TW201828333A - Apparatus for measuring component concentration in developing solution and developing solution management apparatus capable of accurately computing concentration of each component of alkaline developing solution and maintaining and managing developing performance in optimal state - Google Patents

Abstract

The present invention provides a component concentration measurement apparatus for accurately computing the concentration of each component, such as an alkaline component of an alkaline developing solution, dissolved photoresist and absorbed carbon dioxide, from the characteristic value of developing solution and a developing solution management apparatus for maintaining and managing the developing performance of the developing solution in the optimal state. The apparatus for measuring component concentration in developing solution comprises: a measurement portion 1 for measuring a plurality of characteristic values of the developing solution related to the component concentration of an alkaline developing solution that is repeatedly used; a computation portion 2 for computing the component concentration of the developing solution by a multivariate analysis method according to the plurality of characteristic values measured by the measurement portion; and, a display portion DP for displaying at least one of the characteristic values measured by the measurement portion and the component concentration computed by the computation portion 2.

Description

   Component concentration measuring device for developing solution and developing solution management device   

The invention relates to a component concentration measuring device and a developing solution management device for a developing solution that exhibits an alkaline property and is used repeatedly in the development process of a circuit board of a semiconductor or a liquid crystal panel to develop a photoresist film.

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

In the manufacturing processes of semiconductors, liquid crystal panel substrates, etc., in recent years, the size of wafers, glass substrates, and the like have been enlarged, and the miniaturization and high-volume integration of wiring processing have progressed significantly. In such a situation, in order to realize miniaturization and high integration of wiring processing of a large substrate, it is necessary to measure the concentration of the main component of the alkaline developing solution with higher accuracy in order to maintain and manage the developing solution.

As described in Patent Document 1, a conventional measurement of the component concentration of an alkaline developer is obtained by using a concentration between an alkali component of the alkaline developer (hereinafter referred to as "alkaline component concentration") and electrical conductivity. A good linear relationship and a good linear relationship between the concentration of a photoresist that has been dissolved in an alkaline developer (hereinafter referred to as the "dissolved photoresist concentration") and the absorbance.

In addition, alkaline developing solution absorbs carbon dioxide in the air, and easily generates carbonate to deteriorate. In addition, the alkaline developer solution generates a photoresist salt by dissolving the photoresist, and an alkaline component effective for development processing is consumed. Therefore, the repeatedly used alkaline developing solution becomes a multi-component system containing not only an alkali component but also a photoresist, carbon dioxide, and the like. Moreover, each of these components has a different degree of contribution to the development performance. Therefore, in order to be able to maintain and manage the developing performance of the developing solution with high accuracy, it is necessary to consider the influence of these components on the developing performance in consideration of the developing solution management.

In order to solve such a problem, Patent Document 2 discloses a developer preparation device and the like, and measures the ultrasonic wave propagation speed, conductivity, and absorbance of the developer, based on the ultrasonic propagation at the alkali concentration, carbonate concentration, and dissolved resin concentration. The pre-made relationship (matrix) of speed and conductivity and absorbance is used to detect the alkali concentration, carbonate concentration, and dissolved resin concentration of the developing solution, and based on the measured alkali concentration, carbonate concentration, and dissolved resin concentration of the developing solution, and The relationship between the alkali concentration, the carbonate concentration, and the dissolved resin concentration, which can exhibit the solubility of the critical dimension value (line width) to a fixed value, is controlled in advance, and the supply of the developer solution is controlled to adjust the alkali concentration.

In addition, Patent Document 3 discloses a carbonate-based salt concentration measuring device that measures the refractive index, electrical conductivity, and absorbance of a developer and obtains the carbonate-based salt concentration in the developer from these measured values, and includes the carbonate A system for measuring the concentration of a salt system and an alkali developer management system for a control unit that controls the concentration of a carbonate system in a developer.

Advance technical literature Patent literature

Patent Document 1 Japanese Patent No. 2561578

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

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

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

On the other hand, when the characteristic value of the developing solution is the number of concentrations of various components contained in the developing solution, and the concentration of each component is calculated from the measured value of the characteristic value of the developing solution, after measuring a plurality of characteristic values, It is necessary to use an appropriate calculation method for calculating the concentration of each component from the measured values of these characteristic values. However, it is very difficult to appropriately select the characteristic value to be measured and find an appropriate calculation method that can accurately calculate the concentration of each component from the measured value of the characteristic value. Therefore, if the measured characteristic values and calculation methods are not appropriate, there is a problem that sufficient accuracy cannot be calculated for each component concentration.

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

In addition, regarding the concentration of carbon dioxide absorbed by the developing solution (hereinafter referred to as "absorbed carbon dioxide concentration"), the proper characteristic value of the developing solution exhibiting good correlation has not been known, and it is difficult for the conventional system to measure the absorption with high accuracy CO2 concentration.

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

The present invention has been made to solve the above problems. An object of the present invention is to provide a method that can accurately determine the component concentration of a developer from the characteristic values of a multi-component developer, and can analyze the developer without preparing a large number of samples and preparing for measurement. A component concentration measuring device of a developing solution that can display the component concentration and a developing solution management device that provides a more precise management of the component concentration of the developing solution.

The present invention for achieving the foregoing objects is as follows.

(1) A component concentration measuring device for a developing solution, comprising: a measuring section that measures a plurality of characteristic values of the developing solution related to the component concentration of the alkaline developing solution that is repeatedly used; and a computing section based on the aforementioned measuring section. The measured plurality of characteristic values are used to calculate the component concentration of the developing solution by a multivariate analysis method; and a display section displays the characteristic value measured by the measurement section and the component concentration calculated by the calculation section. At least one.

(2) A component concentration measuring device for a developing solution, comprising: a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to the component concentration of a developing solution that exhibits alkalinity that is repeatedly used; When measuring the plurality of characteristic values, the component concentration of the developer is calculated by a multivariate analysis method based on the plurality of characteristic values measured by the measurement section. The measurement data storage section will calculate the component concentration calculated by the calculation section. The component concentration is memorized together with at least one of the time and the elapsed time from the start of the measurement; and the display section stores the component concentration data stored in the measurement data storage section to be stored in the measurement data storage section. The time or the elapsed time from the start of measurement is used as an indicator to display the graph.

(3) A component concentration measuring device for a developing solution, comprising: a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to the component concentration of a developing solution that exhibits alkalinity that is repeatedly used; When the plurality of characteristic values are measured by the measurement unit, the component concentration of the developer is calculated by multivariate analysis based on the plurality of characteristic values measured by the measurement unit; the measurement data storage unit will use the measurement values measured by the measurement unit. The characteristic value and the component concentration calculated by the calculation unit are memorized together with at least one of the time and the elapsed time from the measurement start; and the display unit stores the characteristic value stored in the measurement data storage unit. At least one of the component concentration and the component concentration is displayed in a graph using the time memorized in the measurement data storage unit or the elapsed time from the start of measurement as an index.

(4) The component concentration measuring device for a developer according to (3), further comprising: a display switching means for switching a graph to be displayed on the display section to a graph of characteristic values of the developer or a component of the developer. Concentration chart.

(5) A developing solution management device comprising: a measuring section that measures a plurality of characteristic values of the developing solution related to the component concentration of a developing solution that exhibits alkalinity that is repeatedly used; and a computing section based on the values measured by the measuring section. The plurality of characteristic values is used to calculate the component concentration of the developer by a multivariate analysis method; the display unit displays at least one of the characteristic value measured by the measurement unit and the component concentration calculated by the calculation unit; And the control unit, based on the measured value or calculated value of the management object item selected from the plurality of characteristic values of the developer measured by the measurement unit and the component concentration of the developer calculated by the calculation unit, A control valve provided on a pipeline for supplying a replenishing solution to be replenished to the developer is issued a control signal.

(6) A developer management device, comprising: a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to the component concentration of a developing solution that exhibits alkalinity that is repeatedly used; and a computing section that measures the aforementioned In the case of a plurality of characteristic values, the component concentration of the developer is calculated by a multivariate analysis method based on the plurality of characteristic values measured by the measurement section; the measurement data storage section will use the component concentration calculated by the calculation section , And memorize together with at least one of the time and the elapsed time from the start of the measurement; the display section stores the component concentration data stored in the aforementioned measurement data storage section to memorize the time of the aforementioned measurement data storage section or from The elapsed time from the start of the measurement is used as an indicator to display the graph; and the control unit is based on the characteristic values of the developer solution measured by the measurement unit and the component concentration of the developer solution calculated by the calculation unit. The measured value or calculated value of the selected management target item is set for the The control valve of the filling of pipeline control signals.

(7) A developing solution management device comprising: a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to the component concentration of a developing solution that exhibits alkalinity that is repeatedly used; a computing section that measures the aforementioned In the case of a plurality of characteristic values, the component concentration of the developer is calculated by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit; the measurement data storage unit will use the characteristic values measured by the measurement unit. And the component concentration calculated by the calculation unit, and memorize together with at least one of time and elapsed time from the start of measurement; the display unit stores the characteristic value and component concentration in the measurement data storage unit At least one of which uses the time memorized in the measurement data storage section or the elapsed time from the start of measurement as an indicator to display a graph; and the control section, based on a plurality of characteristic values of the developer measured from the measurement section And the measured value of the item to be managed selected from the component concentration of the developer solution calculated by the calculation unit, or The calculated value sends a control signal to a control valve provided on a pipeline for supplying a replenishing solution to be replenished to the developer.

(8) The developer management device according to (7), further comprising: a display switching means for switching a graph to be displayed on the display section to a graph of a characteristic value of the developer or a graph of a component concentration of the developer. .

(9) The developer management device according to any one of (5) to (8), wherein the measurement unit includes: a first measurement means for measuring the concentration of at least an alkali component among the components of the developer; A characteristic value of the developing solution; and a second measuring means for measuring the characteristic value of the developing solution related to a concentration of at least a photoresist dissolved in the developing solution among the component concentrations of the developing solution.

(10) The developer management device according to (9), wherein the calculation unit includes a calculation block that calculates the concentration of the alkali component of the developer and the concentration of the photoresist, and the control unit includes: a first control block, The control valve sends a control signal, and the concentration of the alkali component calculated by the operation block becomes a predetermined management value; and the second control block sends a control signal to the control valve, and the light calculated by the operation block The concentration of the resist is below a predetermined management value.

(11) The developing solution management device according to (9), wherein the measuring unit further includes a third measuring means for measuring the concentration of the developing solution related to at least the concentration of carbon dioxide absorbed by the developing solution among the components of the developing solution. Characteristic value.

(12) The developer management device according to (11), wherein the calculation unit includes a calculation block that calculates a carbon dioxide concentration of the developer, and the control unit includes a third control block that sends a control signal to the control valve,特性 The characteristic value of the developer measured by the first measurement means becomes a predetermined management value; the fourth control block sends a control signal to the control valve, and the developer is measured by the second measurement means. And the fifth control block sends a control signal to the control valve, and the carbon dioxide concentration calculated by the operation block becomes below the predetermined management value.

(13) The developer management device according to (11), wherein the calculation unit includes a calculation block that calculates a concentration of an alkali component and a concentration of carbon dioxide of the developer, and the control portion includes a first control block that controls the control. The valve sends a control signal, and the concentration of the alkali component calculated by the operation block becomes a predetermined management value. The fourth control block sends a control signal to the control valve, and the development measured by the second measurement means. The characteristic value of the liquid falls into a predetermined management area; and a fifth control block sends a control signal to the control valve, and the carbon dioxide concentration calculated by the calculation block becomes below a predetermined management value.

(14) The developer management device according to (11), wherein the calculation unit includes a calculation block that calculates a concentration of an alkali component of the developer, a concentration of a photoresist, and a concentration of carbon dioxide, and the control unit includes: a first The control block sends a control signal to the control valve, so that the concentration of the alkali component calculated by the calculation block becomes a predetermined management value; the second control block sends a control signal to the control valve, and does not use the calculation block The calculated concentration of the photoresist falls below a predetermined management value; and the fifth control block sends a control signal to the control valve, and the carbon dioxide concentration calculated by the calculation block becomes below a predetermined management value.

According to the present invention, since the component concentration of a multi-component alkaline developer is calculated by an arithmetic means using a multivariate analysis method (for example, a multiple regression analysis method), the measured characteristic value and the specific component concentration are Compared with the conventional method of calculating the component concentration under a predetermined correlation (for example, a linear relationship), the component concentration of the developer can also be calculated with high accuracy from the characteristic value affected by the components of the plurality of developers. In particular, according to the present invention, it is possible to measure the absorbed carbon dioxide concentration of a developer which is conventionally difficult to measure. In addition, compared with the method of preparing the correlation between a plurality of measurement characteristic values and a plurality of component concentrations (matrix) in advance and using the method for calculating the component concentration, the present invention does not need to prepare a large number of samples and perform preliminary measurement. In addition, in the present invention, the measurement results can be easily confirmed.

According to the present invention, since the concentration of each component of a multi-component alkaline developing solution can be measured with higher precision than that known, it is possible to control the concentration of the alkali component, the concentration of the dissolved photoresist, and the concentration of carbon dioxide absorption more accurately than those known. . In addition, according to the present invention, management that controls the conductivity value of the developer to a fixed value and management that controls the absorbance value of the developer to a fixed value or less can be selected.

A‧‧‧component concentration measuring device

B‧‧‧Development process equipment

C‧‧‧Replenishment liquid storage department

D‧‧‧Circulation stirring mechanism

E‧‧‧Developer Management Device

1‧‧‧Measurement Department

11‧‧‧The first measurement method

12‧‧‧Second measurement method

13‧‧‧Third measurement method

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

11b, 12b, 13b‧‧‧Measurement probe

14, 14a, 14b, 14c ‧‧‧ sampling pump

15, 15a, 15b, 15c ‧‧‧ sampling piping

16, 16a, 16b, 16c ‧‧‧ return piping

17‧‧‧ liquid delivery pump

18‧‧‧ liquid delivery piping

19‧‧‧ Waste liquid piping

2‧‧‧ Computing Department

21‧‧‧Operation block using multivariate analysis

22‧‧‧Calculation block using calibration curve method

23‧‧‧ Computing control unit (e.g. computer)

3‧‧‧Control Department

31, 32, 33‧‧‧ control blocks

4‧‧‧ valve

41 ~ 43‧‧‧Control Valve

44, 45‧‧‧ valve

46, 47‧‧‧ Valves for pressurized gas

5‧‧‧ signal line

51 ~ 53‧‧‧Signal cable for measurement data

54‧‧‧ signal line for operation data

55 ~ 57‧‧‧Signal cable for control signal

61‧‧‧Developer storage tank

62‧‧‧ Overflow trough

63‧‧‧ level meter

64‧‧‧Developing chamber cover

65‧‧‧ roller conveyor

66‧‧‧ substrate

67‧‧‧Developer spray head

71‧‧‧ waste liquid pump

72, 74‧‧‧Circulation pump

73, 75‧‧‧ filters

8‧‧‧ fluid line

80‧‧‧Developer solution line

81, 82‧‧‧ replenishing solution (developing solution and / or new solution)

83‧‧‧Pure water pipeline

84‧‧‧ Confluence pipeline

85‧‧‧Circulation pipeline

86‧‧‧Pipe for nitrogen

9‧‧‧ Refill liquid storage tank, others

91, 92‧‧‧ replenishment solution (developing original solution and / or new solution) storage tank

93‧‧‧Add test reagent

10‧‧‧ Measurement data memory

101‧‧‧Memory Block

DP‧‧‧ Display

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

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

FIG. 3 is a flowchart showing a method for measuring a component concentration of a signal flow when a calculation method different from the multivariate analysis method is included.

FIG. 4 is a schematic diagram of a component concentration measuring device for measuring two components of a developing solution.

FIG. 5 is a schematic diagram of a component concentration measuring device for measuring three components of a developing solution.

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

FIG. 7 is a schematic diagram of a component concentration measurement device in a case where the measurement unit and the calculation unit are separated and an inline measurement is performed.

FIG. 8 is a schematic diagram of a component concentration measuring device in a case where the measuring means is composed of a main body and a probe portion.

FIG. 9 is a schematic diagram of a component concentration measurement device including measurement means in parallel.

FIG. 10 is a schematic diagram of a component concentration measurement device in the case where a measurement device for adding a drug is required.

FIG. 11 is a schematic diagram of applying a component concentration measuring device to a developing solution management device.

FIG. 12 is a schematic diagram showing an application example of a component concentration measuring device.

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

FIG. 14 is a flowchart of a developing solution management method in which one of two components of the developing solution is controlled by the component concentration and the other is controlled by the characteristic value.

FIG. 15 is a flowchart of a developing solution management method in which three components of a developing solution are managed by component concentrations.

FIG. 16 is a flowchart of a developing solution management method in which one of the three components of the developer is characterized by the characteristic value and the other two are managed by the component concentration.

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

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

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

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

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

FIG. 22 is a schematic diagram of a developing solution management device in which two components of a developing solution are managed by the component concentrations.

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

FIG. 24 is a schematic diagram of a developing solution management device in which one of the three components of the developing solution is controlled by the characteristic value and the other is controlled by the component concentration.

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

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to appropriate drawings. However, the shape, size, size ratio, and relative arrangement of the devices and the like described in these embodiments should not be limited to the contents illustrated in the scope of the present invention unless there is specific description, but only It is only a schematic illustration as a simple explanation example.

In the following description, as a specific example of the developing solution, a 2.38% tetramethyl ammonium hydroxide aqueous solution (hereinafter, hydroxide Tetramethylammonium is called TMAH.) However, the developer to which the present invention is applied is not limited thereto. Examples of other developing solutions to which the component concentration measuring device and developing solution management device of the developing solution of the present invention can be applied include aqueous solutions of inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, and sodium silicate. And trimethyl monoethanol ammonium hydroxide (choline: choline).

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

In the development processing process, an unnecessary portion of the photoresist film after the exposure processing is dissolved through a developing solution to perform development. The photoresist dissolved in the developing solution generates a photoresist salt with the alkali component of the developing solution. Therefore, if the developing solution is not properly managed, the developing solution will be degraded by the consumption of the alkali component having developing activity as the developing process proceeds, and the developing performance will continue to deteriorate. At the same time, the photoresist dissolved in the developing solution is gradually accumulated in the form of a photoresist salt with an alkali component.

The photoresist dissolved in the developing solution exhibits an interfacial active effect in the developing solution. Therefore, the photoresist dissolved in the developer improves the wettability of the developer for the photoresist film used for the development treatment and improves the affinity of the developer and the photoresist film. Therefore, in a developing solution containing a photoresist moderately, the developing solution is also spread in the fine recessed portions of the photoresist film, and the photoresist film having fine unevenness can be well developed.

Moreover, in recent years, with the increase in the size of the substrate, a large amount of the developing solution is repeatedly used, and therefore the chance of the developing solution being exposed to the air increases. However, when the alkaline developer is exposed to air, it absorbs carbon dioxide in the air. Carbon dioxide is formed between the absorbed carbon dioxide and the alkali component of the developing solution. Therefore, if the developing solution is not properly managed, the alkali component having developing activity in the developing solution will be consumed by carbon dioxide and reduced. At the same time, the carbon dioxide absorbed in the developing solution gradually accumulates in the case of carbonate generated with an alkali component.

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

In this way, unlike the previous recognition that the developing activity of the developing process is deactivated, the photoresist dissolved in the developing solution and the carbon dioxide absorbed will actually help the developing performance of the developing solution. Therefore, it is necessary to manage the developer solution that dissolves the photoresist and absorbs carbon dioxide at the optimal concentration under the condition that the dissolving photoresist and the absorption of carbon dioxide are allowed to dissolve in the developing solution, rather than dissolving the photoresist. And absorb the carbon dioxide completely remove the developer management.

In addition, a part of the photoresist salt, carbonate, etc. generated in the developing solution is dissociated to generate various free ions such as photoresist ion, carbonate ion, bicarbonate ion. Moreover, these free ions can affect the conductivity of the developer at various contributing rates.

The analysis of the component concentration of the conventional alkaline developer is based on the good linear relationship between the alkali component concentration of the developer and the conductivity value of the developer, and the dissolved photoresist concentration of the developer has a good absorbance value with the developer. (Hereinafter referred to as the "learning method"). The developer management accuracy required in the conventional development process also has a small amount of carbon dioxide absorption, which can be fully realized by using this analysis method.

The conductivity value of the developer is a physical property value that depends on the number of charged particles such as ions contained in the developer and the amount of charge thereof. As described above, not only the alkali component is present in the developing solution, but also various free ions derived from the carbon dioxide absorbed by the developing solution and the photoresist dissolved in the developing solution. Therefore, in order to improve the analysis accuracy of the component concentration, it is necessary to use a calculation method that also incorporates the influence of these free ions on the conductivity value of the developing solution.

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

As a result of intensive research on these points, the inventors have found that if a multivariate analysis method (for example, a multiple regression analysis method) is used in the calculation method, the developer can be accurately calculated from the case of using a conventional method. The concentration of each component and the concentration of absorbed carbon dioxide that is difficult to measure conventionally can be measured. In addition, the inventors have found that if the component concentration of the developing solution calculated by a multivariate analysis method (for example, multiple regression analysis method) is used, the dissolved photoresist concentration and carbon dioxide absorption concentration of the developing solution can be maintained and managed in a good condition. status.

The inventor assumes that when a 2.38% TMAH aqueous solution is managed, a TMAH aqueous solution prepared by varying the alkali component concentration, dissolved photoresist concentration, and carbon dioxide absorption concentration as a simulated developer solution is prepared. The inventors carried out experiments to determine the component concentration by using a multiple regression analysis method from various characteristic values measured for these simulated developer samples. Hereinafter, a general calculation method using a multiple regression analysis method will be described. Then, based on an experiment performed by the inventor, a calculation method for a component concentration of a developer using a multiple regression analysis method will be described.

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

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

Mathematical formula 2C = A. S

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

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

For p samples with unknown concentrations, measure p characteristic values. If these characteristic values are set to Au (Au _k ; k = 1 to p), then these characteristic values can be multiplied by S to obtain the required concentration Cu ( Cu _j ; j = 1 to n).

Mathematical formula 4Cu = Au. S

This is the forecast stage.

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

The experiment is based on 11 calibration standard solutions. The conductivity value, the absorbance value and the density value at a wavelength λ = 560nm are measured as the characteristic values of the developing solution. Multiple linear regression analysis ) Calculate the concentration of each component.

The measurement method was performed by adjusting the temperature of the calibration standard solution to 25.0 ° C. The temperature is adjusted by immersing a bottle containing the calibration standard solution in a constant-temperature water tank whose temperature is controlled near 25 ° C for a long time, taking a sample, and then using a temperature controller to set it to 25.0 ° C immediately before the measurement . The conductivity meter is a conductivity meter manufactured by our company. The measurement was performed using a conductivity flow cell made by our company that had been treated with platinum black. The conductivity meter is inputted with the cell constant of the conductivity flow cell confirmed by the calibration operation. The absorbance photometer also uses our products. The absorbance photometer includes a light source section, a photometric section, and a glass flow cell having a wavelength λ = 560 nm. The density measurement uses a densitometer, which is a densitometer using a natural vibration method for obtaining density from a natural vibration frequency measured by exciting a U-shaped tube through a flow channel. The units of the measured conductivity value, absorbance value, and density value are mS / cm, Abs. (Absorbance), and g / cm ^{3, respectively} .

Regarding the method used in the calculation, one of the 11 calibration standard solutions was used as the unknown sample, and the calibration array was obtained based on the remaining 10 standards. The concentration of the assumed unknown sample was calculated, and the known value ( Comparison method (concentration value, weight modulation value measured by other correct analysis methods) for comparison (Leave-One-Out method).

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

In the calculation of MLR-ILS, since the TMAH aqueous solution is strongly alkaline and easily deteriorated due to absorption of carbon dioxide, the concentration matrix used in the calculation uses a titration analysis that can accurately analyze the concentration of the alkali component and the concentration of absorbed carbon dioxide. The calibration standard solution was used to determine the value. However, for the dissolved photoresist concentration, a weight modulation value is used.

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

The density matrix is shown in Table 2 below.

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

The correction matrix is shown in Table 4.

Table 5 presents a comparison of the concentration measurements in Table 2 with the calculated MLR-ILS values in Table 1.

As shown in Table 5, the TMAH concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration obtained by the multiple regression analysis method all correspond to the TMAH concentration, the absorbed carbon dioxide concentration, and the adjusted weight from the titration analysis. The obtained dissolved photoresist concentration is a fairly similar value.

In this way, it is understood that by measuring the conductivity of the alkaline developer, the absorbance at a specific wavelength, and the density, and using a multivariate analysis method (for example, multiple regression analysis method), the alkali component concentration and dissolution resistance of the developer can be measured. Agent concentration and carbon dioxide absorption.

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

Here, the characteristic value of the developer that is “related to the component concentration” refers to a relationship in which the characteristic value is related to the component concentration, and the characteristic value changes as the component concentration changes. For example, among the component concentrations of a developer, the so-called characteristic value a of the developer, which is at least related to the component concentration A, means that when the characteristic value a is to be obtained by using a function with the component concentration as a variable, one of the variables must include the component concentration A . The characteristic value a may be only a function of the component concentration A, but in general, in addition to the component concentration A, it is also formed as a multivariate function using the component concentration B or C as a variable, and a multivariate analysis method (for example, multiple regression analysis Law) is of great significance.

In addition, a component concentration is a degree which shows the relative amount of the component with respect to the whole. The component concentration of a mixed solution, such as a repeatedly used developing solution, may increase or decrease with time. The concentration of the component cannot be determined individually, but it is usually a function of the concentration of other components. Therefore, there are many cases where the relationship between the characteristic value of the developing solution and the component concentration is difficult to display with a flat graph. In such a case, it is not possible to calculate the component concentration from the characteristic value of the developing solution using an algorithm or the like of a calibration curve.

However, if a multivariate analysis method (for example, multiple regression analysis method) is used, as long as a set of measurement values of a plurality of characteristic values related to the component concentration to be calculated is collected, and these measurement values are used in the calculation, that is, A group of component concentrations can be calculated. Even if it is a component concentration that seems difficult to measure based on conventional knowledge, the component concentration measurement using a multivariate analysis method (for example, multiple regression analysis method) can obtain a significant effect that the component concentration can be measured by measuring characteristic values. .

As described above, according to the calculation method of the present invention, the alkali component concentration, the dissolving photoresist concentration, and the dissolving photoresist concentration of the developing solution can be calculated based on the measured values of the characteristic values of the developing solution (for example, conductivity, absorbance at specific wavelength, and density), and Absorption of carbon dioxide concentration. According to the calculation method of the present invention, the concentration of each component can be calculated with higher accuracy than the conventional method.

In addition, since a multivariate analysis method (for example, a multiple regression analysis method) is used in the present invention, the characteristics of the developing solution that is wirelessly related to the specific component concentration of the developing solution can be used in the calculation of the component concentration of the developing solution. value.

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

Furthermore, since the present invention uses a multivariate analysis method (for example, a multiple regression analysis method), it is possible to accurately calculate the carbon dioxide absorption concentration of a developer that is difficult to measure conventionally.

Next, specific embodiments will be described with reference to the drawings. In the following examples, the characteristic values a, b, c,..., The component concentrations A, B, C,... And the like are appropriately described using letters. For a more specific understanding, the characteristic values a, b, c, ... are re-understood respectively as conductivity, absorbance, density, ... at a specific wavelength (for example, λ = 560nm), and component concentrations A, B, C, ... can be re-understood respectively as the concentration of alkali component, the concentration of dissolved photoresist, the concentration of absorbed carbon dioxide, etc.

Among them, the characteristic values a, b, and c are set to electrical conductivity, absorbance and density at a specific wavelength (for example, λ = 560 nm), etc. After all, the concentration of the alkali component of the developer, the concentration of the dissolved photoresist, The combination of the optimal characteristic values in the case of absorbing carbon dioxide concentration and the like is exemplified, but it is not limited thereto. The characteristic values a, b, c, ... can be selected in various combinations according to the component concentrations A, B, C, .... The usable characteristic values include, for example, the conductivity, absorbance, ultrasonic propagation speed, refractive index, density, titration end point, pH, and the like of the developer. Since the developing solution may contain various additives, the component concentration may contain additive concentrations and the like in addition to the three components described above.

In the case of measuring the concentration of the alkali component of the developing solution, the concentration of the dissolved photoresist, and the concentration of carbon dioxide absorption to manage the developing solution, it is suitable to use a combination of conductivity, absorbance at a specific wavelength, and density as characteristic values. The specific wavelength for measuring absorbance is preferably a visible wavelength, preferably a specific wavelength in a wavelength region of 360 to 600 nm, and more preferably a wavelength λ = 480 nm or 560 nm. This is because when the concentration of carbon dioxide absorbed by the developer is small and its change with time is gentle, the conductivity of the developer is in a good linear relationship with the concentration of the alkali component. One of the specific wavelengths of the developer (for example, λ = 560nm) The reason is that the absorbance and dissolved photoresist concentration have a good linear relationship. In addition, a combination of electrical conductivity, absorbance at a specific wavelength and ultrasonic propagation speed, a combination of electrical conductivity, absorbance at a specific wavelength, and refractive index can also be preferably used.

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

FIG. 1 is a flowchart showing a component concentration measurement method according to the present embodiment in which signals flow when a component concentration of two components of a developer is measured from two characteristic values of the developer.

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

FIG. 2 is a flowchart of a component concentration measurement method according to this embodiment, showing the flow of signals when the component concentrations of three or more components of the developer are measured from three or more characteristic values of the developer. .

In the component concentration calculation method of this embodiment, first, in the step of measuring the characteristic values a, b, c, ... of the developing solution, the respective measurement values a _m , b _m , c _m , ... are obtained. The obtained measured values a _m , b _m , c _m ,... Are sent to a calculation step. Next, the calculation step receives the measured values a _m , b _m , c _m , ..., and uses these to calculate the component concentrations A, B, C, ... by a multivariate analysis method (for example, a multiple regression analysis method). . In this way, the component concentrations A, B, C, ... are measured. When this process is repeated, the component concentrations A, B, C, ... of the developer can be continuously measured.

FIG. 3 is a diagram showing the component concentration measurement of the present embodiment in the case where a plurality of component concentrations are measured from characteristic values of a plurality of developing solutions, and the calculation step includes a flow of signals using a method different from the multivariate analysis method. Method flow chart.

This embodiment can be suitably adopted in the case where the characteristic value p of the developer solution, which is related only to the concentration P of a certain component of the developer solution, is used as a measurement target. More specifically, for example, the alkali component concentration and the carbon dioxide absorption concentration of the developing solution can be calculated from the conductivity value and the density value of the developing solution by a multivariate analysis method, and the concentration of the photoresist dissolved in the developing solution can be used and specified. A case where a linear relationship between absorbances at a wavelength (for example, λ = 560 nm) is calculated as a calibration curve and measured.

In the method for measuring the component concentration of the developing solution according to this aspect, in the measuring step, characteristic values a, b, ... of the developing solution having a plurality of component concentrations as variables are measured, and The characteristic values p, ... of the developing solution, and the measured values a _m , b _m , ..., and p _m , ... are sent to a calculation step.

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

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

The step of calculating the component concentration by a calculation method different from the multivariate analysis method (for example, the calibration curve method) is to use the linear relationship between the characteristic value p and the component concentration P that have been obtained in advance as a calibration curve, etc. The measured values of the characteristic values p, ... of the developing solution are used to calculate the component concentrations P, ....

The above method for measuring the component concentration of a developing solution includes: a measuring step of measuring a plurality of characteristic values of the developing solution related to the component concentration of the developing solution; and a calculation step of calculating by a multivariate analysis method based on the measured plurality of characteristic values. Component concentration of the developer.

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

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

Hereinafter, the embodiment relates to a component concentration measuring device for a developing solution of the present invention.

    [First Embodiment]    

FIG. 4 is a schematic diagram of a component concentration measuring device for measuring two components of a developing solution. For convenience of explanation, the component concentration measuring device A of the developing solution is illustrated together with the developing process equipment B in a state of being connected to the developing process equipment B.

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

The development process equipment B is mainly composed of a developer storage tank 61, an overflow tank 62, a development chamber hood 64, a roller conveyor 65, a developer nozzle 67, and the like. The developer is stored in the developer storage tank 61. The developer solution is managed by supplemental supplemental solution, but it is omitted in FIG. 4. The developer storage tank 61 is provided with a liquid level meter 63 and an overflow tank 62 to manage the increase in the amount of liquid caused by the replenishment and replenishment. The developer storage tank 61 and the developer spray head 67 are connected by a developer liquid line 80. The developer stored in the developer storage tank 61 is circulated by a circulation pump 72 provided in the developer liquid line 80 through a filter 73. Conveyed to the developer spray head 67. The roller conveyor 65 is provided above the developer storage tank 61 to carry a substrate 66 formed with a photoresist film. The developer is dropped from the developer spray head 67, and the substrate 66 transferred by the roller conveyor 65 is immersed in the developer through the dropped developer. After that, the developer is recovered by the developer storage tank 61 and stored again. In this way, the developing solution is repeatedly used in the developing process cyclically. In addition, in a developing chamber in a small glass substrate, a treatment that does not absorb carbon dioxide in the air may be applied by filling it with nitrogen or the like. In addition, the degraded developing solution is discharged (drain) by operating the waste liquid pump 71.

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

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

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

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

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

The developing solution collected by the sampling pump 14 from the developing solution storage tank 61 is introduced into the measuring unit 1 of the component concentration measuring device A through a sampling pipe 15. After that, if the temperature adjustment means is provided, the sampled developer solution is sent to the temperature adjustment means to be maintained at a predetermined measurement temperature (for example, 25 ° C.), and is sent to the measurement means 11, 12. The characteristic value a of the developing solution is measured by the first measuring means, and the characteristic value b of the developing solution is measured by the second measuring means. The developer solution 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 developing solution 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 measured data. The signal lines 51 and 52 are sent to an arithmetic block 21 using a multivariate analysis method. The calculation block 21 that has received the measurement values a _m and b _m calculates the component concentrations A and B of the developing solution by calculating these measurement values by a multivariate analysis method. In this way, the component concentrations A and B of the developing solution are measured by the component concentration measuring device A.

The component concentration measuring device A of the embodiment includes a display portion DP. At least one of a characteristic value measured by the measurement unit 1 and a component concentration calculated by the calculation unit 2 is displayed on the display unit DP. As shown in FIG. 4, the component concentrations A and B calculated by the calculation section 2 may be displayed on the display section DP, and the characteristic value (not shown) of the developing solution measured by the measurement section 1 may be displayed. Both sides can also be displayed. In addition, any one of the characteristic value and the component concentration corresponding to each component of the developer may be selected and displayed.

The display portion DP may be a display monitor electrically connected to the component concentration measuring device A, or may be a touch panel computer in which the component concentration measuring device A is installed. In the case of a touch panel computer, the computing unit 2 may be included.

    [Second Embodiment]    

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

The component concentration measuring device A of the embodiment includes a display portion DP. The display section DP can display characteristic values (for example, a _m , b _m , and c _m ) measured by the measurement section 1 and component concentrations (for example, A, B, C) calculated by the calculation section 2. In the embodiment, the display of the display unit DP switching characteristic value and the component concentration can be performed by a switch key BT which is a display switching means provided on the display unit DP screen. In the embodiment, although the display is switched and displayed on the display portion DP, the measured characteristic values (a _m , b _m , c _m ) and the component concentration (A, B, C) may be displayed simultaneously. It is displayed on the display part DP.

In terms of display switching means, a switch to switch the display object displayed on the display part DP to the characteristic value or the component concentration can be installed outside the device, or it can be installed to be displayed on the display part's operable GUI (graphic use User interface). In addition, the display switching means may be the switching of characteristic value display or component concentration display for all components collectively, or it may be possible to switch individually for each component.

    [Third embodiment]    

FIG. 6 is a schematic diagram of a component concentration measuring device having an arithmetic block using an arithmetic method different from the multivariate analysis method in the arithmetic section 2. For example, it is suitable for the case where the characteristic value of a developing solution and the component concentration are grouped from the measured physical property value of the developing solution by a calibration curve method or the like.

The component concentration measuring device A according to this embodiment includes a measuring unit 1 that measures a plurality of characteristic values of a developing solution, and a computing unit 2 that calculates a component concentration of the developing solution from the measured values. The arithmetic unit 2 includes an arithmetic block 21 using a multivariate analysis method, and an arithmetic block 22 using an arithmetic method (for example, a calibration curve method) other than the multivariate analysis method.

The measured value of the characteristic value of the developing solution used for calculation in the multivariate analysis method is an arithmetic block 21 using the multivariate analysis method after being measured by the measurement unit 1 and sent to the arithmetic unit 2. The measured value of the characteristic value of the developer used in a calculation method (such as a calibration curve method) other than the multivariate analysis method is sent to the calculation block 22. By performing calculations in the calculation blocks 21 and 22, the component concentration of the developing solution is calculated.

In addition, the operation block 22 using an operation method other than the multivariate analysis method (for example, the calibration curve method) may be a complex number. There is no restriction on the order of operations using multivariate analysis methods and operations using other methods (such as the calibration curve method). The description of other components and the like which are the same as those of the above embodiment is omitted.

The component concentration measuring device A of the embodiment includes a display portion DP. The component concentration measuring device A includes a measurement data storage unit 10 including a memory block 101. The measurement data storage unit 10 memorizes the component concentration calculated by the calculation unit 2 together with at least one of the measurement time and the elapsed time from the start of the measurement. In addition, the memory block 101 may be configured by a plurality of memory blocks.

As shown in FIG. 6, the display unit DP may store data of component concentrations (for example, A, B, and C) stored in the measurement data storage unit 10 to memorize the measurement time in the measurement data storage unit 10 or from the measurement. The elapsed time from the start of calculation is displayed as a graph.

    [Fourth embodiment]    

FIG. 7 is a schematic diagram of a component concentration measurement device in which the measurement unit 1 and the calculation unit 2 are separated. In the component concentration measuring device A of this embodiment, the measurement section 1 is provided on a bypass line from the developer solution line 80 of the development process equipment B, and the measurement data signal lines 51 to 53 and the calculation section 2 are provided. connection. It may also be directly connected to the developer line 80, other lines, and the like. Instead of the sampling pump 14, a flow regulating valve (not shown) or the like may be used in combination.

The component concentration measuring device A of the embodiment includes a display portion DP. The component concentration measuring device A includes a measurement data storage unit 10 including a memory block 101. The measurement data storage unit 10 includes the characteristic values (for example, a _m , b _m , and c _m ) measured by the measurement unit 1 and the component concentrations (for example, A, B, C) calculated by the calculation unit 2 together with the measurement. At least one of the time and the elapsed time from the start of the measurement is memorized together.

The display unit DP stores at least one of the characteristic values (a _m , b _m , c _m ) and the component concentrations (A, B, C) stored in the measurement data storage unit 10 to memorize the measurement data storage unit 10. The time or the elapsed time from the start of the measurement is used as an indicator to display the graph. In the embodiment, the display part DP can switch the graph display of the characteristic value and the component concentration by a switch key BT which is a display switching means provided on the screen of the display part DP. Although the embodiment shows a case where the graph display is switched and displayed on the display portion DP, the graph display of the characteristic values (a _m , b _m , c _m ) and the component concentration (A, B, C) may be displayed simultaneously Display part DP.

As for the display switching means, a switch for switching a graph of a characteristic value or a graph of component concentration to be displayed on the display part can be installed outside the device, or it can be installed as an operable GUI displayed on the display part. (Graphics user interface). In addition, the display switching means may be the switching of characteristic value display or component concentration display for all components collectively, or it may be possible to switch individually for each component.

    [Fifth embodiment]    

FIG. 8 is a schematic diagram of a component concentration measuring device in a case where the measuring means 11 to 13 for measuring the characteristic value of the developing solution are composed of the respective measuring device bodies 11a, 12a, 13a and the measuring probes 11b, 12b, 13b. The component concentration measuring device of this embodiment includes a display portion DP. The same display as that of the first to fourth embodiments can be performed through the display portion DP.

In this embodiment, the measurement probes 11b to 13b of the measurement means 11 to 13 measure the characteristic value of the developing solution through the developing solution immersed in the developing solution storage tank 61. The measured characteristic value of the developer is sent to the arithmetic unit 2 through the signal lines 51 to 53 for measurement data. The component concentration is calculated in the calculation unit 2 by a multivariate analysis method, and the component concentration of the developing solution is measured.

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

    [Sixth Embodiment]    

FIG. 9 is a schematic diagram of a component concentration measurement device in a case where measurement means in the measurement unit 1 arranged in parallel are provided. The component concentration measuring device of the embodiment includes a display portion DP. The same display as that of the first to fourth embodiments can be performed through the display portion DP.

The measurement means constituting the measurement unit 1 is not limited to the case of being connected in series, and may be connected in parallel. As shown in FIG. 9, the measurement means 11 to 13 may include sampling pipes 15a to 15c, sampling pumps 14a to 14c, and return pipes 16a to 16c, respectively. They may also be connected in parallel through pipes that diverge in the middle . The characteristic value of the developing solution measured by the measuring means 11 to 13 is sent to the arithmetic unit 2. The component concentration of the developer is calculated in the arithmetic unit 2 by a multivariate analysis method.

    [Seventh embodiment]    

FIG. 10 is a schematic diagram of a component concentration measuring device in a case where, for example, an automatic titration device is equipped with a measuring device that requires addition of a drug. In FIG. 10, the third measurement means 13 is a measurement device that requires addition of a drug. The component concentration measuring device of the embodiment includes a display portion DP. The same display as that of the first to fourth embodiments can be performed through the display portion DP.

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

As described above, as shown in the first to seventh embodiments, the component concentration measuring device according to the present invention includes the measuring unit 1 that measures a plurality of characteristic values of the developing solution related to the component concentration of the developing solution; The plurality of characteristic values of the developing solution measured by the section 1 and the component concentration of the developing solution are measured by a multivariate analysis method; and the display section DP.

The measurement unit 1 of the component concentration measuring device A of this embodiment can take various embodiments. The measuring device used as a measuring means is appropriately installed and connected in accordance with the measuring method to be used by the measuring device. Therefore, the measuring unit 1 of the component concentration measuring device of the present invention should be set to the most suitable according to the measuring method Just make up.

The measurement unit 1 may include measurement means necessary for measuring a plurality of characteristic values of the developer. It is desirable that the measurement unit 1 includes a temperature adjustment means (not shown). Although it is desirable that the sampling pump 14, the infusion pump 17, the waste liquid piping 19, and the like are appropriately provided as necessary, it does not necessarily mean that all of them are internal parts of the measurement unit 1.

The measurement unit 1 and the calculation unit 2 may be integrated or separated. The measurement unit 1 and the calculation unit 2 may be interconnected so long as the calculation unit 2 can receive measurement data of characteristic values of the developing solution measured by the measurement unit 1. The measurement unit 1 and the calculation unit 2 are not limited to the case of being connected by a signal line, and may be configured to be capable of transmitting and receiving data wirelessly. It is not necessary to form a measurement unit 1 by integrating a plurality of measurement means in one place, and a specific measurement means may be placed separately.

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

In addition, the measurement of the plurality of characteristic values of the developer in the measurement section 1 of this embodiment is not limited to the order. The arrangement of each measurement means in the measurement unit 1 in the drawings from FIG. 4 to FIG. 10 and the "first" in the description of "first measurement means", "second measurement means", ... The terms "second", "..." and the like do not limit the order of determination in the present invention. The words "first", "second", ... are just for the convenience of distinguishing each of the plurality of measuring means.

For example, if the arithmetic unit 2 of the component concentration measuring device of the present embodiment includes an arithmetic block 21 using a multivariate analysis method, it may further include an arithmetic block using a method other than the multivariate analysis method (for example, a calibration curve method). In this case, the order of operations is not limited.

In the component concentration measuring device of this embodiment, each measuring means constituting the measuring unit 1 is arranged and connected in a manner suitable for the measuring method, and a plurality of characteristic values of the developer are measured. The computing unit 2 receives the measured values measured by the measuring unit 1. The measured value of the characteristic value of the developing solution was calculated by the multivariate analysis method (included in the calculation method).

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

    [Eighth embodiment]    

FIG. 11 is a schematic diagram of a developer management device using the component concentration measuring device of the present embodiment.

In the present embodiment, the component concentration measurement device A is connected to the control unit 3 (control device) that controls the control valves 41 to 43 via a signal line 54 for operation data. The control unit 3 (control device) is connected to each of the control valves 41 to 43 via signal lines 55 to 57 for control signals. 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 supplying pure water. The component concentration measuring device A includes a display portion DP.

The replenishment liquid storage tanks 91 and 92 are pressurized with nitrogen, and pass through the control unit 3 (control device) to open and close the control valves 41 to 43. The replenished replenishment liquid is returned to the developer storage tank 61 by the circulation pump 74 through the circulation line 85 and is stirred. The method, mechanism, and the like of the replenishing operation of the replenishing liquid are described in the embodiments of the developer management method and the developer management device described later.

As described above, the component concentration measuring device according to the present embodiment can be used as a component of the developing solution management device by being combined with a control valve provided on a pipeline for supplying a replenishing solution to the developing solution and a control device for controlling the same.

In addition, the so-called replenishing liquid means, for example, a stock solution, a fresh solution, a regenerating solution, and the like of a developing solution. In some cases, pure water is included. The so-called dope means an unused developing solution having a strong alkali component concentration (for example, a 20 to 25% TMAH aqueous solution). The so-called fresh solution means that the concentration of the alkali component is the same concentration as the concentration used in the development process and is not used (eg, a 2.38% TMAH aqueous solution). The regenerating solution means removing unnecessary substances from the used developing solution to make a reusable developing solution. These differ in use, effect, etc. as a supplement. For example, the original solution is a supplement solution for increasing the concentration of alkali components, reducing the concentration of dissolved photoresist and absorbing carbon dioxide. The new liquid is a supplementary liquid used to maintain or gently increase or decrease the concentration of alkali components, reduce the concentration of dissolved photoresist, and absorb the concentration of carbon dioxide. Pure water is a supplement to reduce the concentration of each component. The same applies to the description of the following embodiments.

In addition, FIG. 11 illustrates a case where the supplementary liquid is supplied from the supplementary liquid storage tanks 91 and 92 through the supplemental liquid pipes 81 and 82, and the pure water is supplied through the pure water pipe 83. This is limited. In some cases, the replenishing liquid is sent from the replenishing liquid storage tanks 91 and 92 to a mixing tank (not shown), and then the replenishing liquid is sent to the developer storage tank 61 after being prepared to a predetermined concentration. In this case, the control valves 41 and 42 are provided in the middle of a pipeline for conveying the developer tank to the developer storage tank 61. In some cases, pure water is not directly supplied to the developer storage tank 61, and at this time, there is no pure water pipe 83, control valve 43, or the like. The same applies to the description of the following embodiments and the following drawings.

The replenishment solution is stored in the replenishment solution storage tanks 91 and 92 of the replenishment solution storage section C. The replenishment liquid storage tanks 91 and 92 are connected to a nitrogen gas line 86 provided with pressurized gas valves 46 and 47, and are pressurized by the nitrogen gas supplied through these lines. In addition, the replenishment liquid storage tanks 91 and 92 are connected to the replenishment liquid lines 81 and 82, respectively, and the replenishment liquid is conveyed through the normally open valves 44, 45. The replenishing liquid lines 81 and 82 and the pure water line 83 are provided with control valves 41 to 43. The control valves 41 to 43 are controlled to be opened and closed by the control unit 3. Through the operation of the control valve, the replenishment liquid stored in the replenishment liquid storage tanks 91 and 92 is pressure-fed, and pure water is delivered. After that, the replenishing liquid is merged with the circulation stirring mechanism D via the merging line 84 and is replenished to the developer storage tank 61 and stirred.

When the replenishment liquid stored in the replenishment liquid storage tanks 91 and 92 is reduced due to replenishment, the supply amount becomes unstable due to the decrease in the internal pressure. Therefore, the valve 46 for the pressurized gas is appropriately opened in response to the decrease in replenishment liquid. 47. Nitrogen is supplied to maintain the internal pressure of the replenishment liquid storage tanks 91 and 92. When the replenishment liquid storage tanks 91 and 92 become empty, the valves 44 and 45 are closed, and a new replenishment liquid storage tank filled with replenishment liquid is replaced, or the replenishment liquid prepared separately is refilled into the empty replenishment liquid storage tank 91 , 92.

    [Ninth Embodiment]    

The component concentration measuring device of the present embodiment can be used in combination with a warning lamp WL, an alarm device WT, and the like, and applied to a concentration abnormality alarm device of a developing solution and the like. FIG. 12 is a schematic diagram 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 component to various devices, systems, and the like.

13 to 17 show a developer management method according to the embodiment.

The developing solution management method of the present invention includes: a measuring step of measuring a plurality of characteristic values of a developing solution related to a component concentration of an alkaline developing solution; and an arithmetic step of calculating a development from the measured plurality of characteristic values by a multivariate analysis method. And a replenishing step of replenishing the developer with a replenishing solution according to a characteristic value of the measured developer solution or a calculated component concentration of the developer solution. The measurement steps and calculation steps are the same as the measurement steps and calculation steps in the aforementioned method for measuring the component concentration of a developer. Therefore, repeated descriptions thereof are omitted in the embodiments of FIGS. 13 to 17 below.

In the following description, the "predetermined management value" means a characteristic value or a component concentration value at which the best liquid performance is exhibited as a developer, and is a characteristic value or a component concentration that is known in advance based on experience, experiments, and the like. value. That is, a numerical value that becomes an index of the developing performance of the developer, such as a line width or a residual film thickness formed on the substrate after development, is a characteristic value or a component concentration value that is predicted in the best state. . The "predetermined management area" is also a range of such management values. The same applies to the description of the developer management device.

FIG. 13 is a flowchart of a developer management method for two components of a developer by component concentration management. The developing solution management method of this embodiment is preferably applicable to an alkaline developing solution that is managed to have a low absorption of carbon dioxide. The alkali component concentration of the developing solution becomes a predetermined management value and the dissolved photoresist concentration becomes Management of the developer in a manner below the predetermined management value.

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

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

The 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 concentration of the component A, the component concentration determination A is larger or smaller than the management value A _0. When it is large, a developing solution is replenished with a replenishing solution (for example, a new developing solution, pure water, etc.) that can dilute the component concentration A. In an hour, a developer is replenished with a replenisher (for example, a developer solution, a fresh solution, and the like) that has the effect of increasing the component concentration A. When the component concentration A is the same as its management value A ₀ , nothing is done.

In the step of adjusting the component concentration B, it is determined whether the component concentration B is larger than the management value B ₀ . When it is large, a replenishing solution (for example, a new developer solution that does not change the alkali component concentration, which is capable of diluting the component concentration B) is used to replenish the developer solution. In hours, do nothing.

14 is a flowchart of a developer management method in a case where one of the two components of the developer is managed by the component concentration and the other is managed by the characteristic value. The developing solution management method of this embodiment is preferably applicable to an alkaline developing solution that is managed to absorb less carbon dioxide. The alkali component concentration of the developing solution can be a predetermined management value and a specific wavelength of the developing solution ( For example, the absorbance at λ = 560 nm) may be used in the case where the developer is managed in a manner below the predetermined management value.

In this embodiment, the component concentration A is managed at a predetermined management value A ₀ , and the measured value b _m of the characteristic value b of the developing solution is managed at a predetermined management value b ₀ or less. The component concentration A is, for example, an alkali 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 developing solution are measured in the 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 developing solution are calculated from the measured values a _m and b _m by a multivariate analysis method. The component concentration A calculated by the calculation step and the measurement value b _m of the characteristic value b measured by the measurement step are sent to the replenishment step.

The replenishing step includes a step of adjusting the component concentration A and a step of adjusting the characteristic value b. Since the procedure of adjusting the component concentration A is the same as that in the case of FIG. 13, its description is omitted.

In the step of adjusting the characteristic value b, its measurement value b _{m is} compared with its management value b ₀ to determine whether it is large. When it is large, a replenishing solution (for example, a new developer solution that does not change the alkali component concentration, which is capable of diluting the component concentration B) is used to replenish the developer solution. In hours, do nothing.

Having monotonically increasing characteristic of the correlation between the concentration and the value b B, b values of transmission characteristics is managed as its management value b ₀ or less, the concentration of component B is a management value managed B become ₀ or less. When the characteristic value b and the component concentration B have a monotonically decreasing correlation, if the magnitude relationship of the judgment is reversed and the operation is performed, the component concentration B can similarly be managed to a management value B ₀ or less.

FIG. 15 is a flowchart of a developing solution management method in which three components of a developing solution are managed by component concentrations. The developing solution management method of this embodiment is preferably applicable to, for example, management of the alkali component concentration of the developing solution to a predetermined management value, management of the dissolved photoresist concentration to a predetermined management value or less, and absorption of carbon dioxide concentration. Cases where management becomes below a predetermined management value.

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

The characteristic values a, b, c, ... of the developing solution are measured in the measurement step, and the measured values a _m , b _m , c _m , ... are sent to the calculation step. In the calculation step, the component concentrations A, B, C, ... of the developing solution are calculated from the measured values a _m , b _m , c _m , ... by a multivariate analysis method. The component concentrations A, B, C, ... calculated by the calculation step are sent to the replenishment 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 concentration of the component A, the component concentration determination A is larger or smaller than the management value A _0. When it is large, a developing solution is replenished with a replenishing solution (for example, a new developing solution, pure water, etc.) that can dilute the component concentration A. In a small amount of time, a developing solution is replenished with a replenishing solution (for example, a developing solution original solution, a new solution, and the like) capable of increasing the component concentration A. When the component concentration A and the management value A ₀ are the same, nothing is done.

In the step of adjusting the component concentration B, it is determined whether the component concentration B is larger than the management value B ₀ . When it is large, a replenishing solution (such as a new developer solution that does not change the alkali component concentration, which is capable of diluting the component concentration B) is used to replenish the developer solution. In hours, do nothing.

In the step of adjusting the component concentration C, it is determined whether the component concentration C is greater than its management value C ₀ . When it is large, a replenishing solution (for example, a new developer solution that does not change the alkali component concentration, which is capable of diluting the component concentration C) is used to replenish the developer solution. In hours, do nothing.

FIG. 16 is a flowchart of a developing solution management method in which one of the three components of the developer is characterized by the characteristic value and the other two are managed by the component concentration. The developing solution management method of this embodiment is preferably applicable to the case where the alkali component concentration of the developing solution can be a predetermined management value, and the absorbance at a specific wavelength (for example, λ = 560 nm) of the developing solution can be a predetermined management value or less. And the case where the developer absorbs the carbon dioxide concentration and the developer can be managed in such a manner that it becomes a predetermined management value or less.

In this embodiment, it is assumed that the component concentration A is managed at a predetermined management value A ₀ , the measured value b _m of the characteristic value b of the developing solution is managed at a predetermined management value b ₀ or less, and the component concentration C is managed at a predetermined management value. C ₀ or less. The component concentration A is, for example, an alkali component concentration, 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, a concentration for absorbing carbon dioxide.

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

The 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. Since the steps of adjusting the component concentration A and the steps of adjusting the component concentration C are the same as those in FIG. 15, descriptions thereof are omitted.

In the step of adjusting the characteristic value b, its measured value b _{m is} compared with its management value b ₀ to determine whether it is large. When it is large, a replenishing solution (for example, a new developer solution that does not change the alkali component concentration, which is capable of diluting the component concentration B) is used to replenish the developer solution. In hours, do nothing.

Having monotonically increasing characteristic of the correlation between the concentration and the value b B, b values of transmission characteristics is managed as its management value b ₀ or less, the concentration of component B is a management value managed B become ₀ or less. When the characteristic value b and the component concentration B have a monotonically decreasing correlation, if the magnitude relationship of the judgment is reversed (that is, b _m <b ₀ ) and the operation is performed, the component concentration B can also be managed as its management value B ₀ or less.

FIG. 17 is a flowchart of a developing solution management method in which two of the three components of the developing solution are managed by characteristic values and the other is managed by the component concentration. The developing solution management method of this embodiment is preferably applicable to a case where the conductivity of the developing solution can be a predetermined management value, the absorbance at a specific wavelength (for example, λ = 560 nm) of the developing solution can be a predetermined management value or less, In addition, the carbon dioxide concentration absorbed by the developing solution may be used in a case where the developing solution is managed such that it becomes a predetermined management value or less.

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

The characteristic values a, b, and c of the developing solution are measured in the measurement step, and the measured values a _m , b _m , and c _m are sent to the calculation step. In the calculation step, the component concentrations A, B, and C of the developing solution are calculated from the measured values a _m , b _m , and c _m by a multivariate analysis method. Measured characteristic value of the measurement step of measuring a value of a _m, b is a value measured characteristic values of _m and b calculated by the calculating step based component concentration C is supplied to the supply step.

The 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. Since the step of adjusting the characteristic value b and the step of adjusting the component concentration C are the same as those in FIG. 16, descriptions thereof are omitted.

In the step of adjusting the characteristic value a, its measurement value a _{m is} compared with its management value a ₀ to determine whether it is larger or smaller. When it is large, a developing solution is replenished with a replenishing solution (such as a developing solution original solution or a fresh solution) that can dilute the component concentration A. In a small amount of time, a developing solution is replenished with a replenishing solution (such as a fresh developing solution or pure water) capable of increasing the component concentration A. Do nothing at the same time.

When the characteristic value a and the component concentration A have a monotonically increasing correlation, the transmission characteristic value a is maintained at its management value a ₀ so that the component concentration A is managed to be its management value A ₀ . When the characteristic value a and the component concentration A have a monotonically decreasing correlation, if the magnitude relationship of the judgment is reversed and operated, the component concentration A can also be managed to its management value A ₀ .

As described above, the developing solution management method shown in FIGS. 13 to 17 includes: a measuring step of measuring a plurality of characteristic values of the developing solution related to the component concentration of the developing solution; and a calculation step of using a plurality of characteristic values based on the measured plurality of characteristic values. The variable analysis method calculates the component concentration of the developer; and the replenishing step, based on the measured value or calculated value of the management target item selected from the plurality of characteristic values of the measured developer and the calculated component concentration of the developer, The developer is replenished.

The measurement step further includes: a measurement step of the measurement characteristic value a, a measurement step of the measurement characteristic value b, a measurement step of the measurement characteristic value c, and the like. However, the order of these steps is not limited. Can also be measured at the same time. The temperature adjustment step, reagent addition step, waste liquid step, etc. may include appropriate necessary steps depending on the measurement method.

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

The replenishing step includes: using the control target item (either the characteristic value or the component concentration of the developer) as the control amount, and supplying the developer to the developer in such a manner as to become the predetermined management value or below the predetermined management value or within the management area. The step of adjusting the component concentration A, the step of adjusting the component concentration B, the step of adjusting the component concentration C, and the like of the replenishment solution. The order is not limited by the order shown in the drawing.

In addition, as the control method, various control methods that can be used for the control in which the control amount is adjusted to the target value can be adopted. In particular, proportional control (P control) (Proportional Control), integral control (I control) (Integral Control), differential control (D control) (Differential Control), and control (PI control (Proportional) -Integral Control). It is more suitable for PID control.

In the embodiment of FIGS. 13 to 17 described above, the component concentration A of the developer is maintained at its management value A ₀ by repeating the measurement steps, calculation steps, and replenishment steps. The component concentration B of the developer is managed at its management value. The component concentration C is equal to or less than B ₀ and the management value C ₀ or less. Therefore, the developing solution management method of the embodiment can maintain the optimal developing performance and achieve a desired line width or residual film thickness.

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

The developing solution management device of this embodiment includes a measuring section 1 that measures a plurality of characteristic values of the developing solution related to the component concentration of the alkaline developing solution, and a computing section 2 that measures from the measuring section 1 by a multivariate analysis method. A plurality of characteristic values to calculate the component concentration of the developing solution; and the control unit 3, based on the characteristic value of the developing solution measured by the measuring unit 1 or the component concentration of the developing solution calculated by the computing unit 2 The control valves 41 to 43 on the liquid replenishment pipeline send out control signals. Since the measurement section 1 and the calculation section 2 of the developer management device of the present invention are the same as the measurement section 1 and the calculation section 2 in the component concentration measurement device of the developer described above, the eighteenth to the twenty-fifth are described below. The overlapping description is omitted in the embodiment.

    [Tenth embodiment]    

FIG. 18 is a schematic diagram for explaining a developing process of the developing solution management device of the present invention. The developing solution management device E of the present invention is illustrated together with the developing process equipment B, the replenishing solution storage section C, the circulation stirring mechanism D, and the like.

The developer management device E of this embodiment includes: a measuring unit 1 including a plurality of measuring means 11 to 13 for measuring a plurality of characteristic values of the developing solution; an arithmetic unit 2 including an arithmetic block 21 using a multivariate analysis method; and a control The unit 3 controls any one of the characteristic value or the component concentration of the developer as a control amount and makes it a predetermined management value or a method within a management area. The developer management device of this embodiment includes control valves 41 to 43 connected to the control unit 3 and controlled.

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

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

The details of the measurement operation and the calculation operation are the same as those of the component concentration measurement device of the developer described above, and therefore are omitted. The control operation will be described below.

The developing solution management device E is connected to the pipelines 81 to 83 (replenishing solution including pure water) to convey the replenishing solution to be replenished to the developing solution. Each of the pipes 81 to 83 is connected to control valves 41 to 43 controlled by the control unit 3 in the developer management device E.

The control unit 3 receives the measurement value of the characteristic value of the developing solution from the measurement unit 1 and the component concentration calculated by the calculation unit 2. The control unit 3 regards the characteristic value or component concentration of the received developer as a control amount, and sends a control signal to the control valves 41 to 43 based on the control amount. The control is performed, for example, such that the control amount becomes a predetermined management value or falls within a predetermined management area.

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

The control valves 41 to 43 are, for example, control valves that are opened while receiving an "open" signal. In the case of an on-off control valve that can perform a predetermined flow rate adjustment when the valve is opened, the control unit 3 can perform a predetermined time. The range sends an "on" signal to a control valve provided on a pipeline for supplying the replenishment solution to be replenished, thereby replenishing the developer with a necessary amount of developer solution required for management of the developer solution.

The control action of the control valve is not limited by this example. When the control valve is switched on and off according to the on-off switching signal, a pulsed on-off switching signal is sent to the control valve at a predetermined time interval through the control unit 3, and the developer is replenished with only the necessary amount of required Replenishment fluid.

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

The control valves 41 to 43 operate based on a control signal from the control unit 3 to supply the developer with an amount of replenisher required for developer management. The control unit 3 sends a control signal to the control valve to be controlled based on the type of replenishment liquid obtained from the received control amount (the characteristic value of the developer or the component concentration) and the necessary replenishment amount, and transmits the necessary replenishment amount.

In this way, with the developer management device of this embodiment, it can be maintained in such a manner that it becomes a predetermined management value or within a predetermined management area based on the measured characteristic value of the developer or the calculated component concentration of the developer. Manage developer.

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

First, the developer solution management is to supply the developer with replenishment solution in such a way that the alkali component concentration, dissolved photoresist concentration, and carbon dioxide absorption concentration of the alkaline developer solution used repeatedly can become predetermined management values. For example, according to the developer management device of the present invention, the alkali component concentration of a 2.38% TMAH aqueous solution can be managed to a predetermined management value within a range of 2.375 to 2.390 (wt%), and more preferably 2.380 (wt%), The dissolved photoresist concentration can be managed to a predetermined management value of 0.40 (wt%) or less, and more preferably 0.15 (wt%), and the absorbed carbon dioxide concentration can be managed to a predetermined management value of 0.40 (wt%) or less. Preferably, more preferably, it is 0.25 (wt%).

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

Third, the developer management is to supply the developer with replenishing solution in such a way that the alkali component concentration, the absorbance at a specific wavelength, and the absorbed carbon dioxide concentration of the alkaline developer used repeatedly can become predetermined management values. For example, according to the developer management device of the present invention, the alkali component concentration of a 2.38% TMAH aqueous solution can be managed to a predetermined management value in a range of 2.375 to 2.390 (wt%), and more preferably 2.380 (wt%), It is possible to manage the absorbance at a wavelength of λ = 560nm (slot optical path length d = 10mm) to a predetermined management value of 1.30 (Abs.) Or less, more preferably 0.50 (Abs.), And to manage the concentration of absorbed carbon dioxide to 0.40 The predetermined management value below (wt%) is better, more preferably 0.25 (wt%).

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

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

Sixth, the development is performed in such a manner that the conductivity of the reused alkaline developer can be a predetermined management value, the absorbance at a specific wavelength can be within a predetermined management area, and the concentration of absorbed carbon dioxide can be below the predetermined management value. Developer management of fluid replenishment. For example, according to the developer management device of the present invention, the conductivity of a 2.38% TMAH aqueous solution can be managed to a predetermined management value in the range of 54.47 to 54.75 (mS / cm), and more preferably 54.58 (mS / cm). It is possible to manage the absorbance at a wavelength of λ = 560nm (slot optical path length d = 10mm) to less than 1.30 (Abs.), More preferably 0.65 (Abs.) Or less, and to manage the concentration of absorbed carbon dioxide to 0.40 (wt%) ) The following is preferred.

Therefore, according to the developing solution management device of this embodiment, compared with a known person, since the concentration of each component or each characteristic value of the developing solution can be managed with high precision in a predetermined management value or a management area, the developing solution can be processed. Maintaining the best developing performance can achieve the desired line width or residual film thickness. In addition, various data and graphs can be displayed on the display portion DP.

    [Eleventh Embodiment]    

Fig. 19 is a schematic diagram for explaining a developing solution management device in which control valves 41 to 43 provided on a pipeline for supplying a replenishing solution to be supplied to the developing solution are external to the developing solution management device of this embodiment.

The developer management device E of this embodiment includes a measurement unit 1 including a plurality of measurement means for measuring a plurality of characteristic values of the developer, an operation unit 2 including an operation block 21 using a multivariate analysis method, and a control unit 3, The control signal 41 to 43 provided on the supply line of the replenishing liquid is controlled by using any one of the characteristic value or the component concentration of the developer as a control amount and making it a predetermined management value or a management area.

In this embodiment, the control valves 41 to 43 controlled by the control unit 3 are not internal components of the developer management device E. It is provided separately from the developer management device E on the pipeline for supplying replenishment. The developer management device E is not connected to these pipes for supplying the replenishing liquid. The other structures and operations are the same as those of the tenth embodiment, and are omitted.

    [Twelfth Embodiment]    

FIG. 20 is a schematic diagram of the developer management device E provided with the arithmetic control unit 23 having both arithmetic functions and control functions.

The developer management device E of the present invention is not limited to the case where the arithmetic unit 2 and the control unit 3 are configured as separate devices. It may be configured as an arithmetic control unit 23 that has both the arithmetic function and the control function. Examples of the arithmetic control unit 23 include a multifunction device such as a computer.

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

The other structures and operations are the same as those of the tenth embodiment, and are omitted.

    [Thirteenth Embodiment]    

FIG. 21 is a schematic diagram of a developer management device that manages two components of a developer. The developer management device E of the present embodiment is preferably applicable to the case where the concentration of the alkali component and the concentration of the dissolving photoresist in the alkaline developer that is managed to absorb less carbon dioxide are managed.

Assume that the first measuring means 11 is a measuring means (for example, a conductivity meter for measuring the conductivity) for measuring the characteristic value of the developing solution related to the concentration of at least the alkali component among the components of the developing solution, and the second measuring means 12 is for measuring the If the component of the developing solution measures at least the characteristic value of the developing solution related to the concentration of the photoresist (for example, an absorbance photometer for measuring absorbance at λ = 560 nm), the arithmetic unit 2 includes a calculation block using a multivariate analysis method. 21. Therefore, the concentration of the alkaline component of the developer and the concentration of the dissolved photoresist can be calculated from the characteristic values of the developer by the multivariate analysis method.

Therefore, the control block 31 sends a control signal to the control valve in such a manner that the conductivity or the concentration of the alkali component of the developing solution can become a predetermined management value, and the control block 32 is a specific wavelength of the developing solution (for example, λ = 560nm) The absorbance or dissolved photoresist concentration can be a predetermined control value or a control block that sends a control signal to the control valve in a manner within the management area, because the control unit 3 is capable of receiving the measured characteristic value of the developer. It is connected to the method of measuring the component concentration of the developer and the measurement unit 1 and the calculation unit 2. Therefore, the developer management device E of this embodiment can make the concentration of the alkali component of the developer into a predetermined management value and dissolve the solution. The developer is maintained and managed so that the photoresist concentration becomes a predetermined management value or within a management area.

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

    [Fourteenth Embodiment]    

FIG. 22 is a schematic diagram of a developing solution management device in which two components of a developing solution are managed by the component concentrations. The developing solution management device of this embodiment is preferably applicable to the case where the concentration of the alkali component of the alkaline developing solution that is managed to not absorb carbon dioxide and the concentration of the dissolved photoresist are managed to a managed concentration value.

Assume that the first measuring means 11 is a measuring means (for example, a conductivity meter for measuring the conductivity) for measuring the characteristic value of the developing solution related to the concentration of at least the alkali component among the components of the developing solution, and the second measuring means 12 is for measuring the If the component of the developing solution measures at least the characteristic value of the developing solution related to the concentration of the photoresist (for example, an absorbance photometer for measuring absorbance at λ = 560 nm), the arithmetic unit 2 includes a calculation block using a multivariate analysis method. 21. Therefore, the concentration of the alkaline component of the developer and the concentration of the dissolved photoresist can be calculated from the characteristic values of the developer by the multivariate analysis method.

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

Other details are the same as those of other embodiments, and are omitted.

    [Fifteenth embodiment]    

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

Assume that the first measuring means 11 is a measuring means (for example, a conductivity meter for measuring the conductivity) for measuring the characteristic value of the developing solution related to the concentration of at least the alkali component among the components of the developing solution, and the second measuring means 12 is for measuring the A measuring means for measuring at least the characteristic value of the developing solution related to the concentration of the photoresist in the component of the developing solution (for example, an absorbance photometer for measuring the absorbance at λ = 560 nm), and the third measuring means measures the content of the developing solution. If the measuring means (for example, a density meter for measuring density) is used to measure at least the characteristic value of the developer that absorbs the carbon dioxide concentration, since the arithmetic unit 2 includes an arithmetic block 21 using a multivariate analysis method, it can be measured by the multivariate analysis method. The characteristic value of the developing solution was used to calculate the alkali component concentration, the dissolved photoresist concentration, and the carbon dioxide absorption concentration of the developing solution.

Therefore, the control block 31 is a control block that sends a control signal to the control valve in such a manner that the conductivity of the developing solution can become a predetermined management value, and the control block 32 is an absorbance at a characteristic wavelength (for example, λ = 560 nm) of the developing solution. It can be a control block that sends a control signal to the control valve in a predetermined management value or in a management area, and the control block 33 sends a control signal to the control valve in such a manner that the carbon dioxide concentration can be a predetermined management value or less. When controlling the block, the control unit 3 is connected to the measurement unit 1 so as to receive the characteristic value of the developer solution measured, and connected to the calculation unit 2 so as to receive the calculated component concentration of the developer solution. The developer management device E according to the embodiment can control the concentration of the alkali component in the developer to a predetermined management value, the dissolved photoresist concentration to a predetermined management value or less, and the absorption carbon dioxide concentration to a predetermined management. The developer is maintained and managed in a manner below the value or the managed value.

Other details are the same as those of other embodiments, and are omitted.

    [Sixteenth embodiment]    

FIG. 24 is a schematic diagram of a developing solution management device in which one of the three components of the developing solution is controlled by the characteristic value and the other is controlled by the component concentration. The developing solution management device of this embodiment is preferably applicable to the alkali component concentration and carbon dioxide absorption concentration management of the alkaline developer, and the dissolving photoresist concentration by a specific wavelength (for example, λ = 560nm). The absorbance in the control.

It is assumed that the first measurement means 11 is a measurement means (for example, a conductivity meter for measuring electrical conductivity) for measuring characteristics of the developer related to the concentration of at least an alkali component among the components of the developer, and the second measurement means 12 is measurement and development. A measuring means (for example, an absorbance photometer for measuring the absorbance at λ = 560 nm) of at least the characteristic value of the developing solution related to the concentration of the photoresist in the component of the solution, and the third measuring means is to measure at least If the measuring means for measuring the characteristic value of the developing solution related to the carbon dioxide concentration (for example, a density meter for measuring density), since the arithmetic unit 2 includes an arithmetic block 21 using a multivariate analysis method, it is possible to obtain the development value measured by the multivariate analysis method. The characteristic value of the liquid was used to calculate the alkali component concentration, the dissolved photoresist concentration, and the carbon dioxide absorption concentration of the developing solution.

Therefore, the control block 31 is a control block that sends a control signal to the control valve in such a way that the concentration of the alkali component can become a predetermined management value, and the control block 32 is based on the absorbance of the characteristic wavelength of the developer (for example, λ = 560 nm). It is a control block that sends a control signal to a control valve in a manner that is a predetermined management value or in a management area. The control block 33 is a control block that sends a control signal to a control valve in a manner that absorbs carbon dioxide concentration and can become a predetermined management value or less. At this time, since the control unit 3 is connected to the measurement unit 1 so as to receive the characteristic value of the measured developer solution, and connected to the calculation unit 2 so as to receive the calculated component concentration of the developer solution, according to this embodiment The developer management device E can control the concentration of the alkali component in the developer to a predetermined management value, the dissolved photoresist concentration to a predetermined management value or less, and the absorption carbon dioxide concentration to a predetermined management value or management. The developer is maintained and managed in a manner below the value.

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

    [Seventeenth Embodiment]    

FIG. 25 is a schematic diagram of a developing solution management device in which three components of the developing solution are managed by the component concentrations. The developing solution management device of this embodiment is preferably applicable to the case where the concentration of the alkali component of the alkaline developing solution, the concentration of the dissolved photoresist, and the concentration of the absorbed carbon dioxide are controlled by the concentration.

Assume that the first measuring means 11 is a measuring means for measuring the characteristic value of the developing solution related to the concentration of at least the alkali component among the components of the developing solution (for example, a conductivity meter for measuring conductivity), and the second measuring means 12 is measuring and developing A measuring means (for example, an absorbance photometer for measuring the absorbance at λ = 560 nm) of a characteristic value of the developing solution in which at least the concentration of the photoresist is dissolved in the component of the liquid, and the third measuring means is to measure at least absorption in the component of the developing solution If the measuring means for measuring the characteristic value of the developing solution related to the carbon dioxide concentration (for example, a density meter for measuring density), since the arithmetic unit 2 includes an arithmetic block 21 using a multivariate analysis method, the developing solution measured by the multivariate analysis method can be used. The characteristic value of the developer is used to calculate the alkali component concentration, the dissolved photoresist concentration, and the carbon dioxide absorption concentration of the developing solution.

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

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

As described above, as shown in the tenth to seventeenth embodiments, the developing solution management device of this embodiment includes the measuring section 1 that measures a plurality of characteristic values of the developing solution related to the component concentration of the alkaline developing solution, and the computing section 2 Using a multivariate analysis method to calculate the component concentration of the developing solution from the plurality of characteristic values measured by the measuring section 1; and the control section 3, based on the characteristic values of the developing solution measured by the measuring section 1 or the computing section 2 The calculated component concentration of the developing solution sends a control signal to the control valves 41 to 43 provided on the pipeline for supplying the replenishing solution to be supplied to the developing solution.

The measurement section 1 and the calculation section 2 in the developer management device of this embodiment can adopt various aspects in the same manner as the measurement section 1 and the calculation section 2 in the developer concentration measurement device.

The control unit 3 in the developer management apparatus of this embodiment does not need to be provided as a separate device from the calculation unit 2, and can also be installed as a control function and a calculation function of an integrated device (for example, a computer). As in FIG. 11, the control unit 3 can be configured separately from the measurement unit 1 and the calculation unit 2. The control unit 3 may be interconnected with the measurement unit 1 and the calculation unit 2 so as to be able to receive the characteristic value measured by the measurement unit 1 or the component concentration calculated by the calculation unit 2 as a control amount. In this way, a necessary control signal can be issued according to the received characteristic value or component concentration.

The pipeline for supplying the replenishment 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 component of the developer management device E. If it communicates with the control part 3 so that it may be controlled by the control signal of the control part 3, it can also be provided outside the developer management apparatus E. As shown in FIG.

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

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

According to the developing solution management device of the present invention, since the developing solution is automatically maintained at always the best developing performance, the product yield is improved, and the replacement operation of the developing solution is not required, which can be expected to help reduce the operating cost Or waste liquid costs.

Claims (14)

    A component concentration measuring device for a developing solution includes: a measuring section that measures a plurality of characteristic values of the developing solution related to a component concentration of a developing solution that is alkaline that is repeatedly used; and a computing section based on the measured by the measuring section. The plurality of characteristic values are used to calculate a component concentration of the developing solution by a multivariate analysis method; and a display unit displays at least one of the characteristic value measured by the measurement unit and the component concentration calculated by the calculation unit. .         A component concentration measuring device for a developing solution includes: a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to the component concentration of a developing solution that exhibits alkalinity that is repeatedly used; and a computing section that measures the foregoing In the case of a plurality of characteristic values, the component concentration of the developer is calculated by a multivariate analysis method based on the plurality of characteristic values measured by the measurement section; the measurement data storage section will use the component concentration calculated by the calculation section , And memorize together with at least one of the time and the elapsed time from the start of the measurement; and the display section, the component concentration data memorized in the aforementioned measurement data storage section to memorize the time or The elapsed time from the start of measurement is used as an indicator to display the graph.         A component concentration measuring device for a developing solution includes: a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to the component concentration of a developing solution that exhibits alkalinity that is repeatedly used; and a calculation section that measures the foregoing In the case of a plurality of characteristic values, the component concentration of the developer is calculated by a multivariate analysis method based on the plurality of characteristic values measured by the measurement unit; the measurement data storage unit will use the characteristic values measured by the measurement unit. And the component concentration calculated by the calculation unit, together with at least one of the time and the elapsed time from the start of measurement; and a display unit that stores the characteristic value and component concentration stored in the measurement data storage unit At least one of the graphs is displayed by using the time memorized in the measurement data storage unit or the elapsed time from the start of measurement as an indicator.         For example, the developer concentration component measuring device of claim 3 further includes display switching means for switching a graph to be displayed on the display section to a graph of characteristic values of the developer or a graph of component concentration of the developer.         A developing solution management device includes: a measuring section that measures a plurality of characteristic values of the developing solution related to a component concentration of a developing solution that exhibits alkalinity that is repeatedly used; and a computing section that is based on the plurality of measured values measured by the measuring section. The characteristic value calculates the component concentration of the developer by a multivariate analysis method; the display section displays at least one of the characteristic value measured by the measurement section and the component concentration calculated by the calculation section; and a control section , Based on the measured value or calculated value of the management target item selected from the plurality of characteristic values of the developing solution measured by the measuring section and the component concentration of the developing solution calculated by the calculating section, A control signal is sent from a control valve on a pipeline for supplying a replenishing solution to be supplied to the developer.         A developing solution management device includes a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to a component concentration of a developing solution that exhibits alkalinity, and a computing section that measures the plurality of characteristics each time the measuring section measures the plurality of characteristics. When the value is calculated, the component concentration of the developer is calculated by multivariate analysis based on the plurality of characteristic values measured by the measurement section; the measurement data storage section will use the component concentration calculated by the calculation section together with the time And at least one of the elapsed time from the start of the measurement is memorized together; the display unit stores the component concentration data memorized in the aforementioned measurement data storage unit to memorize the time in the aforementioned measurement data storage unit or calculate from the measurement start The elapsed time from the beginning is used as an indicator to display the graph; and the control unit is based on the management selected from the plurality of characteristic values of the developing solution measured by the measuring unit and the component concentration of the developing solution calculated by the computing unit. The measured value or calculated value of the target item is set to a replenishment provided to transport the developer to be replenished to the developer. The fluid control valve of the pipeline control signals.         A developing solution management device includes: a measuring section that repeatedly measures a plurality of characteristic values of the developing solution related to a component concentration of a developing solution that exhibits alkalinity; and a computing section that measures the plurality of characteristics each time the measuring section When the value is measured, the component concentration of the developer is calculated by multivariate analysis based on the plurality of characteristic values measured by the measurement unit; the measurement data storage unit will use the characteristic values measured by the measurement unit and The aforementioned component concentration calculated by the arithmetic unit is memorized together with at least one of the time and the elapsed time from the start of measurement; the display unit memorizes at least one of the characteristic value and the constituent concentration of the aforementioned measurement data storage unit Display the chart with the time memorized in the measurement data storage section or the elapsed time from the start of the measurement as an indicator; and the control section, based on the plurality of characteristic values of the developing solution measured by the measurement section and the foregoing The measurement value or calculation of the management target item selected among the component concentrations of the developer solution calculated by the calculation section. The output value sends a control signal to a control valve provided on a pipeline for conveying the replenishing solution to be replenished to the developer.         For example, the developer management device of claim 7 further includes display switching means for switching a graph to be displayed on the display section to a graph of a characteristic value of the developer or a graph of a component concentration of the developer.         The developer management device according to any one of claims 5 to 8, wherein the measurement unit includes: a first measurement means that measures a characteristic value of the developer relative to a concentration of at least an alkali component among the components of the developer; and The second measuring means measures a characteristic value of the developer in relation to a concentration of at least a photoresist dissolved in the developer in a component concentration of the developer.         For example, the developer management device of claim 9, wherein the calculation unit includes a calculation block that calculates the concentration of the alkali component of the developer and the concentration of the photoresist, and the control unit includes a first control block that controls the control valve. Signal, the concentration of the alkali component calculated by the operation block becomes a predetermined management value; and the second control block sends a control signal to the control valve, and the concentration of the photoresist calculated by the operation block becomes Below the established management value.         The developing solution management device according to claim 9, wherein the measuring unit further includes a third measuring means for measuring a characteristic value of the developing solution related to at least a concentration of carbon dioxide absorbed by the developing solution among the components of the developing solution.         For example, the developer management device of claim 11, wherein the calculation unit includes a calculation block that calculates the carbon dioxide concentration of the developer, and the control unit includes a third control block that sends a control signal to the control valve, and uses the first A characteristic value of the developing solution measured by a measuring means becomes a predetermined management value; a fourth control block sends a control signal to the control valve, and the characteristic value of the developing solution measured by the second measuring means falls into A predetermined management area; and a fifth control block that sends a control signal to the control valve so that the concentration of carbon dioxide calculated by the calculation block becomes less than a predetermined management value.         For example, the developer management device of claim 11, wherein the calculation unit includes a calculation block that calculates the concentration of the alkali component and the concentration of carbon dioxide of the developer, and the control unit includes a first control block that sends a control signal to the control valve,俾 The concentration of the alkali component calculated by the calculation block becomes a predetermined management value; the fourth control block sends a control signal to the control valve, and 特性 the characteristic value of the developer measured by the second measurement means falls And the fifth control block sends a control signal to the control valve, and the carbon dioxide concentration calculated by the calculation block becomes equal to or lower than the predetermined management value.         For example, the developer management device of claim 11, wherein the calculation unit includes a calculation block that calculates the concentration of the alkali component, the concentration of the photoresist, and the concentration of carbon dioxide of the developer, and the control unit includes a first control block, The control valve sends out a control signal, and the concentration of the alkali component calculated by the operation block becomes a predetermined management value. The second control block sends a control signal to the control valve, and the photoresist calculated by the operation block. And the fifth control block sends a control signal to the control valve, and the carbon dioxide concentration calculated by the calculation block becomes the predetermined management value or less.