarm part WD is an external output signal terminal that transmits an alarm signal, the external output signal terminal is connected to a device not shown. When the device receives an alarm signal from an external output signal terminal, it can perform a predetermined action. For example, if it is a system containing a concentration monitoring device, the system can be stopped.

In the case where the alarm unit WD is an alarm device that emits an alarm sound, or a warning lamp that lights or flashes the light, it can attract the attention of the operator near the concentration monitoring device. The operator can confirm the state of the concentration monitoring device and take appropriate measures.

In the case where the alarm part WD is a display device that displays warnings, the same can attract the attention of the operator. In addition, when the display device is electrically wired or wirelessly connected to the computing unit 2, the operator who is away from the concentration monitoring device can also draw attention.

When the alarm part WD is a relay terminal that switches the opening and closing of the contact, the device connected to the relay terminal can be switched on and off, enabling the device to perform a predetermined action.

In addition, the alarm unit WD may be provided for each component concentration. By providing the alarm unit WD for each component concentration, the alarm sent by the alarm unit WD can know which component concentration the alarm is for.

[Second Embodiment]

Figure 5 is a schematic diagram of a monitoring device for measuring the concentration of three components of a developer. The developer concentration monitoring device A includes a measurement unit 1 and a calculation unit 2, and is connected to a development process equipment B (developer storage tank 61) via a sampling pipe 15 and a return pipe 16. The measurement unit 1 has the first measurement The member 11, the second measuring member 12, and the third measuring member 13 are used to measure three characteristic values of the developer. The measured values of the measured three characteristic values are sent to the calculation section 2 via the signal lines 51, 52, and 53 for measurement data, and the component concentrations of the three components of the developer are calculated by the multivariate analysis method. The description of the measurement operation, the calculation operation system and the components that are repeated in FIG. 4 is the same as in the first embodiment, so it is omitted.

The concentration monitoring device A of the embodiment includes an alarm unit WD. The alarm unit WD can issue an alarm when at least one of the component concentrations (for example, A, B, or C) calculated by the calculation unit 2 deviates from the set management range.

[Third Embodiment]

FIG. 6 is a schematic diagram of a concentration monitoring device having an arithmetic block using an arithmetic method different from the multivariate analysis method in the arithmetic section 2. It is suitable for the case where the characteristic value of the developer and the component concentration can be determined from the measured physical property value of the developer by the calibration curve method.

The concentration monitoring device A of this embodiment includes a measuring unit 1 that measures a plurality of characteristic values of the developer, and a computing unit 2 that calculates the component concentration of the developer from the measured values. The calculation unit 2 includes a calculation block 21 that uses a multivariate analysis method, and a calculation block 22 that uses a calculation method other than the multivariate analysis method (for example, a calibration curve method).

The measured value of the characteristic value of the developer used for calculation in the multivariate analysis method is measured by the measurement section 1 and sent to the calculation block 21 using the multivariate analysis method in the calculation section 2. Used outside of multivariate analysis The measured value of the characteristic value of the developer in the calculation method (for example, the calibration curve method) is sent to the calculation block 22. By performing calculations in the calculation blocks 21 and 22, the component concentration of the developer is calculated.

In addition, the arithmetic block 22 using an arithmetic method other than the multivariate analysis method (for example, the calibration curve method) may be a complex number. Regarding the calculation using the multivariate analysis method and the calculation using other methods (such as the calibration curve method), the order of the calculation is not limited. The description of other components that overlap with the first and second embodiments is omitted.

The concentration monitoring device A of the embodiment includes an alarm unit WD. The alarm unit WD can be at least among the component concentration calculated by the calculation block 21 of the multivariate analysis method or the component concentration calculated by the calculation block 22 of the calculation method (for example, the calibration curve method) other than the multivariate analysis method. When any one of them deviates from the set management range, an alarm is issued.

[Fourth Embodiment]]

FIG. 7 is a schematic diagram of a concentration monitoring device in which the measuring unit 1 and the computing unit 2 are separately constructed. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

In the concentration monitoring device A of the present embodiment, the measuring section 1 is provided on a pipeline bypassed from the developer pipeline 80 of the developing process equipment B, and the measurement data signal lines 51 to 53 are connected to the computing section 2 . It can also be directly connected to the developer pipeline 80 or other pipelines. It is also possible to use a flow regulating valve (not shown) in combination to replace the sampling pump 14.

[Fifth Embodiment]

FIG. 8 is a schematic diagram of the concentration monitoring device in the case where the measuring members 11 to 13 for measuring the characteristic value of the developer are composed of the respective measuring device main bodies 11a, 12a, 13a and the measuring probes 11b, 12b, 13b. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

In the present embodiment, the measuring probes 11b to 13b of the measuring members 11 to 13 measure the characteristic value of the developer through the developer immersed in the developer storage tank 61. The measured characteristic value of the developer is sent to the computing unit 2 via the signal lines 51 to 53 for measurement data. The component concentration of the developer is measured by calculating the component concentration in the computing unit 2 by using the multivariate analysis method.

Although FIG. 8 shows a case where the measurement unit 1 and the calculation unit 2 are separately constructed, they may be an integrated concentration monitoring device. In this case, the measuring probe immersed in the developer and the measuring device main body arranged in the measuring section 1 of the concentration monitoring device are connected by a cable or the like.

[Sixth Embodiment]

FIG. 9 is a schematic diagram of a concentration monitoring device in a case where the measuring means in the measuring section 1 arranged in parallel are provided. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

The measurement members constituting the measurement unit 1 are not limited to being connected in series, and may be connected in parallel. As shown in Figure 9, the measuring components 11-13 can also be independently equipped with sampling pipes 15a-15c and sampling The pumps 14a to 14c, the return pipes 16a to 16c, etc., may also be connected in parallel by pipes that branch in the middle. The characteristic values of the developer measured by the measuring members 11 to 13 are sent to the computing unit 2. The component concentration of the developer is calculated in the computing section 2 by a multivariate analysis method.

[Seventh Embodiment]

Fig. 10 is a schematic diagram of a concentration monitoring device in a case where a measurement device that requires addition of a drug is provided, such as an automatic titration device. In FIG. 10, the third measurement member 13 is a measurement device that requires addition of a drug. The concentration monitoring device is provided with an alarm unit WD, and can issue an alarm when at least any of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

In this case, in addition to being connected to the sampling pipe 15 and the sampling pump 14, the third measuring member 13 is also connected to the addition reagent 93 via the liquid feeding pipe 18. The reagent addition system is collected by the liquid delivery pump 17 for measurement. The developer after the measurement is discharged (discharged) through the waste liquid pipe 19. Since other measurement operations, calculation operations, etc. are the same as those of the other embodiments, they are omitted.

As described above, as shown in the first to seventh embodiments, the concentration monitoring device of the present invention includes: a measuring unit 1 that measures a plurality of characteristic values of the developer related to the component concentration of the developer; and a computing unit 2 based on the measuring unit 1. Measure multiple characteristic values of the developer and measure the component concentration of the developer by a multivariate analysis method.

The measurement unit 1 of the concentration monitoring device A of this embodiment can take various embodiments. Since the measuring device used as the measuring component has a suitable setting according to the measuring method adopted by the measuring device Or the method of connection, so the measurement unit 1 of the concentration monitoring device of the present invention only needs to be configured most appropriately in accordance with the measurement member.

What is necessary is just to equip the measuring part 1 with the measuring means required to measure the several characteristic value of a developer. It is desirable that the measurement unit 1 includes a temperature adjustment member (not shown). Although it is desirable to appropriately include the sampling pump 14, the liquid feeding pump 17, the waste liquid piping 19, etc., as necessary, it does not mean that all of them need to be internal parts of the measurement unit 1.

In addition, the measurement unit 1 and the calculation unit 2 may be integrated or separate. The measuring unit 1 and the computing unit 2 may be connected to each other so long as the computing unit 2 can receive the measurement data of the characteristic value of the developer measured by the measuring unit 1. The measurement unit 1 and the calculation unit 2 are not limited to the case of being connected by a signal line, and may be configured to be capable of wirelessly transmitting and receiving data (data). There is also no need to gather a plurality of measurement members in one place to form the measurement section 1, and one specific measurement member may be separately arranged.

Each measurement member is not only a method of taking a sample for measurement, but also a method of directly installing in a pipe, or a method of immersing the probe in a liquid. The measurement members can be connected in series or in parallel. It is also possible to configure the measurement unit 1 by various combinations.

In addition, the order of the measurement of the plural characteristic values of the developer in the measuring section 1 of the present embodiment is not limited. The arrangement of the measurement members in the measurement section 1 in the drawings from Fig. 4 to Fig. 10, and the descriptions of "first measurement member", "second measurement member", etc., "first", " The terms "second", etc. do not limit the order of determination in the present invention. The terms "first", "second", ... and so on are just for the convenience of distinguishing each of the plural measurement components.

In addition, if the calculation unit 2 of the concentration monitoring device of the present embodiment includes a calculation block 21 using a multivariate analysis method, it may additionally have a calculation block using a method other than the multivariate analysis method (for example, a calibration curve method). At this time, the order of operations is not limited.

In the concentration monitoring device of this embodiment, the measurement members constituting the measurement section 1 are arranged and connected to suit the measurement method to measure a plurality of characteristic values of the developer, and the computing section 2 receives the development measured by the measurement section 1. The measured value of the characteristic value of the liquid is calculated by the multivariate analysis method (included in the calculation method) to calculate the component concentration of the developer.

Hereinafter, in the eighth embodiment and the ninth embodiment, an application example of the concentration monitoring device of this embodiment will be described. The concentration monitoring device of this embodiment can be applied to various devices or systems as a component.

[Eighth Embodiment]

Figure 11 is a schematic diagram of a developer management device using the concentration monitoring device of this embodiment. The concentration monitoring device includes an alarm unit WD.

In the present embodiment, the concentration monitoring device A is connected to the control unit 3 (control device) that controls the control valves 41 to 43 via a signal line 54 for calculation data. The control part 3 (control device) is connected to each control valve 41-43 by the signal line 55-57 for control signals. The control valves 41 to 43 are respectively provided in the replenishing liquid pipes 81 and 82 for conveying the replenishing liquid from the replenishing liquid storage tanks 91 and 92 and the pure water pipe 83 for conveying pure water.

The replenishing liquid storage tanks 91 and 92 are pressurized by nitrogen gas, and the control valves 41 to 43 are opened and closed through the control unit 3 (control device), and the replenishing liquid is supplied to the developer through the confluence line 84. The replenishing liquid is returned to the developer storage tank 61 via the circulation line 85 by the circulation pump 74 and is stirred. The method, mechanism, etc. of the replenishing operation of the replenisher are described in the embodiments of the developer management method, developer management apparatus, etc. described later.

In this way, the concentration monitoring device of this embodiment can be used as a component of the developer management device by combining with the control valve provided in the pipeline for supplying the replenishing liquid to the developer and the control device for controlling these.

In addition, the so-called replenishing liquid means, for example, the original liquid, fresh liquid, and regenerated liquid of the developer. There are also cases where pure water is included. The so-called stock solution refers to an unused developer solution (such as 20-25% TMAH aqueous solution) with a strong alkali component concentration. The so-called new solution means an unused developer (for example, 2.38% TMAH aqueous solution) with the same concentration of alkali component as the concentration used in the development process. The so-called regenerated liquid means to remove unnecessary materials from the used developer to make a reusable developer. These are different in the use and effect of the supplement liquid. For example, the stock solution is a replenishing solution used to increase the concentration of alkali components, reduce the concentration of dissolved photoresist and the concentration of carbon dioxide absorption. The new liquid is a supplementary liquid used to maintain or gently increase or decrease the concentration of alkali components, reduce the concentration of dissolved photoresist and the concentration of carbon dioxide absorption. Pure water is a replenisher used to reduce the concentration of each component. The same applies to the description of the following embodiments.

11 illustrates the case where the supplementary liquid system is supplied from the supplementary liquid storage tanks 91 and 92 via the supplementary liquid lines 81 and 82, and the pure water system is supplied via the pure water pipeline 83, but it is not This is limited. There are also cases where the replenisher is sent from the replenisher storage tanks 91, 92, etc. to a mixing tank (not shown), where it is prepared to a predetermined concentration, and then sent to the developer storage tank 61. In this case, the control valves 41 and 42 are provided in the middle of the pipeline transporting from the mixing tank to the developer storage tank 61. There may be cases where pure water is not directly supplied to the developer storage tank 61, and there is no pure water pipeline 83, control valve 43, etc. at this time. The same applies to the description of the following embodiments and the following drawings.

The replenishing liquid is stored in the replenishing liquid storage tanks 91 and 92 of the replenishing liquid storage portion C. The replenishing liquid storage tanks 91 and 92 are connected to a pipe 86 for nitrogen gas provided with valves 46 and 47 for pressurized gas, and are pressurized by nitrogen gas supplied through this pipe. In addition, the replenishing liquid pipes 81 and 82 are respectively connected to the replenishing liquid storage tanks 91 and 92, and the replenishing liquid is delivered through the valves 44 and 45 which are normally open. The replenishing liquid pipelines 81 and 82 and the pure water pipeline 83 are provided with control valves 41 to 43, and the control valves 41 to 43 are controlled to open and close by the control unit 3. Through the operation of the control valve, the replenishing liquid stored in the replenishing liquid storage tanks 91 and 92 is sent under pressure and pure water is delivered. After that, the replenishing liquid merges with the circulation stirring mechanism D via the joining pipe 84 and is replenished to the developer storage tank 61 and stirred.

When the replenishing liquid stored in the replenishing liquid storage tanks 91, 92 is reduced due to the replenishment, the supply amount becomes unstable due to the decrease in the internal pressure. Therefore, the maintenance factor should appropriately open the pressurized gas valves 46, 47 in response to the decrease of the replenishing liquid. Nitrogen gas is supplied to maintain the internal pressure of the replenishing liquid storage tanks 91 and 92. When the replenishing liquid storage tanks 91 and 92 become empty, close the valves 44 and 45 and replace them with a new replenishing liquid storage tank filled with the replenishing liquid, or refill the empty replenishing liquid storage tank 91 with a separately prepared replenishing liquid. , 92.

[Ninth Embodiment]

The concentration monitoring device of this embodiment can be combined with the display device DP and used as a component concentration monitor or concentration monitoring device of the developer. It can also be used as the display device DP and the alarm unit WD. Fig. 12 is a schematic diagram showing an application example of the concentration monitoring device of the present invention. In this way, the concentration monitoring device of the present invention can be applied to various devices, systems, etc. as parts.

Hereinafter, FIGS. 13 to 17 show the developer management method related to the embodiment.

The developer management method of the present invention includes: a measuring step of measuring a plurality of characteristic values of the developer related to the component concentration of the alkaline developer; an arithmetic step of calculating the developer from the measured characteristic values by a multivariate analysis method The component concentration of the liquid; and the replenishing step, based on the measured characteristic value of the developer or the calculated component concentration of the developer, to replenish the developer with the replenishing liquid. The measurement steps and calculation steps are the same as the measurement steps and calculation steps in the above-mentioned method for measuring the component concentration of the developer, so the repeated description will be omitted in the following embodiments in FIGS. 13 to 17.

In addition, in the following description, the "predetermined management value" means the characteristic value or component concentration value when the developer exhibits the best liquid performance as a developer. It is a characteristic value or component concentration known in advance based on experience or experiment. value. That is, the value used as an indicator of the developing performance of the developer, such as the line width or the residual film thickness formed on the substrate after development, refers to the predicted value of the characteristic value or the component concentration value in the best state . The "established management area" is also the range of such management values. The same applies to the description of the developer management device.

FIG. 13 is a flowchart of a developer management method for managing two components of a developer by component concentration. The developer management method of this embodiment can be preferably applied to an alkaline developer that is managed so that the absorption of carbon dioxide is low. The concentration of the alkali component of the developer becomes the predetermined management value and the concentration of the dissolved photoresist becomes Manage the condition of the developer solution below the predetermined management value.

In the present embodiment, the component concentration A is managed at a predetermined management value A ₀ , and the component concentration B is managed below the predetermined management value B ₀ . The component concentration A system is, for example, the alkali component concentration, and the component concentration B system is, for example, the dissolved photoresist concentration.

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

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, it is determined whether the component concentration A is larger or smaller than its management value A ₀ . When it is large, replenish the developer with a replenisher (for example, fresh developer solution, pure water, etc.) that can dilute the component concentration A. At the hour, the developer is replenished with a replenisher (for example, a stock solution of the developer, a new solution, etc.) that can increase the concentration of the component A. When the component concentration A is the same as its management value A ₀ , nothing is done.

In the step of adjusting the component concentration B, it is determined whether the component concentration B is greater than its management value B ₀ . When it is large, a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

FIG. 14 is a flowchart of a developer management method in the case where one of the two components of the developer is managed by the component concentration and the other is managed by the characteristic value. The developer management method of this embodiment can be preferably applied to an alkaline developer that is managed so that the absorption of carbon dioxide is low, and the concentration of the alkali component of the developer can be a predetermined management value and a specific wavelength of the developer ( For example, the absorbance in λ=560nm) can be managed in such a way as to be below the predetermined management value.

In the present embodiment, the component concentration A is managed to a predetermined management value A ₀ , and the measured value b _m of the characteristic value b of the developer is managed to be below the predetermined management value b ₀ . The component concentration A is, for example, the alkali component concentration, and the characteristic value b is, for example, the absorbance at a specific wavelength (for example, λ=560 nm).

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

The replenishment step includes the step of adjusting the component concentration A and the step of adjusting the characteristic value b. Since the steps for adjusting the component concentration A are the same as in the case of FIG. 13, the description thereof will be omitted.

In the step of adjusting the characteristic value b, the measured value b _{m is} compared with the management value b ₀ to determine whether it is larger. When it is large, a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

When the characteristic value b and the component concentration B have a monotonically increasing correlation, the transmission characteristic value b is managed to be below its management value b ₀ and the component concentration B is managed to be below its management value B ₀ . When the characteristic value b and the component concentration B have a monotonically decreasing correlation, if the magnitude relationship of the determination is reversed and the operation is performed, the component concentration B can be managed to be below its management value B _{0 in} the same way.

FIG. 15 is a flowchart of a developer management method in which the three components of the developer are managed by the component concentration. The developer management method of this embodiment can be preferably applied to, for example, the concentration of the alkali component of the developer is managed to a predetermined management value, the concentration of the dissolved photoresist is managed to be below the predetermined management value, and the concentration of carbon dioxide absorbed When the management becomes below the predetermined management value, etc.

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

In the measuring step, the characteristic values a, b, c, ... of the developer are measured, and the measured values a _m , b _m , c _m , ... are sent to the calculation step. In the step of calculating, by multivariate analysis from the measured value _{a m, b m, c m} , ... calculate the concentration of the developer components A, B, C, .... The component concentrations A, B, C, ... calculated by the calculation step are sent to the replenishment step.

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

First, in the step of adjusting the component concentration A, it is determined whether the component concentration A is larger or smaller than its management value A ₀ . When it is large, replenish the developer with a replenisher (for example, fresh developer solution, pure water, etc.) that can dilute the component concentration A. At the hour, the developer is replenished with a replenisher (for example, a stock solution of the developer, a new solution, etc.) that can increase the concentration of the component A. When the component concentration A and its management value A ₀ are the same, nothing is done.

In the step of adjusting the component concentration B, it is determined whether the component concentration B is greater than its management value B ₀ . When it is large, replenish the developer with a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is better). Do nothing at the hour.

In the step of adjusting the component concentration C, it is determined whether the component concentration C is greater than its management value C ₀ . When it is large, a replenisher that can dilute the component concentration C (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

FIG. 16 is a flowchart of a developer management method in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration. The developer management method of this embodiment can be preferably applied to the fact that the alkali component concentration of the developer can be a predetermined management value, and the absorbance at a specific wavelength (e.g. λ=560nm) of the developer can be below the predetermined management value. , And the developer's absorbed carbon dioxide concentration can be controlled below the predetermined management value.

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

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

The replenishment step includes the step of adjusting the component concentration A, the step of adjusting the characteristic value b, and the step of adjusting the component concentration C. Since the step of adjusting the component concentration A and the step of adjusting the component concentration C are the same as in FIG. 15, the description thereof will be omitted.

In the step of adjusting the characteristic value b, the measured value b _{m is} compared with the management value b ₀ to determine whether it is larger. When it is large, a replenisher that can dilute the component concentration B (for example, a new developer solution does not change the alkali component concentration, so it is preferable) to replenish the developer. Do nothing at the hour.

When the characteristic value b and the component concentration B have a monotonically increasing correlation, the transmission characteristic value b is managed to be below its management value b ₀ and the component concentration B is managed to be below its management value B ₀ . When the characteristic value b and the component concentration B have a monotonically decreasing correlation, if the magnitude relationship of the judgment is reversed (that is, b _m <b ₀ ), the component concentration B can be managed as its management value B. Below ₀ .

FIG. 17 is a flowchart of a developer management method in which two of the three components of the developer are managed by characteristic values and the other is managed by the component concentration. The developer management method of this embodiment can be preferably applied to the fact that the conductivity of the developer can be a predetermined management value, and the absorbance at a specific wavelength (for example, λ=560nm) of the developer can be below the predetermined management value, And the concentration of carbon dioxide absorbed by the developer can be managed in such a way that the developer can be controlled below the predetermined management value.

In the present embodiment, it is assumed that the measured value a _m of the characteristic value a of the developer is managed at a predetermined management value a ₀ , and the measured value b _m of the characteristic value b of the developer is managed below the predetermined management value b ₀ . The concentration C is managed below the predetermined management value C ₀ . The characteristic value a is, for example, electrical conductivity, the characteristic value b is, for example, the absorbance at a specific wavelength (for example, λ=560 nm), and the component concentration C is, for example, the concentration of absorbed carbon dioxide.

Characteristics of the developer measured in the measurement step values a, b, c, the measured values a _m, b _m, c _m is sent to the calculating step. In the operation step, by multivariate analysis from the measured value a _m, b _m, c _m is calculated concentration of the developer components A, B, C. Measured characteristic value of the measurement step of measuring a value of a _m, b is a value measured characteristic values of _m and b calculated by the calculating step based component concentration C is supplied to the supply step.

The replenishment step includes the step of adjusting the characteristic value a, the step of adjusting the characteristic value b, and the step of adjusting the component concentration C. Since the step of adjusting the characteristic value b and the step of adjusting the component concentration C are the same as those in FIG. 16, the description thereof will be omitted.

In the step of adjusting the characteristic value a, the measured value a _{m is} compared with the management value a ₀ to determine whether it is larger or smaller. When it is large, replenish the developer with a replenisher that can dilute the component concentration A (for example, the original developer solution or a new solution). At small hours, the developer is replenished with a replenisher (for example, fresh developer solution or pure water) that can increase the concentration of component A. Do nothing at the same time.

When the characteristic value a and the component concentration A have a monotonically increasing correlation, the characteristic value a is maintained at its management value a ₀ so that the component concentration A is managed to its management value A ₀ . When the characteristic value a and the component concentration A have a monotonously low correlation, if the magnitude relationship of the judgment is reversed and the operation is performed, the component concentration A can be managed to the management value A _{0 in} the same manner.

Above, the developer management method shown in FIGS. 13 to 17 includes: a measuring step of measuring a plurality of characteristic values of the developer related to the component concentration of the developer; an arithmetic step of measuring a plurality of characteristic values based on the measured characteristic values The variable analysis method calculates the component concentration of the developer; and the replenishment step is based on the measured value or calculated value of the management target item selected from the measured plural characteristic values of the developer and the calculated component concentration of the developer. Developer replenishes replenisher.

The measuring step further includes: a measuring step of measuring the characteristic value a, a measuring step of measuring the characteristic value b, a measuring step of measuring the characteristic value c, etc. However, the order of these steps is not limited. It can also be measured at the same time. In addition, the temperature adjustment step, the reagent addition step, the waste liquid step, etc. may include appropriate necessary steps in accordance with the measurement method.

The calculation step should just include a calculation step for calculating the component concentration using a multivariate analysis method. It may also include a step for calculating the component concentration using a calculation method different from the multivariate analysis method (for example, a calibration curve method).

The replenishment step includes: Regarding the management target item (either the characteristic value or the component concentration of the developer) as the control amount, and using this to become the predetermined management value or below the predetermined management value or within the management area The step of adjusting component concentration A, the step of adjusting component concentration B, the step of adjusting component concentration C,... The order is not limited by the order shown in the figure.

In addition, as the control method, various control methods that can be used for the control to make the control amount conform to the target value can be adopted. Especially proportional control (P control) (Proportional Control), integral control (I control) (Integral Control), differential control (D control) (Differential Control), and a combination of these controls (PI control (Proportional Control) -Integral Control) etc.) is better. More preferably, it is suitable for PID control.

In the embodiment shown in FIGS. 13 to 17 above, by repeating the measurement steps, calculation steps, and replenishment steps, the component concentration A of the developer is maintained at its management value A ₀ , and the component concentration B of the developer is managed to be its management value Below B ₀ , the component concentration C is below its management value C ₀ . Therefore, with the developer management method of the present invention, the best development performance can be maintained, and the desired line width or residual film thickness can be achieved.

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

The developer management device of this embodiment is provided with: a measuring unit 1 which measures plural characteristic values of the developer related to the component concentration of the alkaline developer; and a computing unit 2 which measures from the measuring unit 1 by a multivariate analysis method Calculate the component concentration of the developer from the plurality of characteristic values; and the control section 3, based on the characteristic value of the developer measured by the measuring section 1 or the developer’s component concentration calculated by the calculating section 2 The control valves 41~43 on the pipeline of the replenishing liquid for liquid replenishment send out control signals. Since the measuring section 1 and the calculating section 2 of the developer management device of the present invention are the same as the measuring section 1 and the calculating section 2 in the aforementioned developer component concentration measuring device, the tenth to seventeenth embodiments are described below. Repetitive descriptions are omitted.

[Tenth Embodiment]

FIG. 18 is a schematic diagram for explaining the development process of the developer management device of the present invention. The developer management device E of the present invention is illustrated together with the development process equipment B, the replenishing liquid storage portion C, the circulating stirring mechanism D, and the like.

The developer management device E of the present embodiment includes: a measuring section 1 including a plurality of measuring members 11 to 13 for measuring a plurality of characteristic values of the developer; a calculation section 2 including a calculation block 21 using a multivariate analysis method; and a control section 3. Regarding any of the characteristic value or component concentration of the developer as the control quantity and making it into a predetermined management value or within the management area for control; and the alarm unit WD. In addition, the developer management device of the present embodiment includes control valves 41 to 43 that are connected to the control unit 3 and controlled.

The developer management device E is connected to the developer storage tank 61 through the sampling pipe 15. The developer sampled by the sampling pump 14 is guided into the measurement section 1 through the sampling pipe 15. In the measuring section 1, the measuring members 11 to 13 measure the characteristic value of the developer. The developer after the measurement is returned to the developer storage tank 61 through the return pipe 16.

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

The details of the measurement operation and arithmetic operation are the same as those of the above-mentioned concentration monitoring device for the imaging liquid, so they are omitted, so the control operation will be described below.

The developer management device E is connected to the pipes 81 to 83 (replenishing liquid including pure water) and transports the replenishing liquid to be replenished to the developer. The pipes 81 to 83 are connected to control valves 41 to 43 whose operations are controlled by the control unit 3 in the developer management device E.

The control section 3 receives the measured value of the characteristic value of the developer from the measurement section 1 and the component concentration calculated by the calculation section 2. The control unit 3 regards the characteristic value or component concentration of the received developer as the control quantity, and sends control signals to the control valves 41 to 43 according to the control quantity. The control system is performed so that, for example, the control amount becomes a predetermined management value or within a predetermined management area.

The control unit 3 includes a control block. For example, if the developer management device E manages the three component concentrations A, B, and C of the developer, the control unit 3 includes a control block 31 for controlling the component concentration A and a control block for controlling the component concentration B 32. A control block 33 for controlling the component concentration C. If the concentration of the component to be managed is two, then two control blocks are sufficient. If the concentration of the component to be managed is more than three, the same control block should be provided for it. In this way, the control unit 3 can issue necessary control signals to the control valves 41 to 43.

The control valves 41 to 43 are, for example, control valves that are opened during the reception of an "open" signal. When the flow rate is adjusted in advance so that the valve can deliver a predetermined flow rate when the valve is opened, the control unit 3 is used for a predetermined time. The range sends the "on" signal to the control valve set on the pipeline that transports the replenishing liquid that should be replenished, so as to replenish the developer with the necessary amount of replenishing liquid required for developer management.

The control action of the control valve is not limited by this example. In the case that the control valve switches between the open state and the closed state of the valve according to the open/close switching signal, the pulsed open/close switching signal is sent to the control valve at a predetermined time interval through the control unit 3, and only the necessary amount of the required amount is supplied to the developer. Replenishing fluid.

Furthermore, the control valves 41 to 43 may be those capable of controlling the opening degree of the valve, or may be a combination of a simple flow control valve (needle valve) and an on-off control valve. The control valves 41 to 43 may also be solenoid valves or air pressure operated valves (air operated valves).

The penetration control valves 41 to 43 operate based on the control signal issued by the control unit 3 to replenish the developer with an amount of replenishing liquid required for developer management. The control unit 3 sends a control signal to the control valve to be controlled to deliver the necessary replenishment amount based on the type of replenishing solution and the necessary replenishment amount obtained from the received control amount (the characteristic value or component concentration of the developer).

In this way, with the developer management device of this embodiment, the measured characteristic value of the developer or the calculated component concentration of the developer can be maintained in such a way as to become a predetermined management value or within a predetermined management area. Manage the developer.

More specifically, the following developer management is possible. However, the developer management system exemplified below is an example and is not limited to this.

First, it is the developer management that replenishes the developer with the replenishing solution so that the concentration of the alkali component, the concentration of the dissolved photoresist and the concentration of the carbon dioxide absorbed can each become a predetermined management value for the reused alkaline developer. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), The dissolved photoresist concentration can be managed to a predetermined management value below 0.40 (wt%), preferably 0.15 (wt%), and the absorbed carbon dioxide concentration can be managed to a predetermined management value below 0.40 (wt%) Preferably, it is more preferably 0.25 (wt%).

Second, it is to replenish the developer with the replenishment solution in such a way that the alkali component concentration of the repeatedly used alkaline developer can become the established management value, and the dissolved photoresist concentration and the absorbed carbon dioxide concentration can each become below the established management value. Developer management. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), The concentration of the dissolved photoresist can be controlled to 0.40 (wt%) or less, and the concentration of carbon dioxide absorbed can be controlled to 0.40 (wt%) or less.

Thirdly, it is the developer management that replenishes the developer with the replenisher so that the concentration of the alkali component, the absorbance at a specific wavelength, and the concentration of carbon dioxide absorbed by the repeatedly used alkaline developer can each become a predetermined management value. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), The absorbance in wavelength λ=560nm (cell optical path length d=10mm) can be managed to a predetermined management value below 1.30 (Abs.), preferably 0.50 (Abs.), which can reduce the absorption of carbon dioxide concentration It is better to manage to a predetermined management value of 0.40 (wt%) or less, and more preferably 0.25 (wt%).

Fourth, the concentration of the alkali component of the repeatedly used alkaline developer can become the predetermined management value, the absorbance at a specific wavelength can be within the predetermined management area, and the absorbed carbon dioxide concentration can become below the predetermined management value. Developer management of developer replenishment replenisher. For example, according to the developer management device of the present invention, the alkali component concentration of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 2.375 to 2.390 (wt%), preferably 2.380 (wt%), Absorbance at wavelength λ=560nm (groove optical path length d=10mm) can be managed to be 1.30 (Abs.) or less, more preferably 0.65 (Abs.) or less, and the absorbed carbon dioxide concentration can be managed to 0.40 (wt%) The following is better.

Fifth, the developer management that replenishes the developer with replenishing liquid so that the conductivity of the repeatedly used alkaline developer, the absorbance at a specific wavelength, and the concentration of carbon dioxide absorbed can each become a predetermined management value. For example, according to the developer management device of the present invention, the conductivity of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 54.47~54.75 (mS/cm), preferably 54.58 (mS/cm) , The absorbance in the wavelength λ=560nm (slot optical path length d=10mm) can be managed to a predetermined management value below 1.3 (Abs.), preferably 0.50 (Abs.), and the absorbed carbon dioxide concentration can be managed to A predetermined management value of 0.40 (wt%) or less is preferable, and 0.25 (wt%) is more preferable.

Sixth, it is developed in such a way that the conductivity of the repeatedly used alkaline developer can become the established management value, the absorbance at a specific wavelength can be within the established management area, and the absorbed carbon dioxide concentration can become below the established management value. Liquid replenishment replenishing liquid developer management. For example, according to the developer management device of the present invention, the conductivity of the 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 54.47~54.75 (mS/cm), preferably 54.58 (mS/cm) , The absorbance in the wavelength λ=560nm (the optical path length of the groove d=10mm) can be managed to be 1.30 (Abs.) or less, more preferably 0.65 (Abs.) or less, and the absorbed carbon dioxide concentration can be managed to 0.40 (wt%) ) The following are preferred.

Therefore, according to the developer management device of this embodiment, the concentration of each component or characteristic value of the developer can be managed with high accuracy in a predetermined management value or management area, compared with the prior art. Maintain the best development performance, can achieve the desired line width or residual film thickness. In addition, the alarm unit WD issues an alarm when at least one of the component concentrations calculated by the calculation unit 2 deviates from the set management range.

[Eleventh Embodiment]

Fig. 19 is a schematic diagram for explaining that the control valves 41 to 43 provided on the pipeline for conveying the replenishing liquid to be replenished to the developer are located outside the developer management device of this embodiment.

The developer management device E of the present embodiment includes: a measuring section 1 including a plurality of measurement members for measuring a plurality of characteristic values of the developer; a calculation section 2 including a calculation block 21 using a multivariate analysis method; a control section 3 Either the characteristic value or the component concentration of the developer is used as the control quantity and it becomes the established management value or within the management area to send a control signal to the control valves 41~43 arranged on the replenishing liquid supply line; and WD.

In this embodiment, the control valves 41 to 43 controlled by the control unit 3 are not internal parts of the developer management device E. Separately from the developer management device E, it is installed in the pipeline for conveying the replenisher. The developer management device E is not connected to these pipelines that transport the replenisher.

The other configurations, operations, etc. are the same as those of the tenth embodiment, so they are omitted.

[Twelfth Embodiment]

FIG. 20 is a schematic diagram of a developer management device E provided with an arithmetic control unit 23 having arithmetic function and control function together.

The developer management device E of the present invention is not limited to the case where the calculation section 2 and the control section 3 are configured as separate devices. It may also be configured as the arithmetic control unit 23 that has one of the arithmetic function and the control function. As the calculation control unit 23, for example, a multi-function device such as a computer can be cited. The developer management device E includes an alarm unit WD.

The computer has a wide variety of functions such as input/output functions, sending and receiving functions, calculation functions, control functions, and display functions. Therefore, the calculation function and control function of the developer management device E of the present invention can be realized by a computer. The calculation control unit 23 only needs to be connected to the measurement unit 1 and the control valves 41 to 43. At this time, if it is an arithmetic processing program that calculates the component concentration from the characteristic value of the developer measured by the multivariate analysis method, and sends a control signal to the control valves 41 to 43 to control the amount (the characteristic value of the developer or If the component concentration) becomes a predetermined management value or a control program in a predetermined management area is installed in a computer, the developer can be maintained and managed in a predetermined state.

The other configurations, operations, etc. are the same as those of the tenth embodiment, so they are omitted.

[Thirteenth Embodiment]

Figure 21 is a schematic diagram of a developer management device that manages two components of a developer. The developer management device E of the present embodiment can be suitably used to manage the concentration of the alkali component and the concentration of the dissolved photoresist in an alkaline developer that is managed to absorb less carbon dioxide.

If it is assumed that the first measuring member 11 is a measuring member that measures the characteristic value of the developer related to the concentration of at least the alkali component in the components of the developer (for example, a conductivity meter for measuring electrical conductivity), and the second measuring member 12 is to measure and If the component of the developer solution at least dissolves the characteristic value of the developer solution related to the photoresist concentration (for example, an absorbance photometer that measures the absorbance at λ=560nm), the calculation unit 2 contains a calculation block using a multivariate analysis method. 21. Therefore, the concentration of the alkali component and the concentration of the dissolved photoresist in the developer can be calculated from the characteristic value of the developer measured by the multivariate analysis method.

Therefore, the control block 31 is a control block that sends a control signal to the control valve in such a way that the conductivity or alkali component concentration of the developer can become a predetermined management value, and the control block 32 is a specific wavelength of the developer (for example, λ= When the absorbance or dissolved photoresist concentration in 560nm) can become a predetermined management value or a control block that sends a control signal to the control valve in the management area, because the control unit 3 can receive the measured characteristic value of the developer It is connected to the measuring section 1 and the computing section 2 with the calculated component concentration of the developer. Therefore, the developer management device E of this embodiment can make the concentration of the alkali component of the developer a predetermined management value and dissolve The developer is maintained and managed so that the photoresist concentration becomes a predetermined management value or within the management area.

The other details are the same as the other embodiments, so they are omitted.

[Fourteenth Embodiment]

Fig. 22 is a schematic diagram of a developer management device in which two components of a developer are managed by component concentrations. The developer management device of the present embodiment can be preferably applied to a case where the alkali component concentration and the dissolved photoresist concentration of an alkaline developer managed to not absorb carbon dioxide are managed to manage concentration values.

If it is assumed that the first measuring member 11 is a measuring member that measures the characteristic value of the developer related to the concentration of at least the alkali component in the components of the developer (for example, a conductivity meter for measuring electrical conductivity), and the second measuring member 12 is to measure and If the components of the developer solution at least dissolve the characteristic value of the developer solution related to the photoresist concentration (for example, an absorbance photometer that measures the absorbance at λ=560nm), the calculation unit 2 contains the use of multivariate analysis The calculation block 21 of the method can calculate the alkali component concentration and the dissolved photoresist concentration of the developer from the characteristic value of the developer measured by the multivariate analysis method.

Therefore, if the control block 31 is a control block that sends a control signal to the control valve so that the alkali component concentration can become a predetermined management value, and the control block 32 is a dissolved photoresist concentration that can become a predetermined management value or management If the control block sends a control signal to the control valve below the value, since the control section 3 is connected to the calculation section 2 in a manner that can receive the calculated component concentration of the developer, the developer management device according to this embodiment E. The developer can be maintained and managed so that the concentration of the alkali component of the developer becomes a predetermined management value, and the concentration of the dissolved photoresist becomes the predetermined management value or less.

The other details are the same as the other embodiments, so they are omitted.

[Fifteenth Embodiment]

FIG. 23 is a schematic diagram of a developer management device in which two of the three components of the developer are managed by characteristic values and the other by the component concentration. The developer management device of this embodiment is preferably suitable for the management of the alkali component concentration of the alkaline developer by the conductivity, the dissolved photoresist concentration by the absorbance in a specific wavelength (for example, λ=560nm), and The concentration of absorbed carbon dioxide is managed by the concentration, etc.

If it is assumed that the first measuring member 11 is a measuring member for measuring the characteristic value of the developer related to at least the concentration of the alkali component in the components of the developer (for example, a conductivity meter for measuring conductivity), the second measuring member 12 is for measuring and The component of the developer solution at least dissolves the characteristic value of the developer solution related to the photoresist concentration (for example, measuring the absorbance in λ=560nm The absorbance photometer), and the third measuring means are measuring means for measuring the characteristic value of the developer related to at least the concentration of carbon dioxide absorbed in the components of the developer (for example, a densitometer for measuring density), because the calculation unit 2 contains The operation block 21 of the multivariate analysis method can calculate the alkali component concentration, the dissolved photoresist concentration and the absorbed carbon dioxide concentration of the developer from the characteristic values of the developer measured by the multivariate analysis method.

Therefore, the control block 31 is a control block that sends a control signal to the control valve so that the conductivity of the developer can become a predetermined management value, and the control block 32 is the absorbance in the characteristic wavelength of the developer (for example, λ=560nm). It can be a control block that sends a control signal to the control valve in a manner within a predetermined management value or a management area, and the control block 33 sends a control signal to the control valve in a manner that the absorbed carbon dioxide concentration can become a predetermined management value or below the management value When controlling the block, since the control section 3 is connected to the measuring section 1 in a manner that can receive the measured characteristic value of the developer, and is connected to the computing section 2 in a manner that can receive the calculated component concentration of the developer, it is based on this The embodiment of the developer management device E can manage the alkali component concentration of the developer to the predetermined management value, the dissolved photoresist concentration to be the predetermined management value or less, and the absorbed carbon dioxide concentration to be the predetermined management The developer is maintained and managed below the value or management value.

The other details are the same as the other embodiments, so they are omitted.

[Sixteenth Embodiment]

Figure 24 is the development of a developer management device in which one of the three components of the developer is managed by the characteristic value and the other two are managed by the component concentration Schematic. The developer management device of this embodiment is preferably suitable for the management of the alkali component concentration and the absorbed carbon dioxide concentration of the alkaline developer by the concentration, and the dissolved photoresist concentration by the specific wavelength (for example, λ=560nm) In the case of management, etc.

If it is assumed that the first measuring member 11 is a measuring member for measuring the characteristic value of the developer related to at least the concentration of the alkali component in the components of the developer (for example, a conductivity meter for measuring conductivity), the second measuring member 12 is for measuring and developing The component of the liquid at least dissolves the characteristic value of the developer related to the concentration of the photoresist (for example, an absorbance photometer that measures the absorbance at λ=560nm), and the third measuring means measures at least the component of the developer In the case of a measuring member that absorbs the characteristic value of the developer related to the carbon dioxide concentration (for example, a densitometer for measuring density), since the calculation section 2 includes a calculation block 21 using a multivariate analysis method, it can be obtained from the development measured by the multivariate analysis method. The characteristic value of the liquid, the alkali component concentration, the dissolved photoresist concentration and the carbon dioxide absorption concentration of the developer are calculated.

Therefore, the control block 31 is a control block that sends a control signal to the control valve so that the alkali component concentration can become a predetermined management value, and the control block 32 is the absorbance at the characteristic wavelength of the developer (for example, λ=560nm). A control block that sends a control signal to the control valve when it becomes a predetermined management value or within a management area. The control block 33 is a control block that sends a control signal to the control valve so that the concentration of carbon dioxide absorbed can become the predetermined management value or below the management value. In this case, since the control section 3 is connected to the measuring section 1 in a manner that can receive the measured characteristic value of the developer, and is connected to the computing section 2 in a manner that can receive the calculated component concentration of the developer, it is based on this embodiment. The developer management device E can make the developer The developer is maintained and managed so that the alkali component concentration becomes a predetermined management value, the dissolved photoresist concentration becomes the predetermined management value or less, and the absorbed carbon dioxide concentration becomes the predetermined management value or less.

The other details are the same as the other embodiments, so they are omitted.

[Seventeenth Embodiment]

FIG. 25 is a schematic diagram of a developer management device in which three components of a developer are managed by component concentrations. The developer management device of this embodiment can be preferably applied to the case where the concentration of the alkali component, the concentration of the dissolved photoresist, the concentration of carbon dioxide absorption, etc. of the alkaline developer are managed by the concentration.

If it is assumed that the first measuring member 11 is a measuring member for measuring the characteristic value of the developer related to at least the concentration of the alkali component in the components of the developer (for example, a conductivity meter for measuring conductivity), the second measuring member 12 is for measuring and developing The component of the liquid at least dissolves the characteristic value of the developer related to the concentration of the photoresist (for example, an absorbance photometer that measures the absorbance at λ=560nm), and the third measuring component measures at least the absorption in the component of the developer. In the case of a measuring component (such as a densitometer for measuring density) of the characteristic value of the developer related to the carbon dioxide concentration, since the calculation section 2 contains the calculation block 21 using the multivariate analysis method, it can be obtained from the developer measured by the multivariate analysis method. Calculate the alkali component concentration, dissolved photoresist concentration, and carbon dioxide absorption concentration of the developer.

Therefore, the control block 31 is a control block that sends a control signal to the control valve so that the alkali component concentration can become a predetermined management value, and the control block 32 is such that the container photoresist concentration can become a predetermined management value or below the management value. When the control block sends a control signal to the control valve, and the control block 33 is a control block that sends a control signal to the control valve so that the concentration of carbon dioxide absorbed can become a predetermined management value or below, the control unit 3 can The method of receiving the calculated component concentration of the developer is connected to the calculation unit 2. Therefore, the developer management device E according to this embodiment can make the concentration of the alkali component of the developer reach a predetermined management value and dissolve the photoresist The developer is maintained and managed so that the concentration becomes a predetermined management value or less, and the absorbed carbon dioxide concentration becomes a predetermined management value or less.

The other details are the same as the other embodiments, so they are omitted.

As described above, as shown in the tenth to seventeenth embodiments, the developer management device of this embodiment includes: a measuring unit 1 that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer; and a computing unit 2 , Calculate the component concentration of the developer from the plurality of characteristic values measured by the measuring section 1 by the multivariate analysis method; and the control section 3, based on the characteristic value of the developer measured by the measuring section 1 or the calculation section 2 The calculated component concentration of the developer sends control signals to the control valves 41 to 43 provided on the pipeline for conveying the replenishing liquid to be replenished to the developer.

The measurement unit 1 and the calculation unit 2 in the developer management device of the present embodiment can adopt various aspects similarly to the measurement unit 1 and the calculation unit 2 in the developer concentration monitoring device.

The control unit 3 in the developer management device of this embodiment does not need to be a separate device from the computing unit 2, and can also be installed as an integrated device (such as a computer) for the control function and computing function. Moreover, like FIG. 11, the control unit 3 can also be configured separately from the measurement unit 1 and the calculation unit 2. The control unit 3 only needs to communicate with the measurement unit 1 and the calculation unit 2 so as to be able to receive the characteristic value measured by the measurement unit 1 or the component concentration calculated by the calculation unit 2 as the control quantity. In this way, the necessary control signal can be sent out according to the received characteristic value or component concentration.

Regarding the pipeline for conveying the replenisher, it may be connected to the developer management device E of this embodiment or not. The control valve may not be an internal part of the developer management device E. If the control unit 3 is connected to the control unit 3 by the control signal of the control unit 3, it can also be installed outside the developer management device E.

As described above, according to the developer management device of the present invention, the concentration of each component or the characteristic value of the developer can be managed within a predetermined management value or management range. Therefore, with the developer management device of the present invention, the best development performance can be maintained, and the desired line width or residual film thickness can be achieved.

According to the developer management device of the present invention, since the concentration of each component of the developer is accurately controlled to a predetermined state, the development performance of the developer can be made more accurate and fixed for maintenance and management. Therefore, it can be expected that the development speed during photoresist development can be fixed and stabilized, the line width or residual film thickness of the development process can be fixed, and the product quality can be improved. At the same time, it can be expected to help achieve more miniaturization and high Integration.

According to the developer management device of the present invention, since the developer is automatically maintained at the best developing performance at all times, the product yield is improved, and at the same time, the replacement of the developer is unnecessary, which can be expected to help reduce operating costs. Or waste liquid cost.

1: Measurement department

2: Computing Department

11: The first measurement component

12: The second measuring component

14: Sampling pump

15: Sampling piping

16: Return piping

21: Operation block

51, 52: Signal line for measurement data

61: Developer storage tank

62: overflow trough

63: Liquid level gauge

64: developing room cover

65: Roller conveyor

66: substrate

67: Developer spray head

71: Waste Liquid Pump

72: circulation pump

73: filter

80: Developer pipeline

A: Component concentration measuring device

B: Development process equipment

WD: Alarm Department

Claims (12)

A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and an arithmetic unit based on the aforementioned measurement by the measuring unit A plurality of characteristic values are calculated by a multivariate analysis method to calculate the component concentration of the developer; and an alarm unit that issues an alarm when at least one of the component concentrations calculated by the calculation unit deviates from the set management range. For example, the developer concentration monitoring device of claim 1, wherein as the aforementioned alarm unit, at least one of the following is provided: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, and a warning lamp that lights or flashes light , The display device to display the warning, and the relay terminal to switch the opening and closing of the contact. A developer concentration monitoring device, comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of the alkaline developer that is repeatedly used; and an arithmetic unit based on the measurement by the measuring unit The plurality of characteristic values calculate the component concentration of the developer by a multivariate analysis method, and each component concentration is provided with an alarm unit that generates an alarm when the component concentration calculated by the calculation unit deviates from the set management range. For example, the developer concentration monitoring device of claim 3, wherein as the aforementioned alarm unit, at least one of the following is provided: An external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, a display device that displays a warning, and a relay terminal that switches the contacts on and off. A developer management device comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of a developer that is repeatedly used showing alkalinity; and an arithmetic unit based on the plurality of characteristic values measured by the measuring unit The characteristic value is calculated by the multivariate analysis method of the component concentration of the developer; the alarm unit, when at least one of the component concentrations calculated by the calculation unit deviates from the set management range; and the control unit, based on The measured value or calculated value of the management target item selected from the plurality of characteristic values of the developer measured by the measuring unit and the component concentration of the developer calculated by the calculating unit are set for conveying The control valve on the pipeline of the replenishing liquid to be replenished to the aforementioned developer sends a control signal. For example, the developer management device of claim 5, which, as an alarm unit, has at least one of the following: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, and a warning display The display device, and the relay terminal for switching the opening and closing of the contact. According to the developer management device of claim 5 or 6, wherein the component concentration is the concentration of the alkali component of the developer and the concentration of the photoresist, and the measuring unit includes: a first measuring member that measures the components of the developer at least The characteristic value of the developer related to the concentration of the alkali component; and a second measuring means for measuring the characteristic value of the developer related to the concentration of the photoresist at least dissolved in the developer in the component of the developer, and the aforementioned calculation The section is provided with a calculation block for calculating the concentration of the alkali component of the developer and the concentration of the photoresist. According to the developer management device of claim 5 or 6, wherein the component concentration is the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide, and the measurement unit includes: a first measurement means for measuring and developing The characteristic value of the developer related to the concentration of at least the alkali component among the components of the liquid; the second measuring means measures the characteristic of the developer related to the concentration of the photoresist at least dissolved in the developer in the component of the developer Value; and a third measuring means for measuring the characteristic value of the developer related to at least the concentration of carbon dioxide absorbed by the developer among the components of the developer, and the calculation unit is equipped to calculate the concentration of the alkali component of the developer, light The calculation block of the concentration of the resist and the concentration of carbon dioxide. A developer management device comprising: a measuring unit that measures a plurality of characteristic values of the developer related to the component concentration of a developer that is repeatedly used showing alkalinity; and an arithmetic unit based on the plurality of characteristic values measured by the measuring unit The characteristic value is calculated by the multivariate analysis method to calculate the component concentration of the aforementioned developer Degree; and the control unit, based on the measured value or calculated value of the management target item selected from the plurality of characteristic values of the developer measured by the measuring unit and the component concentration of the developer calculated by the calculating unit , To send a control signal to the control valve set on the pipeline for conveying the replenishing liquid to be replenished to the developer, and to control the deviation of the component concentration calculated by the calculation unit according to the concentration of each component The alarm section that issues an alarm when it is in the range. For example, the developer management device of claim 9, which, as an alarm unit, has at least one of the following: an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning lamp that lights or flashes a light, and a warning display The display device, and the relay terminal for switching the opening and closing of the contact. According to the developer management device of claim 9 or 10, wherein the component concentration is the concentration of the alkali component of the developer and the concentration of the photoresist, and the measurement unit includes: a first measuring member that measures the concentration of the component in the developer At least the characteristic value of the developer related to the concentration of the alkali component; and a second measuring means for measuring the characteristic value of the developer related to the concentration of the photoresist at least dissolved in the developer in the component of the developer; The calculation unit includes a calculation block for calculating the concentration of the alkali component of the developer and the concentration of the photoresist. Such as the developer management device of claim 9 or 10, wherein the aforementioned components The concentration is the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide. The measurement unit includes: a first measuring means for measuring the concentration of the developer related to the concentration of at least the alkali component in the component of the developer Characteristic value; a second measuring means for measuring the characteristic value of the developer in relation to the concentration of at least the photoresist dissolved in the developer among the components of the developer; and a third measuring means for measuring the composition of the developer Among them, the characteristic value of the developer is related to at least the concentration of carbon dioxide absorbed by the developer, and the calculation unit includes a calculation block for calculating the concentration of the alkali component of the developer, the concentration of the photoresist, and the concentration of carbon dioxide.

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