TW201704902A - Component concentration measuring method and apparatus for developing solution, and developing solution managing method and apparatus provides a highly precise component concentration estimation method and apparatus - Google Patents

Abstract

The disclosure provides a component concentration estimation method and apparatus capable of precisely calculating the concentration of each component of an alkaline developing solution, such as an alkaline component, dissolved photoresist, absorbed carbon dioxide and the like, according to characteristic values of the developing solution, and a management method and apparatus capable of maintaining and managing the developing performance of the developing solution in the best condition. The present invention uses a measurement unit 1 to measure a plurality of characteristic values of the developing solution related to the component concentration of the developing solution. The plurality of measured characteristic values are sent to a calculation unit 2, which calculates the component concentration of the developing solution with multivariate analysis. The control unit 3 is configured to: set any one of the measured characteristic value and the calculated alkaline component concentration as a predetermined management value, allow any one of the measured characteristic value and the calculated photoresist concentration to be in a predetermined management range, and supply a replenishing solution, such as primary solution, new solution or pure water, to the developing solution in such a manner that the measured characteristic value and the calculated photoresist concentration are in a predetermined management range.

Description

Method and device for measuring component concentration of developing solution, and developing solution management method and device

The present invention relates to a component concentration measuring method, a component concentration measuring device, and a developer management system for developing an alkaline developing solution for developing a photoresist film in a developing process of a circuit board of a semiconductor or a liquid crystal panel. Method and developer management device.

In the development process of photolithography for performing fine wiring processing such as semiconductors and liquid crystal panels, an alkaline developing solution is used for dissolving a chemical solution for forming a photoresist on a substrate (hereinafter referred to as " Alkaline developer").

In recent years, in the process of semiconductors and liquid crystal panel substrates, there has been a great progress in increasing the size of wafers and glass substrates, miniaturization of wiring processes, and high-density integration. In such a situation, in order to achieve the miniaturization and high-density integration of the wiring processing of the large substrate, it is necessary to measure the concentration of the main component of the alkaline developing solution with higher precision to maintain the management developer.

The measurement of the component concentration of the conventional alkaline developer is as described in Patent Document 1 below, and the concentration of the alkaline component (hereinafter referred to as "alkaline component concentration") and the conductivity of the alkaline developer are used. A good linear relationship can be obtained between the point of obtaining a good linear relationship and the concentration of the photoresist dissolved in the alkaline developing solution (hereinafter referred to as "dissolved photoresist concentration") and the absorbance.

However, the alkaline developing solution is easily deteriorated by absorbing carbon dioxide in the air to form carbonate. Further, the alkaline developing solution generates a photoresist salt due to dissolution of the photoresist, and consumes an alkaline component which is effective in development processing. Therefore, the reusable alkaline developing solution is not only an alkaline component but a multi-component system which also contains a photoresist and carbon dioxide. In addition, the components affect the developing performance at different contribution rates. Therefore, in order to maintain the development performance of the developing developer with high precision, it is necessary to carry out developer management in consideration of the influence of the components on the developing performance.

In order to solve the above problem, Patent Document 2 listed below discloses a developer liquid preparation device and the like, which measures the ultrasonic wave propagation speed, conductivity, and absorbance of the developer, and is based on the previously established ultrasonic wave propagation speed, conductivity, and absorbance. The relationship between the alkaline concentration, the carbonate concentration, and the dissolved resin concentration (matrix) to detect the alkaline concentration, the carbonate concentration, and the dissolved resin concentration of the developer, and then based on the measured alkaline concentration of the developer The relationship between the carbonate concentration and the dissolved resin concentration, and the alkali concentration, the carbonate concentration, and the dissolved resin concentration which are previously established so that the CD value (CD: Critical Dimension) (line width) becomes a certain value. The supply of the developer solution is controlled to adjust the alkali concentration.

In addition, the following Patent Document 3 discloses an alkaline developer management system and the like, and includes a carbonic acid salt concentration measuring device that measures a refractive index, a conductivity, and an absorbance of a developer, and obtains a developer from the measured values. The carbonic acid salt concentration in the medium; and the control unit controls the carbonic acid salt concentration in the carbonic acid salt concentration measuring device and the developing solution.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent No. 2561778

Patent Document 2 Japanese Patent Laid-Open Publication No. 2008-283162

Patent Document 3 Japanese Patent Laid-Open No. 2011-128455

However, the ultrasonic propagation velocity value and the refractive index value of the alkaline developing solution are characteristic values indicating the overall properties of the chemical liquid of the alkaline developing solution belonging to the multi-component system. In general, this characteristic value indicating the overall properties of the liquid is not necessarily related to the concentration of a specific component in the liquid. This means that the characteristic value of the overall properties of the liquid is usually related to each concentration of the various components in the liquid. Therefore, in the case where the component concentration of the developer is calculated from the measured value of the characteristic value of the overall property of the chemical solution, it is assumed that a certain characteristic value is only related to a specific component concentration (for example, there is a linear relationship) and other components are ignored. The influence of the characteristic value may cause a problem that the concentration of the specific component cannot be calculated with sufficient accuracy.

On the other hand, in the case where the concentration of each component is calculated from the measured value of the characteristic value of the developer as a function of the concentration of the developer in the characteristic value of the developer, it is necessary to measure a plurality of characteristic values. An appropriate calculation method for calculating the concentration of each component from the measured values of the characteristic values. However, it is extremely difficult to appropriately select the characteristic value to be measured and to find an appropriate calculation method capable of accurately calculating the concentration of each component from the measured value of the characteristic value. Therefore, if the measured characteristic value and the calculation method are not appropriate, the problem of the concentration of each component cannot be calculated with sufficient accuracy.

Further, in a liquid of a multi-component system, generally, the concentration of a certain component is not independent of the concentration of other components. In the liquid of the multi-component system, there is a correlation in which the concentration of one component changes and the concentration of other components also changes. This makes it more difficult to calculate the component concentration with high precision and to manage the developer with high precision.

In addition, regarding the concentration of carbon dioxide absorbed by the developer (hereinafter referred to as "absorbed carbon dioxide concentration"), it has not been known in the past which appropriate characteristic value of the developer exhibits a good relationship with the concentration of absorbed carbon dioxide, and is difficult to be high. Accurately measure the concentration of absorbed carbon dioxide.

Further, in Patent Document 2, in order to detect the component concentration of the developer, it is necessary to obtain a correlation (matrix table) of characteristic values such as the component concentration of the developer and the ultrasonic wave propagation velocity in advance. However, at this time, when the correlation (matrix table) is rough, the component concentration cannot be accurately calculated. In order to accurately calculate the component concentration, the correlation between the characteristic value of the developer for calculation and the component concentration (matrix table) must be sufficiently dense. Therefore, the more you want to improve the accuracy of the calculation of the component concentration, you must More samples were prepared to determine the correlation between the concentration of the components and the characteristic values of the developer. The amount of work required to prepare the dense correlation (matrix table) as described above is extremely large, which is a problem in achieving high-precision measurement of the concentration of the developer solution.

The present invention has been made in order to solve the above problems. An object of the present invention is to provide a developer capable of accurately measuring a component concentration of a developer from a characteristic value of a developer belonging to a multi-component system, and capable of analyzing a component concentration of a developer without preparation and preliminary measurement of a large number of samples. The method and apparatus for measuring the component concentration, and the developer management method and apparatus capable of more precisely managing the concentration of the component of the developer.

In order to achieve the above object, the present invention includes a step of calculating a component concentration of a developer by a multivariate analysis method (for example, a complex regression analysis method) and a calculation unit. That is, the present invention provides the following component concentration measuring method, component concentration measuring device, developing solution management method, and developing solution management device.

(1) A method for measuring a component concentration of a developer, comprising the steps of: measuring a plurality of characteristic values of a developer associated with a component concentration of a repeatedly used developer; and determining The plurality of characteristic values are a step of calculating the component concentration of the developer by multivariate analysis.

(2) A component concentration measuring device for a developing solution, comprising: a measuring unit that measures a plurality of characteristic values of a developing solution relating to a component concentration of a re-used alkaline developing solution; and an arithmetic unit according to the calculation unit The component concentration of the developer is calculated by a multivariate analysis method by a plurality of characteristic values measured by the measuring unit.

(3) A developer management method comprising the steps of: measuring a plurality of characteristic values of a developer associated with a component concentration of a repetitive alkaline developer; and measuring a plurality of characteristics a value obtained by calculating a component concentration of the developer by a multivariate analysis method; and selecting a plurality of characteristic values of the developer measured by the step of performing the measurement and a component concentration of the developer calculated by the step of calculating The measurement value or the calculated value of the management target item, and the step of replenishing the replenishing liquid to the developer.

(4) A developer management apparatus comprising: a measurement unit that measures a plurality of characteristic values of a developer associated with a component concentration of an alkaline developer that is repeatedly used; and an operation unit that is based on a measurement unit The plurality of characteristic values are measured, and the component concentration of the developer is calculated by the multivariate analysis method; and the control unit is based on a plurality of characteristic values of the developer measured by the measuring unit and the composition of the developer calculated by the calculation unit. The measured value or the calculated value of the management target item selected among the concentrations gives a control signal to the control valve provided in the flow path for supplying the replenishing liquid supplied to the developing solution.

(5) The developing solution management device according to the above (4), wherein the measuring unit includes: a first measuring means for measuring a characteristic value of the developing solution relating to a concentration of at least an alkaline component in a component of the developing solution; The second measuring means measures the characteristic value of the developing solution relating to the concentration of at least the photoresist dissolved in the developing solution among the components of the developing solution.

(6) The developer management device according to the above (5), wherein the calculation unit includes a calculation block for calculating the concentration of the alkaline component of the developer and the concentration of the photoresist; and the control unit includes: calculating by the calculation block a control block for issuing a control signal to the control valve in such a manner that the concentration of the alkaline component becomes a predetermined management value; and a control signal is issued to the control valve such that the concentration of the photoresist calculated by the calculation block becomes a predetermined management value or less Control block.

(7) The developer management device according to (5), wherein the measuring unit further includes a third measuring means for measuring a concentration of carbon dioxide absorbed by at least the developing solution among the components of the developing solution. The characteristic value of the developer.

(8) The developer management device according to (7), wherein the calculation unit includes a calculation block for calculating a concentration of carbon dioxide in the developer; and the control unit includes: the characteristic value of the developer measured by the first measurement means is predetermined a control block for issuing a control signal to the control valve in a manner of managing values; a control block for issuing a control signal to the control valve in such a manner that the characteristic value of the developer measured by the second measuring means falls within a predetermined management area; A control block for issuing a control signal to the control valve in such a manner that the concentration of carbon dioxide calculated by the calculation block becomes equal to or less than a predetermined management value.

(9) The developer management device according to the above (7), wherein the calculation unit includes a calculation block for calculating the concentration of the alkaline component of the developer and the concentration of carbon dioxide; and the control unit includes the alkaline component calculated by the calculation block. The control block sends a control signal to the control valve in such a manner that the concentration becomes a predetermined management value; the control signal is sent to the control valve in such a manner that the characteristic value of the developer measured by the second measuring means falls within a predetermined management area And a control block for issuing a control signal to the control valve such that the concentration of carbon dioxide calculated by the calculation block becomes equal to or less than a predetermined management value.

(10) The developer management device according to (7) above, wherein the calculation unit includes a calculation block for calculating a concentration of an alkaline component of the developer, a concentration of the photoresist, and a concentration of carbon dioxide; and the control unit includes: a control block for issuing a control signal to the control valve in such a manner that the calculated concentration of the alkaline component becomes a predetermined management value; and a control signal is issued to the control valve such that the concentration of the photoresist calculated by the calculation block becomes equal to or less than a predetermined management value a control block; and a control block for issuing a control signal to the control valve in such a manner that the concentration of carbon dioxide calculated by the calculation block becomes equal to or less than a predetermined management value.

According to the present invention, a multi-component system is calculated by using a multivariate analysis method (for example, complex regression analysis) The concentration of the component of the alkaline developing solution is therefore a conventional method of calculating the component concentration as compared with a predetermined correlation (for example, a linear relationship) between the measured characteristic value and the specific component concentration, even if it is subjected to plural The characteristic value affected by the developer component can still accurately calculate the component concentration of the developer. Specifically, according to the present invention, it is possible to measure the concentration of absorbed carbon dioxide of a developer which is conventionally difficult to measure. Further, the present invention does not require preparation of a large number of samples for performing preliminary measurement, as compared with a method for preparing a correlation between a plurality of measured characteristic values and a plurality of component concentrations (matrix table) for calculating the component concentration. .

According to the present invention, since the concentration of each component of the alkaline developing solution belonging to the multi-component system can be measured with higher precision than the prior art, the alkaline component concentration, the dissolved photoresist concentration, and the absorption can be controlled more accurately than the prior art. Carbon dioxide concentration. Further, according to the present invention, it is also possible to select a management in which the conductivity value of the developer is controlled to a certain level, and the absorbance value of the developer is controlled to be equal to or lower than a certain absorbance value.

1‧‧‧Determination Department

2‧‧‧ Calculation Department

3‧‧‧Control Department

4‧‧‧ valve

5‧‧‧ signal line

6‧‧‧Developing equipment

7‧‧‧Developing equipment

8‧‧‧ fluid lines

9‧‧‧Replenishment tank

11‧‧‧First measure

12‧‧‧Second measure

13‧‧‧ Third measure

11a, 12a, 13a‧‧‧measurement device body

11b, 12b, 13b‧‧‧ assay probe

14, 14a, 14b, 14c‧‧ ‧ sampling pump

15, 15a, 15b, 15c‧‧‧ sampling piping

16, 16a, 16b, 16c‧‧‧ reflow piping

17‧‧‧ Liquid pump

18‧‧‧ Liquid supply piping

19‧‧‧Waste piping

21‧‧‧ calculus with multivariate analysis

22‧‧‧Study block using the calibration curve method

31, 32, 33‧‧‧ control blocks

23‧‧‧ Calculation Control Department (eg computer)

41 to 43‧‧‧ control valve

44, 45‧‧‧ valve

46, 47‧‧‧ Valves for pressurized gas

51 to 53‧‧‧ Signal line for measurement data

54‧‧‧Signal lines for calculation data

55 to 57‧‧‧ Signal lines for control signals

61‧‧‧ developer storage tank

62‧‧‧Overflow trough

63‧‧‧liquid level meter

64‧‧‧Development room shield

65‧‧‧Roller conveyor

66‧‧‧Substrate

67‧‧‧Developing sprinkler

71‧‧‧Waste pump

72, 74‧‧‧ Circulating pump

73, 75‧‧‧ filter

80‧‧‧developer line

81, 82‧‧ ‧ replenishing solution (developer stock solution and / or new Liquid)

83‧‧‧Pure water pipeline

84‧‧‧Confluence pipeline

85‧‧‧Circulation line

86‧‧‧Nitrogen pipeline

91, 92‧‧‧ replenishing liquid (developer stock solution and / or new liquid) storage tank

93‧‧‧Adding reagents

A‧‧‧ component concentration measuring device

B‧‧‧Developing process equipment

C‧‧‧Replenishment Storage Department

D‧‧‧Circulating mixing mechanism

E‧‧‧ developer management device

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

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

Fig. 3 is a flow chart showing a method of measuring a component concentration of a flow containing a signal different from the calculation method of the multivariate analysis method.

Fig. 4 is a schematic view showing a device for measuring a component concentration of two components of a developer.

Fig. 5 is a schematic view showing a device for measuring a component concentration of three components of a developer.

Fig. 6 is a schematic diagram of a component concentration measuring device having a calculation block performed by an arithmetic method different from the multivariate analysis method in the calculation unit.

Fig. 7 is a schematic diagram of a component concentration measuring device when the measurement unit and the calculation unit are individually independent and measured in an inline manner.

Fig. 8 is a schematic view showing a component concentration measuring device when the measuring means is constituted by a main body and a probe portion.

Fig. 9 is a schematic view showing a component concentration measuring device in which measurement means are arranged in parallel.

Fig. 10 is a schematic view showing a component concentration measuring device in a case where a measuring device to which a drug is to be added is disposed.

Fig. 11 is a schematic view showing the application of the component concentration measuring device to the developer management device.

Fig. 12 is a schematic view showing an application example of the component concentration measuring device.

Figure 13 is a flow chart showing a developer management method for managing two components of a developer by a component concentration.

Fig. 14 is a flow chart showing a method of managing a developer which manages one of the two components of the developer by the component concentration and manages the other component by the property value.

Fig. 15 is a flow chart showing a developer management method for managing three components of a developer by a component concentration.

Fig. 16 is a flow chart showing a method of managing a developer for managing the remaining two components by one of the three components of the developer by the characteristic value.

Fig. 17 is a flow chart showing a method of managing a developer for managing the remaining components by three components of the three components of the developer by characteristic values.

Fig. 18 is a schematic view for explaining the developing process of the developer management device of the present invention.

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

Fig. 20 is a schematic diagram of a developer management device having an arithmetic control unit having both an arithmetic function and a control function.

Fig. 21 is a schematic view showing a developer management device for managing two components of the developer.

Fig. 22 is a schematic view showing a developer management device for managing two components of a developer by a component concentration.

Fig. 23 is a schematic diagram of a developer management apparatus which manages the remaining components by the three components of the developer by the characteristic values.

Fig. 24 is a schematic view showing a developer management device for managing one of the three components of the developer by the characteristic value and managing the remaining two components by the component concentration.

Fig. 25 is a schematic view showing a developer management apparatus for managing three components of a developer by a component concentration.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, the shape, the size, the size ratio, the relative arrangement, and the like of the apparatus and the like described in the following embodiments are not limited to the scope of the invention unless otherwise specified. It is merely schematically illustrated as an illustrative example.

Further, in the following description, in the specific example of the developer, an aqueous solution of 2.38% tetramethylammonium hydroxide mainly used in the process of the semiconductor and liquid crystal panel substrate (hereinafter, tetramethyl group) is selected. Description of ammonium hydroxide is called TMAH). However, the developer to which the present invention is applied is not limited thereto. Examples of other developing solutions that can be applied to the component concentration measuring device and the developer managing device of the developing solution of the present invention include inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, and sodium citrate. An aqueous solution of an aqueous solution and an organic compound such as trimethyl monoethanol ammonium hydroxide (choline).

Further, in the multivariate analysis method (for example, the complex regression analysis method), when the concentration of the component is calculated, the concentration of the component concentration is not determined, but in the following description, the alkaline component concentration and the dissolved photoresist concentration are determined. The concentration of the component such as the concentration of absorbed carbon dioxide is the concentration calculated by the concentration by weight percentage (wt%). The "dissolved photoresist concentration" refers to a concentration at which the dissolved photoresist is converted into a resist amount; the "absorbed carbon dioxide concentration" refers to a concentration at which the absorbed carbon dioxide is converted into carbon dioxide.

In the development processing, development is performed by dissolving the photoresist film in the developing solution with an unnecessary portion after the exposure process. The photoresist dissolved in the developer forms a photoresist salt between the alkaline component of the developer. Therefore, if the developer management is not properly managed, as the development process proceeds, the developer is degraded by the consumption of the alkaline component having the development activity, and the development performance is deteriorated. At the same time, in the developing solution, the dissolved photoresist is continuously accumulated in the form of a photoresist salt formed with an alkaline component.

The photoresist dissolved in the developer exhibits an interfacial activity in the developer. Therefore, the photoresist dissolved in the developing solution enhances the wettability of the developing solution to the photoresist film for development processing, and improves the affinity between the developing solution and the resist film. Therefore, the developing solution containing the photoresist is appropriately inserted into the fine concave portion of the photoresist film, and the development process can be favorably performed on the photoresist film having the fine unevenness.

Further, in the development processing in recent years, with the enlargement of the substrate, a large amount of the developer is repeatedly used, and the chance of the developer being exposed to the air is increased. However, the alkaline developer absorbs carbon dioxide in the air once exposed to the air. The absorbed carbon dioxide forms a carbonate with the alkaline component of the developer. Therefore, if the developer management is not properly managed, the developing alkaline component in the developer is reduced by the absorbed carbon dioxide. At the same time, in the developer, the absorbed carbon dioxide is continuously accumulated in the form of a carbonate formed with an alkaline component.

The carbonate in the developer is alkaline in the developer, so it has a developing effect. For example, in the case of a 2.38% aqueous solution of TMAH, Development can be carried out as long as the carbon dioxide in the developer is about 0.4% by weight or less.

As described above, unlike the conventional one, it is considered that the photoresist dissolved in the developer and the absorbed carbon dioxide are useless substances in the development treatment, and actually contribute to the developing performance of the developer. Therefore, what is necessary is to allow the solution of the dissolved photoresist and the absorbed carbon dioxide to be maintained at the optimum concentration of the developer under the slight solubility of the solution in the developing solution, and to dissolve the photoresist and absorb it. Developer management for complete removal of carbon dioxide.

Further, regarding the photoresist salt and the carbonate formed in the developer, a part of the free ions such as photoresist ions, carbonate ions, and hydrogen carbonate ions are generated by dissociation. In addition, the free ions affect the conductivity of the developer at various contributions.

The component concentration analysis of the conventional alkaline developing solution has a good linear relationship between the alkaline component concentration of the developer and the conductivity value of the developer, and the dissolved photoresist concentration of the developer and the absorbance value of the developer. This is a good linear relationship (hereinafter referred to as the "known method"). Moreover, since the amount of carbon dioxide absorbed is not so large, the developer management precision required in the conventional development process has been sufficiently achieved by the above analysis method.

The conductivity value of the developer is a physical property value depending on the number of charged particles such as ions contained in the developer and the amount of charge thereof. In the developing solution, as described above, not only an alkaline component but also various kinds of free ions derived from the photoresist dissolved in the developing solution and the carbon dioxide absorbed by the developing solution are present. Therefore, in order to improve the analysis accuracy of the component concentration, it is necessary to make The calculation method of the influence of the free ions on the conductivity value of the developer is also included.

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

The inventors of the present invention have continued to study the above-mentioned various points and found that as long as the calculation method uses a multivariate analysis method (for example, a complex regression analysis method), it is possible to calculate the components of the developer more accurately than using conventional techniques. Concentration and ability to measure the concentration of absorbed carbon dioxide that was difficult to measure in the past. Further, the inventors have found that by using the component concentration of the developer calculated by the multivariate analysis method (for example, complex regression analysis), the dissolved photoresist concentration and the absorbed carbon dioxide concentration of the developer can be maintained in a good state. .

The inventors of the present invention envisaged a management situation in which a 2.38% TMAH aqueous solution was carried out, and a TMAH aqueous solution having various changes in the concentration of the basic component, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration was prepared as a simulated developer sample. The inventors of the present invention conducted experiments in which the component concentrations were determined by complex regression analysis from various characteristic values measured for the simulated developer samples. In the following, the general calculation method by complex regression analysis will be described first, and then according to the case. The experiment conducted by the inventor used the calculation method of the component concentration of the developer using the complex regression analysis method.

Complex regression analysis consists of two phases: the correction phase and the prediction phase. In the complex regression analysis of the n-component system, m calibration standard solutions were prepared. The concentration of the jth component present in the i-th solution is expressed as C _ij . Here, i=1 to m, j=1 to n. For each of the m standard solutions, p characteristic values (for example, physical properties such as absorbance and conductivity at a certain wavelength) A _ik (k=1 to p) were measured. The concentration data and the characteristic data can be aggregated into a matrix form (C, A).

The matrix to which the two matrices are associated is referred to as a correction matrix, here represented by the code S (S _kj ; k = 1 to p, j = 1 to n).

C=A. S

It is possible to calculate S from the known C and A (the content of A is a heterogeneous measurement value even if it is not purely homogeneous. For example, conductivity and absorbance and density), S is calculated, which is a correction phase. At this time, it must be p>=n and m>=np. Since each element of S is an unknown number, it is preferably m>np, and the least squares calculation is performed as follows.

Wherein, the T of the upper mark represents the transposed matrix, and the upper mark of -1 represents the inverse matrix.

As long as the p characteristic values are determined for the sample liquid of unknown concentration, the specific values are Au (Au _k ; k = 1 to p), and by multiplying S, the desired concentration Cu (Cu _j ; j can be obtained. =1 to n).

Cu=Au. S

The above is the forecasting stage.

The inventors of the present invention conducted the following experiment: a used alkaline developer (2.38% TMAH aqueous solution) was regarded as a multi-component system composed of three components of an alkaline component, a dissolved photoresist, and a carbon dioxide absorption (n=3). Taking three physical property values (p=3), that is, the conductivity value of the developer, the absorbance value of the specific wavelength, and the density value as the characteristic values of the developer, from the characteristic values, by the above complex regression analysis The concentration of each component was calculated by the method. The inventor of the present invention prepared a standard calibration solution of 2.38% TMAH aqueous solution as a developing solution, and prepared 11 calibration standard solutions (m=11, which have various changes in alkaline component concentration (TMAH concentration), dissolved photoresist concentration, and absorbed carbon dioxide concentration. Satisfy p>=n and m>np).

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

Regarding the manner in which the measurement was carried out, the temperature of the calibration standard solution was adjusted to 25.0 ° C. The temperature adjustment method is as follows: the bottle with the calibration standard solution is immersed in a constant temperature water bath with a temperature management at 25 ° C for a long time, and sampling is performed in this state, and the temperature controller is adjusted again to 25.0 ° C immediately before the measurement is performed. . The conductivity meter is a conductivity meter manufactured by our company. The measurement was carried out using a conductivity flow cell manufactured by our company which was subjected to platinum black treatment. A conductivity constant of the conductivity flow path confirmed by the calibration operation is input to the conductivity meter. The spectrophotometer is also used in the spectrophotometer. It is an absorption photometer which has a light source part of a wavelength λ=560 nm, a photometry part, and a glass flow-through groove. In the density measurement, a density meter using a natural vibration method, that is, a natural vibration frequency measured by applying vibration to a U-shaped tube flow groove, is used to determine the density. The units of the measured conductivity value, absorbance value, and density value were mS/cm, Abs. (Absorbance), and g/cm ^{3 , respectively} .

Regarding the tactics used in the calculation (leave-cross-validation method; Leave-One-Out method), one of the 11 calibration standard solutions is selected as the unknown sample, and the correction matrix is obtained by the remaining 10 criteria to calculate the assumed The concentration of the unknown sample is then compared to known values (concentration values and weight modulation values determined by other correct analytical methods).

Table 1 below shows the results of the MLR-ILS calculation.

In view of the fact that the TMAH aqueous solution is strongly alkaline and easily absorbs carbon dioxide and deteriorates, in the calculation of MLR-ILS, the value of the concentration matrix used in the calculation is based on a titration analysis capable of correctly analyzing the concentration of the alkaline component and the concentration of the absorbed carbon dioxide. Determine the calibration standard solution. Among them, the weight modulation value is used for the dissolved photoresist concentration.

The titration method is based on hydrochloric acid as a titration reagent and titration. As the titration device, an automatic titrator GT-200 manufactured by Mitsubishi Chemical Analytech Co., Ltd. was used.

Table 2 below shows the concentration matrix table.

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

Table 4 below shows the correction matrix.

Table 5 below shows the comparison of the concentration measurement values of Table 2 above with the MLR-ILS calculation values of Table 1 above.

As shown in Table 5 above, the TMAH concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration obtained by the complex regression analysis are both obtained from the TMAH concentration and the absorbed carbon dioxide concentration measured by the titration and from the adjusted weight. The dissolved photoresist concentrations are very similar.

As described above, it is understood that by measuring the conductivity of the alkaline developing solution, the absorbance at a specific wavelength, and the density, by using a multivariate analysis method (for example, complex regression analysis), it is possible to measure the alkaline component concentration of the developer and dissolve it. Photoresist concentration, and absorption of carbon dioxide concentration.

Multivariate analysis (for example, complex regression analysis) has a good effect in calculating the concentration of a plurality of components. By measuring a plurality of characteristic values a, b, c, ... of the developer, the component concentrations A, B, C, can be obtained from the measured values by multivariate analysis (for example, complex regression analysis). .. At this time, at least one of the characteristic values associated with the concentration of the component to be taken must be at least one measured and used in the calculation.

Here, the characteristic value of the developer which is "related to the component concentration" means that the characteristic value is related to the concentration of the component, and there is a relationship that the characteristic value changes in accordance with the change in the concentration of the component. For example, a certain characteristic value a of the developer associated with at least the component concentration A of the component concentration of the developer means that when the characteristic value a is obtained by a function of the component concentration as a variable, at least one of the variables is at least Contains component concentration A. Although the characteristic value a may be a function of only the component concentration A, a multivariate analysis method (for example, complex regression analysis) is generally used in addition to the component concentration A to form a multivariate function having the component concentrations B and C as variables. ) is of great significance.

Further, the component concentration is a measure indicating the relative amount of the component with respect to the whole. The concentration of the component of the mixed solution in which the developer is reused over time is usually a function of the concentration of other components, and cannot be determined solely by the components thereof. Therefore, the relationship between the characteristic value of the developer and the component concentration is often difficult to express as a flat graph. At this time, the component concentration cannot be calculated from the characteristic value of the developer by an algorithm using a calibration curve or the like.

On the other hand, if a multivariate analysis method (for example, a complex regression analysis method) is used, a set of measured values of a plurality of characteristic values related to the concentration of the component to be calculated is collected, and the measured values are used for calculation, and then calculated. A concentration of a component. The component concentration measurement by the multivariate analysis method (for example, the complex regression analysis method) can obtain a remarkable effect of measuring the component concentration by measuring the characteristic value even in a conventionally known concentration of a component which is difficult to measure.

As described above, according to the calculation method of the present invention, the alkaline component concentration, the dissolved photoresist concentration, and the developer concentration of the developer can be calculated from the measured values of the characteristic values (for example, conductivity, specific wavelength absorbance, and density) of the developer. Absorb carbon dioxide concentration. According to the calculation method of the present invention, the concentration of each component can be calculated with higher precision than the conventional technique.

Further, in the present invention, since the multivariate analysis method (for example, the complex regression analysis method) is used, it is also possible to use a developer having a wireless relationship with a specific component concentration of the developer in the calculation of the component concentration of the developer. Characteristic value.

Further, according to the present invention, preparation and preliminary measurement of an extremely large number of samples necessary for realizing high-precision measurement are not required in the invention of the aforementioned Patent Document 2. (In the case of the above-mentioned experimental example, if the developer has the number of components n=3, the number of characteristic values to be measured is p=3, and the number of samples satisfying m>=np is prepared (for example, p=11 samples). It is sufficient to carry out the measurement. If the number of components is n=2, the number of samples can be less.)

Further, in the present invention, since the multivariate analysis method (for example, the complex regression analysis method) is used, the concentration of the absorbed carbon dioxide of the developer which is difficult to measure can be accurately calculated.

Next, a specific embodiment will be described with reference to the drawings. In the following examples, the letter characteristic values a, b, c, ... and the component concentrations A, B, C, ..., etc. are appropriately used for explanation. To further understand the specifics, the characteristic values a, b, c, ... can be interpreted as conductivity, absorbance, density, etc. of a specific wavelength (for example, λ = 560 nm); B, C, ... can be interpreted as alkaline component concentration, dissolved photoresist concentration, absorbed carbon dioxide concentration, etc., respectively.

However, it is assumed that the characteristic values a, b, and c are conductivity, absorbance at a specific wavelength (for example, λ = 560 nm), density, and the like, and the basic component concentration, the dissolved photoresist concentration, the absorbed carbon dioxide concentration, and the like of the developer are simply calculated by the present invention. The instant combination of the best characteristic values is not limited thereto. The characteristic values a, b, c, ... are capable of selecting various combinations corresponding to the component concentrations A, B, C, . Examples of the characteristic values that can be used include conductivity of the developer, absorbance, ultrasonic propagation speed, refractive index, density, titration end point, pH, and the like. In some cases, the developer may contain various additives, and thus the component concentration may include the additive concentration or the like in addition to the above three components.

In the case where the developer concentration is measured, the dissolved photoresist concentration, and the carbon dioxide concentration are measured to manage the developer, the characteristic value is preferably a combination of conductivity, absorbance at a specific wavelength, and density. The specific wavelength at which the absorbance is measured is preferably an absorbance at a specific wavelength in the visible light wavelength range, more preferably an absorbance at a specific wavelength in the wavelength range of 360 nm to 600 nm, and preferably an absorbance at a wavelength λ = 480 nm or 560 nm. This is because the conductivity of the developer is small when the concentration of carbon dioxide absorbed by the developer is small, and it changes with time and time. It has a good linear relationship with the concentration of the alkaline component, and the absorbance of the specific wavelength of the developer (for example, λ = 560 nm) has a good linear relationship with the concentration of the dissolved photoresist. Further, it is preferable to use a combination of conductivity, specific wavelength absorbance, ultrasonic propagation speed, conductivity, specific wavelength absorbance, refractive index, and the like.

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

[First Embodiment]

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

In the component concentration calculation method of the present embodiment, first, in the step of measuring the characteristic values a and b of the developer, the measured values a _m and b _{m of the} respective characteristic values are obtained. The obtained measured values a _m and b _m are transmitted to the calculation step. Next, the calculation step receives the measured values a _m and b _m , and uses the measured values to calculate the component concentrations A and B by multivariate analysis (for example, complex regression analysis). Thus, the component concentrations A and B were measured. Further, by repeating this flow, the component concentrations A and B of the developer can be continuously measured.

[Second embodiment]

FIG. 2 is a flow chart showing a method of measuring a component concentration in the embodiment of the flow rate when the component concentration of three or more components of the developer is measured from three or more characteristic values of the developer. .

In the component concentration calculation method of the present embodiment, first, in the step of measuring the characteristic values a, b, c, ... of the developer, the measured values a _m , b _m , and c _{m of the} respective characteristic values are obtained. The obtained measured values a _m , b _m , c _m , ... are transmitted to the calculation step. Next, the calculation step receives the measured values a _m , b _m , and c _m , and the component concentrations A, B, C, . . . are calculated by multivariate analysis (for example, complex regression analysis) using the measured values. Thus, the component concentrations A, B, C, ... were measured. Further, by repeating this flow, the component concentrations A, B, C, ... of the developer can be continuously measured.

[Third embodiment]

Fig. 3 is a view showing the composition of the embodiment in the flow of a signal when a step of measuring a plurality of component concentrations from a characteristic value of a plurality of developing solutions further includes a step different from the multivariate analysis method. Flow chart of the concentration determination method.

This embodiment is suitable for use in the measurement object using the characteristic value p of the developer which is only related to the concentration P of a certain component of the developer. More specifically, for example, measurement may be carried out as follows: from the conductivity value and the density value of the developer, the alkaline component concentration and the absorbed carbon dioxide concentration of the developer are calculated by a multivariate analysis method; The linear relationship between the dissolved photoresist concentration and the absorbance at a specific wavelength (for example, λ = 560 nm) is used in the form of a calibration curve to calculate the dissolved photoresist concentration of the developer.

In the method for measuring the component concentration of the developer according to the embodiment, in the measurement step, the characteristic values a, b, ... of the developer having a plurality of component concentrations as variables are measured, and only the component concentration P is used as a variable. The characteristic values p, ... of the developing solution are transmitted to the calculation steps by the measured values a _m , b _m , ..., and p _m , .

The calculation step includes a step of calculating a component concentration by a multivariate analysis method (for example, a complex regression analysis method), and a step of calculating a component concentration by a calculation method different from the multivariate analysis method (for example, a calibration curve method). . The calculations performed in these steps are not limited. It can also be done at the same time.

The step of calculating the component concentration by the multivariate analysis method (for example, complex regression analysis) is performed by multivariate analysis from the measured values of the characteristic values a, b, ... of the developer measured in the measurement step. The method (for example, complex regression analysis) calculates the component concentrations A, B, ....

The step of calculating the component concentration by an arithmetic method different from the multivariate analysis method (for example, the calibration curve method) is to use a linear relationship between the characteristic value p obtained in advance and the component concentration P, for example, in the form of a calibration curve. On the other hand, the component concentrations P, ... are calculated from the measured values of the characteristic values p, ... of the developer measured in the measurement step.

As described above, in the first embodiment to the third embodiment, the method for measuring the component concentration of the developer according to the present invention includes a measurement step of measuring a plurality of characteristic values of the developer associated with the component concentration of the developer; And the calculation step is to calculate the component concentration of the developer by a multivariate analysis method based on the measured plurality of characteristic values.

The measurement step includes a measurement step of measuring the characteristic value a, a measurement step of measuring the characteristic value b, a measurement step of measuring the characteristic value c, and the like. But the order of these steps is not limited. It can also be measured at the same time. Further, a necessary step such as a temperature adjustment step, a reagent addition step, and a waste liquid step may be appropriately included in accordance with the measurement method.

The calculation step may also include a calculation step of calculating the concentration of the component by multivariate analysis. The step of calculating the component concentration by an arithmetic method different from the multivariate analysis method (for example, the calibration curve method) may be included.

Hereinafter, the fourth to twelfth embodiments are the component concentration measuring devices of the developing solution according to the present invention.

[Fourth embodiment]

Fig. 4 is a schematic view showing a device for measuring a component concentration of two components of a developer. For convenience of explanation, the component concentration measuring device A of the developing solution is connected to the developing process device B, and is illustrated together with the developing process device B.

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

The developing process apparatus B is mainly composed of a developer storage tank 61, an overflow flow tank 62, a development chamber hood 64, a roller conveyor 65, a developer shower head 67 And so on. The developer storage tank 61 is stored with a developer. The developer is supplemented with a replenishing solution to manage the components, but is omitted in Fig. 4. The developer storage tank 61 is provided with a liquid level gauge 63 and an overflow tank 62, and manages an increase in the amount of liquid caused by the supply of the replenishing liquid. The developer storage tank 61 and the developer shower head 67 are connected to each other through the developer line 80. The developer stored in the developer storage tank 61 is sent to the developer shower head 67 through a filter 73 through a circulation pump 72 provided in the developer line 80. Roller conveyor 65 is arranged in the developer Above the storage tank 61, a substrate 66 on which a photoresist film is formed is conveyed. The developer is dropped from the developer shower head 67. The substrate 66 conveyed by the roller conveyor 65 is immersed in the developer by passing through the dripped developer. Then, the developer is recovered and returned to the developer storage tank 61 to be stored again. As described above, the developer is recycled and reused in the developing process. Further, in the developing chamber of a small-sized glass substrate, treatment such as avoiding absorption of carbon dioxide in the air by filling with nitrogen or the like is also performed. Further, the deteriorated developing solution is treated with waste liquid (drain) by causing the waste liquid pump 71 to operate.

Next, the component concentration measuring device A of the developing solution of the present embodiment will be described. The component concentration measuring device according to the present embodiment is a component concentration measuring device that samples a developer to measure a characteristic value.

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

The measurement unit 1 includes a sampling pump 14, a first measurement means 11, and a second measurement means 12 (the first measurement means 11 and the second measurement means 12 are sometimes referred to as measurement means). The measuring means 11, 12 are connected in series to the rear stage of the sampling pump 14. The measuring unit 1 preferably includes a temperature adjusting means (not shown) for stabilizing the sampled developer to a predetermined temperature in order to improve the measurement accuracy. At this time, the temperature adjustment means is preferably disposed before the measuring means. The sampling pipe 15 is connected to the sampling pump 14 of the measuring unit 1, and the return pipe 16 is connected to a pipe at the end of the measuring means.

The calculation unit 2 includes a calculation block 21 performed by a multivariate analysis method. The calculation block 21 by the multivariate analysis method is connected to the first measurement means 11 disposed in the measurement unit 1 via the measurement data signal line 51, and is connected to the second measurement unit 1 via the measurement data signal line 52. The measuring means 12 are connected.

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

The developer liquid collected from the developer storage tank 61 by the sampling pump 14 is guided to the measurement unit 1 of the component concentration measuring device A through the sampling pipe 15. Then, if the temperature adjustment means is provided, the sampled developer is sent to the temperature adjustment means, and is maintained at a predetermined measurement temperature (for example, 25 ° C) and then sent to the measurement means 11 and 12. In the first measuring means, the characteristic value a of the developing solution is measured, and in the second measuring means, the characteristic value b of the developing solution is measured. 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 means 11 and the measured value b _m of the characteristic value b of the developing solution measured by the second measuring means 12 are respectively passed through the measurement data. Signal lines 51, 52 are passed to a calculus block 21 that is performed by multivariate analysis. The calculation 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 by the multivariate analysis method. In this manner, the component concentrations A and B of the developer are measured by the component concentration measuring device A.

[Fifth Embodiment]

Fig. 5 is a schematic view showing a device for measuring a component concentration of three components of a developer. The component concentration measuring device A of the developer includes the measuring unit 1 and the calculating unit 2, and is connected to the developing process device B (developing solution storage tank 61) through the sampling pipe 15 and the return pipe 16. The measurement unit 1 includes first measurement means 11, second measurement means 12, and third measurement means 13, and the three characteristic values of the developer are measured by the measurement means. The measured values of the three characteristic values measured are transmitted to the calculation unit 2 via the measurement data signal lines 51, 52, and 53, and the component concentrations of the three components of the developer are calculated by the multivariate analysis method. The measurement operation, the calculation operation, and the description of the members overlapping with the fourth embodiment are the same as those of the fourth embodiment, and therefore will not be described.

[Sixth embodiment]

Fig. 6 is a schematic diagram of a component concentration measuring device having a calculation block performed by a calculation method different from the multivariate analysis method in the calculation unit 2. For example, when the combination of the characteristic value and the component concentration of the developer is present, the component concentration of the developer can be measured from the measured physical property value of the developer by a calibration curve method or the like.

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

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

Further, the calculation block 22 performed by an arithmetic method other than the multivariate analysis method (for example, the calibration curve method) may be plural. Regarding the calculations performed by the multivariate analysis method and the calculations performed by methods other than the multivariate analysis method (for example, the calibration curve method), the calculation order is not limited. The description of the remaining members and the like which are repeated in the fourth and fifth embodiments will be omitted.

[Seventh embodiment]

Fig. 7 is a schematic diagram of a component concentration measuring device in which the measuring unit 1 and the calculating unit 2 are independently configured.

In the component concentration measuring apparatus A of the present embodiment, the measuring unit 1 is disposed in a line bypassed from the developing solution line 80 of the developing process equipment B, and a signal line for measuring data is used between the calculating unit 2 and the calculation unit 2 51 to 53 connections. It can also be directly connected to the developer line 80 and other lines. The sampling pump 14 can also be used as a combined flow regulating valve (not shown) or the like.

[Eighth Embodiment]

Fig. 8 is a schematic view showing the measurement means 11 to 13 for measuring the characteristic values of the developer, which are component concentration measuring devices when the measurement device bodies 11a, 12a, 13a and the measurement probes 11b, 12b, and 13b are respectively formed.

In the present embodiment, the measurement probes 11b to 13b of the measurement means 11 to 13 are immersed in the developer stored in the developer storage tank 61, thereby measuring the characteristic value of the developer. The characteristic values of the measured developer are transmitted to the calculation unit 2 via the measurement data signal lines 51 to 53. The calculation unit 2 calculates the component concentration by the multivariate analysis method, thereby measuring the component concentration of the developer.

In the eighth drawing, the measurement unit 1 and the calculation unit 2 are separately configured as separate components, but they may be a component concentration measurement device that is integrally formed. In this case, the measurement probe immersed in the developer and the measurement device disposed in the measurement unit 1 of the component concentration measurement device are connected by a cable or the like.

[Ninth Embodiment]

Fig. 9 is a schematic view showing a component concentration measuring device when the measuring means in the measuring unit 1 is arranged in parallel.

The measurement means constituting the measurement unit 1 is not limited to being connected in series, and may be connected in parallel. As shown in Fig. 9, the measurement means 11 to 13 may be provided with sampling lines 15a to 15c, sampling pumps 14a to 14c, return pipes 16a to 16c, and the like, respectively, or by means of pipes which are branched from the way. Connect in parallel. The characteristic values of the developer measured by the measuring means 11 to 13 are transmitted to the calculation unit 2. In the calculation unit 2, the component concentration of the developer is calculated by the multivariate analysis method.

[Tenth embodiment]

Fig. 10 is a schematic view showing a component concentration measuring device provided with a measuring device to which a drug is added, such as an automatic titration device. In Fig. 10, the third measuring means 13 is a measuring device to which a drug must be added.

At this time, the third measuring means 13 is connected to the sampling pipe 15 and the sampling pump 14, and is also connected to the additive reagent 93 through the liquid supply pipe 18. The test reagent is added for measurement by the liquid feeding pump 17. The developer after the measurement is passed through the waste liquid pipe 19 and treated (discharged) with the waste liquid. The rest of the measurement operation and the calculation operation are the same as those of the other embodiments, and therefore will be omitted.

As described in the fourth embodiment to the tenth embodiment, the component concentration measuring apparatus according to the present invention includes the measuring unit 1 that measures a plurality of characteristic values of the developer associated with the component concentration of the developer; In the portion 2, the component concentration of the developer is measured by a multivariate analysis method based on a plurality of characteristic values of the developer measured by the measuring unit 1.

The measurement unit 1 of the component concentration measuring apparatus A of the present embodiment can adopt various embodiments. The measuring device used in the measuring device has a setting method and a connecting method which are suitable depending on the measurement method used in the measuring device. Therefore, the measuring unit 1 of the component concentration measuring device according to the present invention is configured to be the most corresponding to the measuring means. Good composition can be.

In the measurement unit 1, it is only necessary to arrange a measurement means necessary for measuring a plurality of characteristic values of the developer. Better to have temperature Degree adjustment means (not shown). The sampling pump 14, the liquid feeding pump 17, the waste liquid pipe 19, and the like are preferably disposed as appropriate, but are not necessarily internal members of the measuring unit 1.

Further, the measurement unit 1 and the calculation unit 2 may be integrally formed or may be configured separately. The measurement unit 1 and the calculation unit 2 may communicate with each other so that the calculation unit 2 can receive the measurement data of the characteristic value of the developer measured by the measurement unit 1. The measurement unit 1 and the calculation unit 2 are not limited to being connected via a signal line, and may be configured to be capable of transmitting and receiving data by means of a wireless signal. It is not necessary to concentrate the plurality of measurement means in one place to constitute the measurement unit 1, and the specific measurement means may be separately and independently assembled.

Each measurement means is not limited to a method of performing measurement by sampling, and may be a method of directly attaching to a pipe, or a method of immersing a probe in a liquid. Each measurement means may be connected in series or in parallel. The measurement unit 1 can also be configured by a combination of the above various aspects.

In addition, the order of measurement of the plurality of characteristic values of the developer in the measuring unit 1 of the present embodiment is not limited. The arrangement of each measurement means in the measurement unit 1 in the drawings of Fig. 4 to Fig. 10, and the "first" and "first" in the descriptions of "first measurement means", "second measurement means", and the like. The terms "second", "..." are not intended to limit the order of the assays of the invention. The terms "first", "second", ... are simply used to facilitate the differentiation of each of the plurality of measurement means.

Further, the calculation unit 2 of the component concentration measuring apparatus according to the present embodiment includes a calculation block by multivariate analysis. 21, in addition, may also have a calculation block performed by a method other than the multivariate analysis method (for example, the calibration curve method). In addition, the order of calculations is not limited.

In the component concentration measuring apparatus according to the present embodiment, each measuring means constituting the measuring unit 1 is connected so as to be suitable for the measurement method, and a plurality of characteristic values of the developing solution are measured, and the calculating unit 2 receives the measurement by the measuring unit 1. The measured value of the characteristic value of the obtained developer is used to calculate the component concentration of the developer by a multivariate analysis method (calculation method including a multivariate analysis method).

In the eleventh embodiment and the twelfth embodiment, an application example of the component concentration measuring device according to the present embodiment will be described. The component concentration measuring device of the present embodiment can be applied to various devices and systems as a single member.

[Eleventh Embodiment]

Fig. 11 is a schematic view showing a developer management device using the component concentration measuring device of the present embodiment.

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

The replenishing liquid storage tanks 91 and 92 are pressurized with nitrogen gas, and the control unit 3 (control device) opens and closes the control valves 41 to 43 to replenish the liquid. The over-combination line 84 is supplied to the developer. The replenished replenishing liquid is returned to the developing solution storage tank 61 via the circulation line 85 by the circulation pump 74 to be stirred. The method and the mechanism of the replenishment operation of the replenishing liquid are described in the examples of the developer management method and the developer management device which will be described later.

As described above, the component concentration measuring device according to the present embodiment can be used as a developer management by combining with a control valve provided in a flow path for supplying a replenishing liquid supplied to a developing solution, and a control device for controlling the control valves. A component of the device is utilized.

In addition, the replenishing liquid is, for example, a stock solution of a developing solution, a new liquid, a regenerating liquid, or the like. There are also cases including pure water. The so-called stock solution refers to an unused developer (for example, 20% to 25% TMAH aqueous solution) having a concentrated alkaline component concentration. The so-called new liquid refers to a developer having the same concentration of the alkaline component as the concentration used in the development process and not used (for example, 2.38% TMAH aqueous solution). The regenerant is a developer that can be reused from the used developer to remove unwanted substances from the solution. Each of the above various replenishing liquids has different replenishing liquid uses and effects. For example, the stock solution is a replenisher for increasing the concentration of the alkaline component, and the dissolved photoresist concentration and the absorbed carbon dioxide concentration are lowered. The new liquid is a replenisher for maintaining or slowly increasing or decreasing the concentration of the alkaline component to reduce the concentration of the dissolved photoresist and the concentration of the absorbed carbon dioxide. Pure water is a replenisher for reducing the concentration of each component. The same is true in the description of the following embodiments.

In addition, in FIG. 11, the replenishing liquid is supplied from the replenishing liquid storage tanks 91 and 92 via the replenishing liquid lines 81 and 82, and the pure water is supplied through the pure water line 83, but this is not And limited. supplement The liquid is first transferred from the replenishing liquid storage tanks 91, 92 and the like to a mixing tank (not shown), and is transported to the developing solution storage tank 61 after the preparation tank is prepared to have a predetermined concentration. At this time, the control valve is disposed in the middle of the line for conveying the replenishing liquid from the mixing tank to the developing solution storage tank 61. There is also no supply of pure water directly to the developer storage tank 61. At this time, the pure water pipe 83 and the control valve 43 are not present. 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 unit C. The replenishing liquid storage tanks 91 and 92 are connected to a nitrogen gas line 86 including the pressurized gas valves 46 and 47, and are pressurized by nitrogen gas supplied through the piping. Further, the replenishing liquid storage tanks 91 and 92 are connected to the replenishing liquid pipes 81 and 82, respectively, and the replenishing liquid is supplied through the valves 44 and 45 in the normally open state. The replenishing liquid pipes 81 and 82 and the pure water pipe 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. By the operation of the control valve, the replenishing liquid stored in the replenishing liquid storage tanks 91, 92 and the pure water are conveyed. Then, the replenishing liquid is merged with the circulation stirring mechanism D through the joining line 84, and is supplied to the developing solution storage tank 61 to be stirred.

When the replenishing liquid stored in the replenishing liquid storage tanks 91, 92 is reduced by replenishment, the internal pressure thereof is lowered, and the supply amount becomes unstable. Therefore, the pressurized gas valve 46, 47 The nitrogen supply is appropriately opened, and the supply is maintained so that the internal pressure of the replenishing liquid storage tanks 91 and 92 is maintained. When the replenishing liquid storage tanks 91, 92 are empty, the valves 44, 45 are closed, replaced with a new replenishing liquid storage tank filled with the replenishing liquid, or refilled with the empty replenishing liquid storage tanks 91, 92. An additional replenisher.

[Twelfth Embodiment]

The component concentration measuring device of the present embodiment can be used as a component concentration monitor of a developer and a component concentration monitoring device in combination with the display device DP. Further, it can be applied to the concentration abnormality warning device of the developer or the like in combination with the warning light WL and the warning device WT. Fig. 12 is a schematic view showing an application example of the component concentration measuring device of the present invention. As described above, the component concentration measuring device of the present invention can be applied as a member to various devices and systems.

Hereinafter, the thirteenth to seventeenth embodiments are the developer management methods according to the present invention.

The developer management method of the present invention includes a measuring step of measuring a plurality of characteristic values of the developer associated with the component concentration of the alkaline alkaline developing solution; and the calculating step is based on the measured plurality of characteristic values. The component concentration of the developer is calculated by the multivariate analysis method; and the replenishing step is to supply the replenishing solution to the developer based on the measured characteristic value of the developer and the calculated component concentration of the developer. Since the measurement procedure and the calculation procedure are the same as the measurement procedure and the calculation procedure in the above-described method for measuring the component concentration of the developer, the repeated description of the thirteenth to seventeenth embodiments will be omitted.

In the following description, the "predetermined management value" refers to a characteristic value or a concentration value which is obtained in advance as an optimum liquid chemical performance as a developing solution, and is known in advance from an empirical or experimental basis. . In other words, for example, the numerical value as the development performance index of the developer as the line width and the residual film thickness formed on the substrate after development becomes The value of the characteristic value or the component concentration value of the optimum state is known in advance. Similarly, the "predetermined management area" refers to the range of the above management values. The same applies to the description of the developer management device.

[Thirteenth Embodiment]

Figure 13 is a flow chart showing a developer management method for managing two components of a developer by a component concentration. The developer management method of the present embodiment is preferably applied to an operation in which an alkaline developer having a low concentration of carbon dioxide is managed in order to keep the concentration of the alkaline component of the developer into a predetermined state. The developer is managed in such a manner that the dissolved photoresist concentration is equal to or less than a predetermined management value.

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

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

The replenishing 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 judged whether the component concentration A is larger or smaller than the management value A ₀ . When it is relatively large, a replenishing liquid (for example, a developing solution new liquid, pure water, or the like) which produces a diluted component concentration A is added to the developing solution. When it is relatively small, a replenishing liquid (for example, a developing solution stock solution and a new liquid) which increases the concentration of the component A is supplied to the developing solution. When the component concentration A is the same as its management value A ₀ , no action is taken.

In the step of adjusting the component concentration B, it is judged whether or not the component concentration B is larger than the management value B ₀ . When it is relatively large, a replenishing liquid which acts to dilute the concentration B is generated (for example, since the new liquid of the developing solution does not change the concentration of the alkaline component, the replenishing liquid is preferably a new liquid of the developing solution) and is supplied to the developing solution. When it is small, no action is taken.

[Fourteenth Embodiment]

Fig. 14 is a flow chart showing a developer management method in which one of the two components of the developer is managed by the component concentration and the other component is managed by the property value. The developer management method of the present embodiment is preferably applied to an operation in which an alkaline developer having a low concentration of carbon dioxide is managed in order to keep the concentration of the alkaline component of the developer into a predetermined state. The developer is managed in such a manner that the absorbance at a specific wavelength (for example, λ = 560 nm) of the developer is equal to or less than a predetermined management value.

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 equal to or lower than a predetermined management value b ₀ . The component concentration A is, for example, an alkaline component concentration, and the characteristic value b is, for example, an absorbance at a specific wavelength (for example, λ = 560 nm).

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

The replenishing step includes a step of adjusting the component concentration A and a step of adjusting the characteristic value b. The step of adjusting the component concentration A is the same as that of the thirteenth embodiment, and the description thereof will be omitted.

In the step of adjusting the characteristic value b, it is judged whether or not the measured value b _m is larger than the management value b ₀ . When it is relatively large, a replenishing liquid which acts to dilute the concentration B is generated (for example, since the new liquid of the developing solution does not change the concentration of the alkaline component, the replenishing liquid is preferably a new liquid of the developing solution) and is supplied to the developing solution. When it is small, no action is taken.

When the characteristic value b and the component concentration B have a monotonically increasing correlation, the characteristic value b is managed to be equal to or lower than the management value b ₀ or less, and the component concentration B is managed to be equal to or lower than the management value B ₀ . When the characteristic value b has a monotonously decreasing correlation with the component concentration B, it is possible to manage the component concentration B to be equal to or less than the management value B ₀ as long as the magnitude relationship of the determination is reversed.

[Fifteenth Embodiment]

Fig. 15 is a flow chart showing a developer management method for managing three components of a developer by a component concentration. The developer management method of the present embodiment is preferably applied, for example, to the case where the developer is alkaline. The component concentration management is a predetermined management value, the dissolved photoresist concentration is managed to be below a predetermined management value, and the absorbed carbon dioxide concentration is managed to be below a predetermined management value.

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

The characteristic values a, b, c, ... of the developing solution are measured in a measuring step, and the measured values a _m , b _m , c _m , . . . are transmitted to the calculation step. In the calculation step, the component concentrations A, B, C, ... of the developer are measured by the multivariate analysis method from the measured values a _m , b _m , c _m , . The component concentrations A, B, C, ... calculated by the calculation step are transmitted to the replenishing step.

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

First, in the step of adjusting the component concentration A, it is judged whether the component concentration A is larger or smaller than the management value A ₀ . When it is relatively large, a replenishing liquid (for example, a developing solution new liquid, pure water, or the like) which produces a diluted component concentration A is added to the developing solution. When it is relatively small, a replenishing liquid (for example, a developing solution stock solution and a new liquid) which increases the concentration of the component A is supplied to the developing solution. When the component concentration A is the same as its management value A ₀ , no action is taken.

In the step of adjusting the component concentration B, it is judged whether or not the component concentration B is larger than the management value B ₀ . When it is relatively large, a replenishing liquid which acts to dilute the concentration B is generated (for example, since the new liquid of the developing solution does not change the concentration of the alkaline component, the replenishing liquid is preferably a new liquid of the developing solution) and is supplied to the developing solution. When it is small, no action is taken.

In the step of adjusting the component concentration C, it is judged whether or not the component concentration C is larger than the management value C ₀ . When it is relatively large, a replenishing liquid which acts to dilute the concentration C is generated (for example, since the developer liquid does not change the alkali component concentration, the replenishing liquid is preferably a developer liquid) and is supplied to the developer. When it is small, no action is taken.

[Sixteenth Embodiment]

Fig. 16 is a flow chart showing a method of managing a developer for managing the remaining two components by one of the three components of the developer by the characteristic value. The developer management method of the present embodiment is preferably applied to a case where the alkali component concentration of the developer is a predetermined management value, and the absorbance at a specific wavelength (for example, λ = 560 nm) of the developer is predetermined. The developer is managed below the management value and the concentration of the absorbed carbon dioxide of the developer is equal to or less than a 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 equal to or lower than a predetermined management value b ₀ , and the component concentration C is managed to be predetermined. The management value is below C ₀ . The component concentration A is, for example, an alkaline component concentration, and the characteristic value b is, for example, an absorbance at a specific wavelength (for example, λ = 560 nm), and the component concentration C is, for example, an absorbed carbon dioxide concentration.

In the step of measuring characteristics of the developer measured values a, b, c, some of the steps of calculating a _m, b _m, c _m values transferred to the assay. In the calculation step, the component concentrations A, B, and C of the developer are measured by multivariate analysis from the measured values a _m , b _m , and c _m . The component concentrations A and C calculated by the calculation step and the measured value b _m of the characteristic value b measured by the measurement step are transmitted to the replenishing step.

The replenishing step includes a step of adjusting the component concentration A, a step of adjusting the characteristic value b, and a step of adjusting the component concentration C. The step of adjusting the component concentration A and the step of adjusting the component concentration C are the same as those of the fifteenth embodiment, and thus the description thereof will be omitted.

In the step of adjusting the characteristic value b, it is judged whether or not the measured value b _m is larger than the management value b ₀ . When it is relatively large, a replenishing liquid which acts to dilute the concentration B is generated (for example, since the new liquid of the developing solution does not change the concentration of the alkaline component, the replenishing liquid is preferably a new liquid of the developing solution) and is supplied to the developing solution. When it is small, no action is taken.

When the characteristic value b and the component concentration B have a monotonically increasing correlation, the characteristic value b is managed to be equal to or lower than the management value b ₀ or less, and the component concentration B is managed to be equal to or lower than the management value B ₀ . When the characteristic value b and the component concentration B have a monotonically decreasing correlation, the component concentration B can be made the management value B ₀ as long as the magnitude relationship of the judgment is reversed (that is, b _m <b ₀ ). Manage in the following ways.

[Seventeenth Embodiment]

Fig. 17 is a flow chart showing a method of managing a developer for managing the remaining components by three components of the three components of the developer by characteristic values. The developer management method of the present embodiment is preferably applied to a case where the conductivity of the developer is made predetermined. The developer is managed such that the absorbance of the specific wavelength of the developer (for example, λ = 560 nm) is equal to or lower than a predetermined management value, and the concentration of the absorbed carbon dioxide of the developer is equal to or less than a predetermined management value.

In the present embodiment, the measured value a _m of the characteristic value a of the developer 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 equal to or less than a predetermined management value b ₀ . The component concentration C is managed to be equal to or lower than a predetermined management value C ₀ . The characteristic value a is, for example, conductivity, and the characteristic value b is, for example, an absorbance at a specific wavelength (for example, λ = 560 nm), and the component concentration C is, for example, an absorbed carbon dioxide concentration.

In the step of measuring characteristics of the developer measured values a, b, c, some of the steps of calculating a _m, b _m, c _m values transferred to the assay. In the calculation step, the component concentrations A, B, and C of the developer are measured by multivariate analysis from the measured values a _m , b _m , and c _m . To determine the characteristic values obtained in the measurement step of measuring a value of a _m, b measured values b _m, and by the step of calculating a component concentration C is calculated based transferred to recharge step.

The replenishing step includes a step of adjusting the characteristic value a, a step of adjusting the characteristic value b, and a step of adjusting the component concentration C. The step of adjusting the characteristic value b and the step of adjusting the component concentration C are the same as those of the sixteenth embodiment, and thus the description thereof will be omitted.

In the step of adjusting the characteristic value a, it is judged whether the measured value a _m is larger or smaller than the management value a ₀ . When it is relatively large, a replenishing liquid (for example, a developing solution stock solution or a new liquid) which produces a diluted component concentration A is supplied to the developing solution. When it is relatively small, a replenishing liquid (for example, a new liquid solution or pure water) which increases the concentration of the component A is supplied to the developer. When the same, no action is taken.

When the characteristic value a has a monotonically increasing correlation with the component concentration A, it is managed such that the component concentration A is maintained at its management value a ₀ so that the component concentration A becomes its management value A ₀ . When the characteristic value a has a monotonously decreasing correlation with the component concentration A, the system can be managed such that the component concentration A becomes the management value A ₀ as long as the magnitude relationship of the determination is reversed.

As described in the thirteenth to seventeenth embodiments, the developer management method of the present invention includes a measurement step of measuring a plurality of characteristic values of the developer associated with the component concentration of the developer; a step of calculating a component concentration of the developer by a multivariate analysis method based on the measured plurality of characteristic values; and a replenishing step based on the plurality of characteristic values from the measured developer and the calculated developer The measured value or the calculated value of the management target item selected among the component concentrations is added to the developer.

The measurement step includes a measurement step of measuring the characteristic value a, a measurement step of measuring the characteristic value b, a measurement step of measuring the characteristic value c, and the like. But the order of these steps is not limited. It can also be measured at the same time. Further, a necessary step such as a temperature adjustment step, a reagent addition step, and a waste liquid step may be appropriately included in accordance with the measurement method.

The calculation step may also include a calculation step of calculating the concentration of the component by multivariate analysis. The step of calculating the component concentration by an arithmetic method different from the multivariate analysis method (for example, the calibration curve method) may be included.

The replenishing step includes controlling the object item (the characteristic value of the developing solution and the component concentration) as a control amount to make the control The step of adjusting the component concentration A to replenish the replenishing liquid to the adjusting component concentration A of the developing solution, the step of adjusting the component concentration B, or the step of adjusting the component concentration C, or the amount of the predetermined management value or the predetermined management value or less in the management region. . The order of the steps is limited to the order shown in the drawings.

Further, regarding the manner of control, various control methods used to control the control amount in accordance with the target value can be employed. Specifically, proportional control (P control), integral control (I control), differential control (D control), and control (PI control, etc.) in which these control methods are combined are preferable. Better for PID control.

In the thirteenth to seventeenth embodiments, the measurement step, the calculation step, and the replenishment step are repeated, and the component concentration A of the developer is maintained at the management value A ₀ , and the component concentration B of the developer is The management is below its management value B ₀ , and the component concentration C is managed below its management value C ₀ . Therefore, with the developer management method of the present invention, it is possible to maintain optimum developing performance, and it is possible to achieve a desired line width and residual film thickness.

Hereinafter, the eighteenth to twenty-fifth embodiments are related to the developer management device of the present invention.

The developer management device according to the present embodiment includes the measurement unit 1 that measures a plurality of characteristic values of the developer associated with the component concentration of the alkaline developer, and the calculation unit 2 that is obtained from the measurement unit 1 The characteristic value is calculated by the multivariate analysis method, and the control unit 3 is based on the characteristic value of the developer measured by the measurement unit 1 or the component concentration of the developer calculated by the calculation unit 2 Provided to the control valve 41 for conveying the flow path of the replenishing liquid supplied to the developing solution to 43 sends a control signal. The measurement unit 1 and the calculation unit 2 of the developer management device of the present invention are the same as the measurement unit 1 and the calculation unit 2 in the component concentration measurement device for the developer described above, and therefore, the following eighteenth to twentieth embodiments In the fifth embodiment, the repeated description will be omitted.

[Eighteenth Embodiment]

Fig. 18 is a schematic view for explaining the developing process of the developer management device of the present invention. The developer management device E of the present invention is shown together with the development process equipment B, the replenishing liquid storage unit C, the circulation agitation mechanism D, and the like.

The developer management device E of the present embodiment includes a measurement unit 1 including a plurality of measurement means 11 to 13 for measuring a plurality of characteristic values of the developer, and a calculation unit 2 including a calculation block by multivariate analysis. 21; and the control unit 3 controls one of the characteristic value and the component concentration of the developer as a control amount so that the control amount becomes a predetermined management value or a management region. Further, 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 measuring unit 1 through the sampling pipe 15. In the measuring unit 1, the characteristic values of the developing solution are measured by the respective measuring means 11 to 13. The developer after the measurement is returned to the developer storage tank 61 through the return pipe 16 .

The calculation unit 2 receives a set of measured values of a plurality of characteristic values of the developer measured by the measuring unit 1. The calculation department 2 receives from the receiving The set of measured values obtained was calculated by multivariate analysis to determine the concentration of the developer.

The details of the measurement operation and the calculation operation are the same as those of the above-described component concentration measuring device for the developer, and therefore will not be described. Hereinafter, the control operation will be described.

The developer management device E is connected to the lines 81 to 83 for supplying the replenishing liquid supplied to the developer (pure water is also included as a replenishing liquid). Each of the conduits 81 to 83 is connected to the control valves 41 to 43 which are positioned in the developer management device E and whose operation is controlled by the control unit 3.

The control unit 3 receives the measured value of the characteristic value of the developer from the measuring unit 1 and receives the calculated component concentration from the calculating unit 2. The control unit 3 sets a control value for the control valves 41 to 43 based on the control amount by using the received characteristic value or component concentration of the developer as a control amount. The control is performed, for example, such that the amount of control becomes a predetermined management value or becomes within a predetermined management area.

The control unit 3 is provided with a control block. For example, if the developer management device E is to manage 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 32 for controlling the component concentration B. Control block 33 for controlling the concentration C of the component. If the concentration of the components to be managed is two, the control block can be two. Further, if more than three components are to be managed, the same control block is configured accordingly. Thus, the control unit 3 can issue the required 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 the "on" signal and are pre-adjusted for the flow rate to be opened. When the valve is capable of delivering an opening/closing control valve of a predetermined flow rate, the control unit 3 transmits an "on" signal to the control valve provided in the flow path of the replenishing liquid to be replenished for a predetermined period of time, thereby making the developing solution The replenishing liquid required for management is supplied to the developer only in an amount necessary.

The control action of the control valve is not limited to the above example. When the control valve switches the open state and the closed state of the valve by the opening and closing switching signal, the control unit 3 transmits a pulse-type opening and closing switching signal to the control valve at predetermined time intervals, thereby making the required The replenisher is replenished to the developer in only the necessary amount.

Further, the control valves 41 to 43 may be control valves capable of controlling the valve opening degree, or may simply be a combination of a flow regulating valve (needle valve) and an opening and closing control valve. The control valves 41 to 43 may be solenoid valves or air operated valves (air operated valves).

The control valves 41 to 43 operate in accordance with a control signal from the control unit 3, whereby the replenishing liquid required for the developer management is supplied to the developer. The control unit 3 controls the type of the replenishing liquid obtained from the received control amount (the characteristic value or the component concentration of the developing solution) and the required replenishment amount thereof in order to deliver the required replenishment amount. The control valve sends a control signal.

According to the developer management device of the present embodiment, it is possible to set the characteristic value or the component concentration to a predetermined management value or to be predetermined based on the measured characteristic value of the developer or the calculated component concentration of the developer. The management of the developer is maintained in a manner within the management area.

More specifically, developer management as listed below can be performed. However, the developer management listed below is merely illustrative and is not limited thereto.

The first type of developer management is to supply the replenishing liquid to the developer so that the alkaline component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration of the repeatedly used alkaline developing solution become predetermined management values for each. For example, the developer management apparatus according to the present invention can be managed to have a predetermined management value in which the alkaline component concentration of the 2.38% TMAH aqueous solution is preferably from 2.375 (wt%) to 2.390 (wt%), more preferably 2.380 (wt%); a predetermined management value of a dissolved photoresist concentration of preferably 0.40 (wt%) or less, more preferably 0.15 (wt%); and a predetermined management of an absorption carbon dioxide concentration of preferably 0.40 (wt%) or less; The value is more preferably 0.25 (wt%).

The second developer management is to replenish the replenishing liquid so that the alkaline component concentration of the re-used developer becomes a predetermined management value, and the dissolved photoresist concentration and the absorbed carbon dioxide concentration are equal to or less than a predetermined management value for each developer. To the developer. For example, the developer management apparatus according to the present invention can be managed to have a predetermined management value in which the alkaline component concentration of the 2.38% TMAH aqueous solution is preferably from 2.375 (wt%) to 2.390 (wt%), more preferably 2.380 (wt%); the dissolved photoresist concentration is preferably 0.40 (wt%) or less; the absorbed carbon dioxide concentration is preferably 0.40 (wt%) or less.

The third developer management is to supply the replenishing liquid to the developer so that the alkaline component concentration of the reusable alkaline developing solution, the absorbance at a specific wavelength, and the absorbed carbon dioxide concentration become predetermined management values for each. For example, the developer management device according to the present invention, The concentration of the basic component of the 2.38% TMAH aqueous solution can be managed to be a predetermined management value in the range of 2.375 (wt%) to 2.390 (wt%), more preferably 2.380 (wt%); preferably the wavelength is The absorbance at λ = 560 nm (cell optical path length d = 10 mm) is managed to be a predetermined management value of 1.30 (Abs.) or less, more preferably 0.50 (Abs.); and the absorbed carbon dioxide concentration is preferably 0.40 (wt%). The predetermined management value below is more preferably 0.25 (wt%).

The fourth developer management is such that the alkaline component concentration of the repeatedly used alkaline developer is predetermined, the absorbance at a specific wavelength is within a predetermined management region, and the absorbed carbon dioxide concentration is equal to or less than a predetermined management value. Replenish the replenisher to the developer. For example, the developer management apparatus according to the present invention can be managed to have a predetermined management value in which the alkaline component concentration of the 2.38% TMAH aqueous solution is preferably from 2.375 (wt%) to 2.390 (wt%), more preferably 2.380 (wt%); the absorbance of the wavelength λ = 560 nm (the groove optical path length d = 10 mm) is preferably 1.30 (Abs.) or less, more preferably 0.65 (Abs.) or less; the absorbed carbon dioxide concentration is preferably 0.40 (wt%). )the following.

The fifth type of developer management is to supply the replenishing liquid to the developing solution such that the conductivity of the repeatedly used alkaline developing solution, the absorbance at a specific wavelength, and the absorbed carbon dioxide concentration become predetermined management values of each. For example, the developer management apparatus according to the present invention can manage a predetermined management value in which the conductivity of the 2.38% TMAH aqueous solution is preferably in the range of 54.47 (mS/cm) to 54.75 (mS/cm), more preferably 54.58 (mS/cm); absorbance at a wavelength λ = 560 nm (slot light path length d = 10 mm) is preferably a predetermined management value of 1.3 (Abs.) or less, more preferably 0.50 (Abs.); It is a predetermined management value of 0.40 (wt%) or less, more preferably 0.25 (wt%).

The sixth type of developer management is a method in which the conductivity of the repeatedly used alkaline developer is a predetermined management value, the absorbance at a specific wavelength is within a predetermined management region, and the absorbed carbon dioxide concentration is equal to or lower than a predetermined management value. Replenish the replenisher to the developer. For example, the developer management apparatus according to the present invention can manage a predetermined management value in which the conductivity of the 2.38% TMAH aqueous solution is preferably in the range of 54.47 (mS/cm) to 54.75 (mS/cm), more preferably 54.58 (mS/cm); absorbance at a wavelength λ = 560 nm (slot light path length d = 10 mm) is preferably 1.30 (Abs.) or less, more preferably 0.65 (Abs.) or less; and the absorbed carbon dioxide concentration is preferably 0.40 (wt). %)the following.

Therefore, according to the developer management device of the present embodiment, it is possible to manage the concentration of each component of the developer or each characteristic value to a predetermined management value or management area with higher precision than the prior art, so that development can be performed. The liquid is maintained at an optimum developing performance so that the desired line width and residual film thickness can be achieved.

[Nineteenth Embodiment]

Fig. 19 is a schematic view for explaining a developing solution management device of an embodiment in which the control valves 41 to 43 which are provided in the flow path of the replenishing liquid supplied to the developing solution are disposed outside the developing solution management device of the present embodiment.

The developer management device E of the present embodiment includes a measurement unit 1 including a plurality of measurement means for measuring a plurality of characteristic values of the developer, and the calculation unit 2 includes a calculation block 21 by a multivariate analysis method; The control unit 3 uses one of the characteristic value and the component concentration of the developer as a control amount so that the control amount becomes a predetermined management. The value or the manner in the management area gives a control signal to the control valves 41 to 43 provided in the replenishing line of the replenishing liquid.

In the present embodiment, the control valves 41 to 43 controlled by the control unit 3 are not internal members of the developer management device E. It is provided in a conduit for conveying the replenishing liquid independently of the developer management device E. The developer management device E is not connected to the pipes that deliver the replenishing liquid.

The rest of the configuration, operation, and the like are the same as those in the eighteenth embodiment, and therefore will not be described.

[Twentyth embodiment]

Fig. 20 is a schematic diagram of a developer management device E having an arithmetic control unit 23 having both an arithmetic function and a control function.

The developer management device E of the present invention is not limited to the configuration in which the calculation unit 2 and the control unit 3 are individually independent devices. It is also possible to constitute an integrated calculation control unit 23 that has both an arithmetic function and a control function. The calculation control unit 23 is, for example, a multi-function device such as a computer.

The computer system has a wide range of functions such as input/output function, signal transmission and reception function, calculation function, control function, and display function. Therefore, the calculation function and the control function of the developer management device E of the present invention can be realized by a computer. The calculation control unit 23 may be connected to the measurement unit 1 and the control valves 41 to 43. In this case, a calculation processing program for calculating the component concentration from the measured characteristic value of the developer by the multivariate analysis method is installed in the computer, and the control amount (the characteristic value or the component concentration of the developer) is predetermined. The management value or the control program for issuing control signals to the control valves 41 to 43 in a predetermined management area enables the developer to be maintained in a predetermined state.

The rest of the configuration, operation, and the like are the same as those in the eighteenth embodiment, and therefore will not be described.

[Twenty-first embodiment]

Fig. 21 is a schematic view showing a developer management device for managing two components of the developer. The developer management device E of the present embodiment is preferably applied to a case where the alkaline component concentration and the dissolved photoresist concentration of the alkaline developer which is managed so as to reduce the absorption of carbon dioxide are used.

The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of a developing solution having a concentration of at least an alkaline component in a component of a developing solution, and causing the second measuring means 12 In order to measure the characteristic value of the developer relating to at least the dissolved photoresist concentration in the composition of the developer (for example, an absorptiometer that measures the absorbance at a wavelength of λ = 560 nm), the calculation unit 2 contains multivariate Since the calculation block 21 is performed by the analysis method, the alkaline component concentration and the dissolved photoresist concentration of the developer can be calculated from the measured characteristic values of the developer by the multivariate analysis method.

In this way, when the control block 31 is a control block that sends a control signal to the control valve in such a manner that the conductivity or the alkaline component concentration of the developer becomes a predetermined management value, the control block 32 is such that the specific wavelength of the developer ( For example, when the absorbance or the dissolved photoresist concentration of λ = 560 nm becomes a predetermined management value or a control block for issuing a control signal to the control valve in a management area, the control unit 3 is capable of receiving the measured characteristics of the developer. The value and the calculated concentration of the developer Since the mode is connected to the measurement unit 1 and the calculation unit 2, the developer management device E of the present embodiment can set the concentration of the alkaline component of the developer to a predetermined management value and set the concentration of the dissolved photoresist to a predetermined value. Maintain management of the developer in a manner that manages the value or management area.

The rest of the details are the same as in the other embodiments, and therefore will be omitted.

[Twenty-second embodiment]

Fig. 22 is a schematic view showing a developer management device for managing two components of a developer by a component concentration. The developer management device according to the present embodiment is preferably applied to a case where the alkali component concentration and the dissolved photoresist concentration of the alkaline developer which is managed to avoid absorption of carbon dioxide are managed as the management concentration value.

The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of a developing solution having a concentration of at least an alkaline component in a component of a developing solution, and causing the second measuring means 12 In order to measure the characteristic value of the developer associated with at least the dissolved photoresist concentration in the composition of the developer (for example, an absorptiometer that measures the absorbance at λ = 560 nm), the calculation unit 2 contains multivariate analysis. Since the square 21 is calculated by the method, the alkaline component concentration and the dissolved photoresist concentration of the developer can be calculated from the measured characteristic values of the developer by the multivariate analysis method.

In this way, as long as the control block 31 is a control block that sends a control signal to the control valve in such a manner that the alkaline component concentration becomes a predetermined management value, the control block 32 is such that the dissolved photoresist concentration is The control unit 3 sends a control signal to the control valve in a manner that is less than a predetermined management value or a management value. The control unit 3 is connected to the calculation unit 2 so as to be able to receive the calculated concentration of the developer solution. In the developer management device E of the present embodiment, the developer can be maintained by setting the alkaline component concentration of the developer to a predetermined management value and setting the dissolved photoresist concentration to a predetermined management value or less.

The rest of the details are the same as in the other embodiments, and therefore will be omitted.

[Twenty-third embodiment]

Fig. 23 is a schematic diagram of a developer management apparatus which manages the remaining components by the three components of the developer by the characteristic values. The developer management device according to the present embodiment is preferably applied to a case where the alkaline component concentration of the alkaline developer is controlled by the conductivity, and the solubility is managed by the absorbance at a specific wavelength (for example, λ = 560 nm). The concentration of the photoresist is controlled by the concentration to absorb the concentration of carbon dioxide.

The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of a developing solution having a concentration of at least an alkaline component in a component of a developing solution, and causing the second measuring means 12 A measuring means for measuring a characteristic value of a developing solution relating to at least a dissolved photoresist concentration in a component of a developing solution (for example, an absorptiometer for measuring an absorbance of λ = 560 nm), and a third measuring means 13 for measuring and developing The concentration of at least the absorbed carbon dioxide in the liquid component is determined by the characteristic value of the developer (for example, the density of the density is measured) In the calculation unit 2, since the calculation unit 2 includes the calculation block 21 by the multivariate analysis method, the alkaline component concentration and the dissolved photoresist of the developer can be calculated from the measured characteristic values of the developer by the multivariate analysis method. Concentration, and absorption of carbon dioxide concentration.

In this way, when the control block 31 is a control block for issuing a control signal to the control valve in such a manner that the conductivity of the developer becomes a predetermined management value, the control block 32 is such that the characteristic wavelength of the developer (for example, λ = 560 nm). The control block for issuing a control signal to the control valve in a manner that the absorbance becomes a predetermined management value or a management area, and the control block 33 sends a control signal to the control valve in such a manner that the absorbed carbon dioxide concentration becomes a predetermined management value or a management value or less. When the control unit 3 is connected to the measurement unit 1 so as to be able to receive the measured component concentration of the developer, the control unit 3 is connected to the calculation unit 2 so as to be able to receive the measured characteristic value of the developer. In addition, the developer management device E of the present embodiment can make the alkaline component concentration of the developer into a predetermined management value, set the dissolved photoresist concentration to a predetermined management value or less, and absorb carbon dioxide. The management of the developer is maintained in such a manner that the concentration becomes a predetermined management value or a management value or less.

The rest of the details are the same as in the other embodiments, and therefore will be omitted.

[Twenty-fourth embodiment]

Fig. 24 is a schematic view showing a developer management device for managing one of the three components of the developer by the characteristic value and managing the remaining two components by the component concentration. The developer management device of the embodiment is preferably It is suitable for the case where the concentration of the alkaline component of the alkaline developing solution and the concentration of the absorbed carbon dioxide are managed by the concentration, and the concentration of the dissolved photoresist is managed by the absorbance of a specific wavelength (for example, λ = 560 nm).

The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of a developing solution having a concentration of at least an alkaline component in a component of a developing solution, and causing the second measuring means 12 A measuring means for measuring a characteristic value of a developing solution relating to at least a dissolved photoresist concentration in a component of a developing solution (for example, an absorptiometer for measuring an absorbance of λ = 560 nm), and a third measuring means for measuring and developing a liquid The measuring unit 2 (for example, a density meter for measuring density) in which at least the carbon dioxide concentration is absorbed in the component, the calculation unit 2 includes the calculation block 21 by the multivariate analysis method. The multivariate analysis method calculates the alkaline component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration of the developer from the measured characteristic values of the developer.

In this way, when the control block 31 is a control block for issuing a control signal to the control valve in such a manner that the alkali component concentration becomes a predetermined management value, the control block 32 is such that the characteristic wavelength of the developer (for example, λ = 560 nm). The control block for issuing a control signal to the control valve in a manner that the absorbance becomes a predetermined management value or a management area, and the control block 33 sends a control signal to the control valve in such a manner that the absorbed carbon dioxide concentration becomes a predetermined management value or a management value or less. In the case of the control unit, the control unit 3 is connected to the measurement unit 2 so as to be able to receive the measured characteristic value of the developer, and is connected to the calculation unit 2 so as to be able to receive the component concentration of the calculated developer. Together, so by this implementation In the developer management device E of the aspect, the concentration of the alkaline component of the developer is set to a predetermined management value, the concentration of the dissolved photoresist is equal to or less than a predetermined management value or management value, and the concentration of the absorbed carbon dioxide is a predetermined management value. Or manage the developer in a manner that is less than the management value.

The rest of the details are the same as in the other embodiments, and therefore will be omitted.

[Twenty-fifth embodiment]

Fig. 25 is a schematic view showing a developer management apparatus for managing three components of a developer by a component concentration. The developer management device according to the present embodiment is preferably applied to a case where the alkaline component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration of the alkaline developer are managed by the concentration.

The first measuring means 11 is a measuring means (for example, a conductivity meter for measuring conductivity) for measuring a characteristic value of a developing solution having a concentration of at least an alkaline component in a component of a developing solution, and causing the second measuring means 12 A measuring means for measuring a characteristic value of a developing solution relating to at least a dissolved photoresist concentration in a component of a developing solution (for example, an absorptiometer for measuring an absorbance of λ = 560 nm), and a third measuring means for measuring and developing a liquid The measuring unit 2 (for example, a density meter for measuring density) in which at least the carbon dioxide concentration is absorbed in the component, the calculation unit 2 includes the calculation block 21 by the multivariate analysis method. The multivariate analysis method calculates the alkaline component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration of the developer from the measured characteristic values of the developer.

In this way, when the control block 31 is a control block for issuing a control signal to the control valve in such a manner that the alkali component concentration becomes a predetermined management value, the control block 32 is such that the dissolved photoresist concentration becomes a predetermined management value or management value. In the following manner, the control block for issuing a control signal to the control valve, and the control block 33 is a control block for issuing a control signal to the control valve in such a manner that the absorbed carbon dioxide concentration becomes a predetermined management value or a management value or less, since the control unit 3 Since the calculation unit 2 can be connected to the calculation unit 2 so that the concentration of the component of the developer can be received, the developer management device E of the present embodiment can set the alkaline component concentration of the developer to a predetermined management value. The management developer is maintained such that the dissolved photoresist concentration is equal to or less than a predetermined management value or management value, and the absorbed carbon dioxide concentration is equal to or lower than a predetermined management value or management value.

The rest of the details are the same as in the other embodiments, and therefore will be omitted.

As described in the eighteenth to twenty-fifth embodiments, the developer management device of the present embodiment includes the measuring unit 1 for measuring the plural amount of the developer associated with the component concentration of the alkaline developer. The calculation unit 2 calculates the component concentration of the developer from the plurality of characteristic values measured by the measurement unit 1 by the multivariate analysis method, and the control unit 3 develops based on the measurement unit 1 The characteristic value of the liquid or the component concentration of the developer calculated by the calculation unit 2 gives a control signal to the control valves 41 to 43 provided in the flow path for supplying the replenishing liquid supplied to the developer.

In the measurement unit 1 and the calculation unit 2 in the developer concentration measuring apparatus of the developer, the measurement unit 1 and the calculation unit 2 in the developer management device of the present embodiment can adopt many different aspects.

The control unit 3 in the developer management device according to the present embodiment does not have to be disposed separately from the device of the calculation unit 2, and can be installed as a control function and an arithmetic function of an integrated device (for example, a computer). Further, as shown in FIG. 11, the control unit 3 may be configured to be independent of the measurement unit 1 and the calculation unit 2, respectively. The control unit 3 may 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 as the control amount or the component concentration calculated by the calculation unit 2. In this way, the desired control signal can be emitted based on the received characteristic values and component concentrations.

The pipe for conveying the replenishing liquid may be connected to the developer management device E of the present embodiment or may not be connected. The control valve may not be an internal member of the developer management device E. The control unit 3 may be disposed outside the developer management device E so as to be in communication with the control unit 3 by the control signal from the control unit 3.

As described above, according to the developer management device of the present invention, it is possible to manage the concentration of each component of the developer or each characteristic value within a predetermined management value or management range. Therefore, with the developer management device of the present invention, it is possible to maintain an optimum developing performance, and it is possible to achieve a desired line width and residual film thickness.

According to the developer management apparatus of the present invention, since the concentration of each component of the developer is accurately controlled to a predetermined state, the development performance of the developer can be maintained with higher precision. Therefore, the developing speed at the time of developing the photoresist is stabilized at a constant speed, and the line width and the residual film thickness formed by the development processing are set to be constant, so that the quality of the product is improved, and it is expected to contribute to further miniaturization and high density product. Physicalization.

According to the developer management apparatus of the present invention, since the developer is automatically and always maintained at an optimum developing performance, the yield of the product is improved, and the replacement operation of the developer is no longer required, it is expected to contribute to the reduction of the running cost. And waste liquid costs.

1‧‧‧Determination Department

2‧‧‧ Calculation Department

3‧‧‧Control Department

11‧‧‧First measure

12‧‧‧Second measure

13‧‧‧ Third measure

14‧‧‧Sampling pump

15‧‧‧Sampling piping

16‧‧‧Reflow piping

21‧‧‧ calculus with multivariate analysis

31, 32, 33‧‧‧ control blocks

41 to 43‧‧‧ control valve

44, 45‧‧‧ valve

46, 47‧‧‧ Valves for pressurized gas

55 to 57‧‧‧ Signal lines for control signals

61‧‧‧ developer storage tank

62‧‧‧Overflow trough

63‧‧‧liquid level meter

64‧‧‧Development room shield

65‧‧‧Roller conveyor

66‧‧‧Substrate

67‧‧‧Developing sprinkler

71‧‧‧Waste pump

72, 74‧‧‧ Circulating pump

73, 75‧‧‧ filter

80‧‧‧developer line

81, 82‧‧‧ Pipes for replenishing liquid (developer stock solution and/or new liquid)

83‧‧‧Pure water pipeline

84‧‧‧Confluence pipeline

85‧‧‧Circulation line

86‧‧‧Nitrogen pipeline

91, 92‧‧‧ replenishing liquid (developer stock solution and / or new liquid) storage tank

B‧‧‧Developing process equipment

C‧‧‧Replenishment Storage Department

D‧‧‧Circulating mixing mechanism

E‧‧‧ developer management device

Claims (10)

A method for measuring a component concentration of a developer, comprising the steps of: measuring a plurality of characteristic values of the developer associated with a concentration of a component of the alkaline developer repeatedly used; and A plurality of characteristic values, the step of calculating the component concentration of the developer by multivariate analysis. A component concentration measuring device for a developing solution includes a measuring unit that measures a plurality of characteristic values of the developing solution associated with a component concentration of an alkaline developing solution that is repeatedly used, and a calculation unit The plurality of characteristic values measured by the measuring unit are used to calculate the component concentration of the developer by a multivariate analysis method. A developer management method comprising the steps of: measuring a plurality of characteristic values of the developer associated with a concentration of a component of a re-used alkaline developer; and determining the plurality of characteristic values a step of calculating a component concentration of the developer by a multivariate analysis method; and a component of the developer calculated based on a plurality of characteristic values of the developer measured by the step of measuring the above and a step of calculating the above The measured value or the calculated value of the management target item selected among the concentrations, and the step of replenishing the replenishing liquid to the developing solution. A developer management device comprising: a measuring unit that measures a plurality of characteristic values of the developer corresponding to a concentration of a component of an alkaline developer that is repeatedly used; The calculation unit calculates the component concentration of the developer by the multivariate analysis method based on the plurality of characteristic values measured by the measurement unit, and the control unit is based on the developer from the measurement unit measured by the measurement unit. a plurality of characteristic values and a measured value or a calculated value of the management target item selected from the component concentrations of the developer calculated by the calculation unit, and the control valve provided to the flow path for supplying the replenishing liquid supplied to the developer is controlled signal. The developer management device according to claim 4, wherein the measurement unit includes: a first measurement means for measuring a characteristic value of the developer corresponding to a concentration of at least an alkaline component in a component of the developer; and a second The measuring means measures the characteristic value of the developing solution relating to the concentration of the photoresist dissolved in at least the developing solution among the components of the developing solution. The developer management device according to claim 5, wherein the calculation unit includes a calculation block for calculating a concentration of the alkaline component of the developer and a concentration of the photoresist, and the control unit includes an alkalinity calculated by the calculation block a control block for issuing a control signal to the control valve in such a manner that the concentration of the component becomes a predetermined management value; and a control signal is issued to the control valve such that the concentration of the photoresist calculated by the calculation block becomes equal to or less than a predetermined management value Control block. The developer management device according to claim 5, wherein the measurement unit further includes a third measurement means for measuring the concentration of carbon dioxide absorbed by at least the developer in the component of the developer The characteristic value of the developer. The developer management device according to claim 7, wherein the calculation unit includes a calculation block for calculating a concentration of carbon dioxide in the developer; and the control unit includes: a characteristic value of the developer measured by the first measurement means a control block for issuing a control signal to the control valve in a manner of a predetermined management value; the control signal is sent to the control valve in such a manner that the characteristic value of the developer determined by the second measuring means falls within a predetermined management area a control block; and a control block for issuing a control signal to the control valve such that the concentration of carbon dioxide calculated by the calculation block is equal to or less than a predetermined management value. The developer management device according to claim 7, wherein the calculation unit includes a calculation block for calculating a concentration of an alkaline component of the developer and a concentration of carbon dioxide, and the control unit includes an alkaline component calculated by the calculation block. a control block for issuing a control signal to the control valve in such a manner that the concentration becomes a predetermined management value; and the control valve is issued in such a manner that the characteristic value of the developer measured by the second measuring means falls within a predetermined management area Control block for control signals; and A control block for issuing a control signal to the control valve in such a manner that the concentration of carbon dioxide calculated by the calculation block is equal to or lower than a predetermined management value. The developer management device according to claim 7, wherein the calculation unit includes a calculation block for calculating a concentration of the alkaline component of the developer, a concentration of the photoresist, and a concentration of carbon dioxide; and the control unit includes: a control block for issuing a control signal to the control valve in such a manner that the calculated concentration of the alkaline component becomes a predetermined management value; and the control valve is set such that the concentration of the photoresist calculated by the calculation block is equal to or less than a predetermined management value a control block for issuing a control signal; and a control block for issuing a control signal to the control valve such that the concentration of carbon dioxide calculated by the calculation block is equal to or less than a predetermined management value.