KR20180087124A - Developing solution management apparatus - Google Patents

Abstract

An objective of the present invention is to provide a developing solution management device which can realize development treatment that is capable of maintaining desired development performance and a desired line width and a residual film thickness of a wiring pattern on a substrate. To achieve the objective, the developing solution management device (D) of the present invention comprises a control means (21) and a display means (22). The control means (21) includes: a data memory part (23) which stores conductivity data having conductivity values of the developing solution that have already been confirmed to become certain development performance for each concentration region specified by using, as indexes, dissolved photoresist concentration and absorbed carbon dioxide concentration of a developing solution showing alkalinity and repeatedly used; and a control part (31) which emits a control signal to control valves installed in a pipeline for supplying a supplementary solution to the developing solution so that conductivity values of the developing solution become a control target value by measured values of the dissolved photoresist concentration and measured values of the absorbed carbon dioxide concentration of the developing solution. The display means (22) displays at least any one of the conductivity value or the alkali component concentration value among a conductivity value, an alkali component concentration value, a dissolved photoresist concentration value, and an absorbed carbon dioxide concentration value obtained from the developing solution.

Description

{DEVELOPING SOLUTION MANAGEMENT APPARATUS}

The present invention relates to a developer management apparatus, and more particularly to a developer management apparatus which exhibits alkalinity and is repeatedly used to develop a photoresist film in a semiconductor or liquid crystal panel development process of a circuit board.

2. Description of the Related Art In a photolithographic development process for realizing fine wiring in a semiconductor or liquid crystal panel, a developing solution exhibiting alkalinity (hereinafter referred to as " alkaline developing solution ") is used as a chemical solution for dissolving a photoresist formed on a substrate .

BACKGROUND ART [0002] In recent semiconductor and liquid crystal panel substrate manufacturing processes, miniaturization and integration of wafers and glass substrates have become more and more widespread. Under such circumstances, it has become necessary to maintain the concentration of the main component of the alkaline developer more accurately by measuring the concentration of the alkaline developer in order to realize miniaturization and high integration of wiring processing of the large-sized substrate, and to maintain the developer.

Conventionally, the measurement of the component concentration of the alkaline developer has been performed using a product in which a good linear relationship is obtained between the alkali component concentration (hereinafter referred to as " alkali component concentration ") of the alkaline developer and the conductivity.

However, in recent years, the development processing increases the chance that the alkaline developer comes in contact with air, and the alkaline developer absorbs the carbon dioxide in the air, so that the absorption amount of the carbon dioxide in the alkaline developer is increased. When the concentration of absorbed carbon dioxide becomes high, there arises a problem that, in the developer solution management by the conventional method, the predetermined line width processing can not be maintained.

This problem occurs because the alkali component having the developing activity in the alkaline developer is consumed in the reaction for generating the carbonate by the absorption of the carbon dioxide. Further, an alkali component having a developing activity in an alkaline developer is consumed by dissolution of a photoresist and also by a reaction in which a photoresist salt is generated.

In response to such a problem, various attempts have been made to manage the developers to replenish the reduced alkaline components consumed. In these attempts, by measuring the carbonate concentration, the alkali component consumed in the reaction for generating the carbonate is supplemented with the replenishing liquid to try to stabilize the concentration of the alkali component having the developing activity. The same is true for the alkali component consumed by dissolving the photoresist. These are based on the viewpoint that an alkali component which has become a carbonate or a photoresist salt is inactivated due to loss of development activity (for example, Patent Document 2).

Japanese Patent No. 2561578 Japanese Patent Application Laid-Open No. 2008-283162

However, even with these various developer management attempts, it was still difficult to realize satisfactory developer management.

The present inventors have made intensive studies on developing solution management and found that some of the carbonate or resist salinity developing solution is liberated and contributes to the developing effect and that the developing effect on these components, The inventors of the present invention have obtained the knowledge that the developer management considering the contribution also can be realized by managing the conductivity value of the developer and that the management value of such conductivity is variously varied depending on the absorbed carbon dioxide concentration and the dissolved photoresist concentration.

This is because the alkali component which has become the carbonate or the photoresist salt is not inactivated but is partially liberated and contributes to the developing action and is liberated from the alkaline component having the developing activity and the carbonate salt and the resist salt, Components are all acting on the conductivity. That is, the inventors have found that the total amount of components having a developing action is managed optimally by managing the conductivity value of the developing solution, leading to the present invention.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a developer management apparatus capable of achieving a predetermined developing performance for a photoresist.

In order to achieve the above object, the developer managing apparatus of the present invention is characterized in that it is preliminarily confirmed that a predetermined developing performance is achieved for each density region specified with the concentration of the dissolved photoresist and the absorbed carbon dioxide concentration of the alkaline developer, A data storage unit for storing conductivity data having a conductivity value of the developing solution stored in the data storage unit of the concentration region specified by the measurement value of the concentration of dissolved photoresist and the measured value of the absorbed carbon dioxide concentration, And control means for issuing a control signal to a control valve provided in a conduit for conveying a replenishing liquid replenished to the developing solution so that the conductivity value of the developing solution becomes the control target value, The conductivity value, the alkali component concentration And the display means for dissolution of the photoresist concentration value and absorb the carbon dioxide concentration at least conductivity values and the alkaline component concentration of the values displayed either one.

It is preferable that the developer management apparatus of the present invention further comprises display switching means for switching the display object displayed on the display means.

The developer managing apparatus of the present invention is characterized in that the conductivity value of the developer which has been confirmed to have a predetermined developing performance for each concentration region specified by using the dissolved photoresist concentration and the absorbed carbon dioxide concentration of the alkaline developer, Wherein the conductivity value stored in the data storage unit of the concentration region specified by the measured value of the dissolved photoresist concentration of the developer and the measured value of the absorbed carbon dioxide concentration is set to a control target value And control means for issuing a control signal to a control valve provided in a conduit for feeding a replenishing liquid replenished to the developing solution so that the conductivity of the developing solution becomes the control target value; The component concentration value, the dissolved photoresist concentration value By a conductivity value of at least either one of the alkaline component and of the absorbed carbon dioxide concentration value pixel value, an indicator of elapsed time from the measurement time or the measurement start, and the display means for displaying the graph.

It is preferable that the developer management apparatus of the present invention further comprises display switching means for switching the display object displayed on the display means.

According to the developer managing apparatus of the present invention, even if the developer has any dissolved photoresist concentration and absorbed carbon dioxide concentration, the component having activity in the developing action in the developer is kept constant, so that desired developing performance can be maintained, It is possible to realize a developing process capable of maintaining the desired line width and the thickness of the residual film. In addition, various data and graphs can be displayed.

According to a preferred aspect of the developer management device of the present invention, the developer concentration of the developing solution, which includes the characteristic value of the developing solution correlated with the dissolved photoresist concentration of the developing solution and the characteristic value of the developing solution correlated with the absorbed carbon dioxide concentration of the developer The method according to claim 1, further comprising a plurality of measurement devices for measuring a plurality of characteristic values, wherein the control means is configured to calculate, from a plurality of characteristic values of the developer measured by the plurality of measurement devices, And a calculation unit for calculating a measured value of the concentration and a measured value of the absorbed carbon dioxide concentration.

According to a preferred aspect of the developer management device of the present invention, the developer concentration of the developing solution, which includes the characteristic value of the developing solution correlated with the dissolved photoresist concentration of the developing solution and the characteristic value of the developing solution correlated with the absorbed carbon dioxide concentration of the developer A plurality of measurement apparatuses for measuring a plurality of characteristic values and a plurality of characteristic values of the developer measured by the plurality of measurement apparatuses, a multivariate analysis method is used to calculate a measured value of the dissolved photoresist concentration of the developer, And calculating means for calculating a measured value of the concentration.

According to a preferred aspect of the developer management device of the present invention, a density meter is provided, and the control means controls the density value of the developer measured by the density meter based on the correspondence between the concentration of absorbed carbon dioxide in the developer and the density And a calculation unit for calculating the absorbed carbon dioxide concentration value of the developer from the measured value.

According to a preferred aspect of the developer management device of the present invention, the density of the developer is determined from the density value of the developer measured by the density meter based on the correspondence between the density meter and the absorbed carbon dioxide concentration of the developer, And a calculation unit for calculating a value.

According to the developer managing apparatus of the present invention, it is confirmed in advance that a predetermined developing performance is achieved for each concentration region specified with the absorbance and the absorbed carbon dioxide concentration correlated with the dissolved photoresist concentration of the alkaline developing developing developer A data storage unit for storing the alkali component concentration data having the alkali component concentration value of the developer; a data storage unit for storing the alkali component concentration data stored in the data storage unit of the concentration region specified by the absorbance of the developer and the measured value of the absorbed carbon dioxide concentration And a control section for issuing a control signal to a control valve provided in a channel for feeding a replenishing liquid replenished to the developing solution so that the alkali component concentration of the developing solution becomes the control target value, The alkaline component concentration obtained from the developer Value, the absorbance values are correlated with the dissolved photoresist concentration, and, at least one of absorbing the carbon dioxide concentration values and the display means for displaying the alkali component concentration value.

According to the developer managing apparatus of the present invention, it is confirmed in advance that a predetermined developing performance is achieved for each concentration region specified with the absorbance and the absorbed carbon dioxide concentration correlated with the dissolved photoresist concentration of the alkaline developing developing developer A data storage unit for storing the alkali component concentration data having the alkali component concentration value of the developer; a data storage unit for storing the alkali component concentration data stored in the data storage unit of the concentration region specified by the absorbance of the developer and the measured value of the absorbed carbon dioxide concentration And a control section for issuing a control signal to a control valve provided in a channel for feeding a replenishing liquid replenished to the developing solution so that the alkali component concentration of the developing solution becomes the control target value, The alkaline component concentration obtained from the developer Values, in the dissolved photo absorption values correlated with the resist concentration, and, absorbing carbon dioxide concentration value of at least the alkaline component concentration value, an indicator of elapsed time from the measurement time or the measurement started to be provided with a display means for displaying the graph.

According to the developer management apparatus of the present invention, it is preferable to further include display switching means for switching the display object displayed on the display means.

According to the present invention, even if the developer has any dissolved photoresist concentration and absorbed carbon dioxide concentration, since the active component in the developing action in the developer is kept constant, the desired developing performance can be maintained and the desired line width of the wiring pattern on the substrate It is possible to realize a developing process capable of maintaining the residual film thickness. In addition, various data and graphs can be displayed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a developing process for explaining a developer managing apparatus of a first embodiment. FIG.
2 is a schematic view of a developing process for describing the developer managing apparatus of the second embodiment.
3 is a schematic view of a developing process for explaining the developer managing apparatus of the third embodiment.
4 is a schematic view of a developing process for describing the developer managing apparatus of the fourth embodiment.
5 is a graph showing the relationship between the absorbed carbon dioxide concentration and the density of the developer.
6 is a schematic diagram of a developing process for explaining the developer management apparatus of the fifth embodiment.
7 is a schematic view of a developing process for describing the developer managing apparatus of the sixth embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as appropriate. It should be noted, however, that the scope of the present invention is not limited to those shown in the drawings, unless otherwise specified. As a simple explanation example, it is only schematically shown.

In the following description, as a concrete example of the developer, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (hereinafter, referred to as TMAH), which is mainly used in a semiconductor or liquid crystal panel substrate manufacturing process, . However, the developer to which the present invention is applied is not limited to this. Examples of other developing solutions to which the method and apparatus for managing developer 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 aqueous solutions of trimethylmonoethanol ammonium hydroxide (choline) And an aqueous solution of an organic compound.

In the following description, the component concentration such as the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration is the concentration based on the weight percent concentration (wt%). The "dissolved photoresist concentration" refers to the concentration when the dissolved photoresist is converted into the amount of photoresist, and the "absorbed carbon dioxide concentration" refers to the concentration when the absorbed carbon dioxide is converted into the amount of carbon dioxide.

In the development processing process, development is carried out by dissolving unnecessary portions of the photoresist film after the exposure processing. The photoresist dissolved in the developing solution generates a photoresist salt with the alkali component of the developing solution. For this reason, unless the developer is properly managed, as the developing process proceeds, the developer is consumed by the alkaline component having the developing activity and deteriorates, and the developing performance deteriorates. Simultaneously, the dissolved photoresist is accumulated as a photoresist salt with the alkali component in the developer.

The photoresist dissolved in the developer shows a surfactant activity in the developer. Therefore, the photoresist dissolved in the developer enhances the wettability of the photoresist film provided in the development process with respect to the developer, and improves the affinity between the developer and the photoresist film. Therefore, in a developing solution suitably containing a photoresist, the developer is uniformly and uniformly spread even in the fine recesses of the photoresist film, so that the development processing of the photoresist film having fine irregularities can be satisfactorily performed.

Further, in the recent development processing, as the substrate is enlarged, a large amount of the developer is repeatedly used, so that the developer is more likely to be exposed to the air. Absorbed. The absorbed carbon dioxide generates a carbonate between itself and the alkali component of the developer. For this reason, unless the developer is appropriately managed, the developer is consumed by the carbon dioxide absorbed in the alkaline component having the developing activity and decreases. At the same time, the absorbed carbon dioxide accumulates as a carbonate with the alkali component in the developer.

However, since the carbonate in the developer shows alkalinity in the developer, it has a developing effect.

Unlike the conventional recognition that the photoresist dissolved in the developing solution or the absorbed carbon dioxide inactivates the developing activity of the developing treatment, it actually contributes to the developing performance of the developing solution. Therefore, it is necessary to manage the developer to maintain them at an optimum concentration while permitting the dissolved photoresist and the absorbed carbon dioxide to be dissolved in the developer, rather than performing the developer control such that the dissolved photoresist and the absorbed carbon dioxide are completely eliminated .

In addition, the photoresist salt or carbonate generated in the developing solution partially dissociates and generates various free ions such as photoresist ions, carbonate ions, and hydrogen carbonate ions. These free ions affect the conductivity of the developer with various contribution rates.

With respect to these points, the inventor of the present invention has studied extensively on developing solution management, and found that some of the carbonate or resist salinity developing solution is liberated and contributes to the developing effect, and that the developing effect from these components, And that the management value of such conductivity is variously varied depending on the absorbed carbon dioxide concentration and the concentration of the dissolved photoresist.

Therefore, the inventor assumed the case where the aqueous solution of TMAH was to be managed as a developing solution, and the relationship between the desired developing performance on the photoresist and the conductivity value of the developing solution was obtained by variously changing the dissolved photoresist concentration and the absorbed carbon dioxide concentration.

(Absorbance at a wavelength of 560 nm corresponding to an absorbance of 0.0 to 1.3 (abs)) (hereinafter, also referred to as a concentration and absorbance at a wavelength of 560 nm) in a range of 0.0 to 1.3 (wt% A sample of a developer of aqueous solution of TMAH was prepared. The inventors of the present invention conducted an experiment for measuring the conductivity, the absorbed carbon dioxide concentration, and the dissolved photoresist concentration of these developers and confirming the correlation with the developing performance, the conductivity, the absorbed carbon dioxide concentration, and the dissolved photoresist concentration component . A matrix (combination table) in which the absorbed carbon dioxide concentrations are arranged vertically or horizontally as one item, and the dissolved photoresist concentration is set as another item in the horizontal or vertical direction is prepared. For each combination of the absorbed carbon dioxide concentration and the dissolved photoresist concentration, the conductivity of the developer, which satisfies the desired developing performance for the photoresist, was determined and written in the respective columns to complete the matrix.

Here, the predetermined developing performance means the developing performance of the developing solution when the line width of the wiring pattern on the substrate and the thickness of the residual film to be realized in the developing process are realized.

Representative measurement results of the absorbed carbon dioxide concentration, dissolved photoresist concentration, and conductivity of each sample are illustrated. When the absorbed carbon dioxide concentration is 0.0 (wt%) and the dissolved photoresist concentration is 0.0 (wt%) (equivalent to 0.0 (abs)) (so-called fresh solution), the conductivity of the developer Was 54.58 (mS / cm).

When the absorbed carbon dioxide concentration is 0.0 (wt%) and the dissolved photoresist concentration is 0.25 (wt%) (equivalent to 0.8abs), the conductivity of the developer capable of exhibiting predetermined developing performance is 54.55 (mS / cm) When the photoresist concentration was 0.40 (wt%) (equivalent to 1.3abs), the conductivity of the developer was 54.53 (mS / cm).

When the dissolved photoresist concentration is 0.0 (wt%) (corresponding to 0.0 (abs)) and the absorbed carbon dioxide concentration is 0.6 (wt%), the conductivity of the developer is 54.60 (mS / cm) and the absorbed carbon dioxide concentration is 1.3 (wt%), the conductivity of the developer was 54.75 (mS / cm).

When the absorbed carbon dioxide concentration is 0.6 (wt%) and the dissolved photoresist concentration is 0.22 (wt%) (equivalent to 0.7abs), the conductivity of the developer is 54.60 (mS / cm) and the dissolved photoresist concentration is 0.40 wt%) (equivalent to 1.3abs), the conductivity of the developer was 54.58 (mS / cm).

When the absorbed carbon dioxide concentration is 1.3 (wt%) and the dissolved photoresist concentration is 0.22 (wt%) (equivalent to 0.7abs), the conductivity of the developer is 54.75 (mS / cm) and the dissolved photoresist concentration is 0.40 wt%) (equivalent to 1.3abs), the conductivity of the developer was 54.75 (mS / cm).

In the experiment described above, the management value of the conductivity tends to increase when the absorbed carbon dioxide concentration increases in a certain concentration region, and the control value of the conductivity tends to decrease as the concentration of the dissolved photoresist increases.

In the experiment described above, the conductivity of the developer of each sample was measured by a conductivity meter. The absorbed carbon dioxide concentration was measured by a titration method. The dissolved photoresist concentration was used as the weight preparation value. Titration is neutralization titration using hydrochloric acid as titration reagent. As an titration apparatus, an automatic titration apparatus GT-200 manufactured by Mitsubishi Chemical Corporation was used.

The conductivity, the absorbed carbon dioxide concentration, and the dissolved photoresist concentration described above are for finding the relationship between the conductivity, the absorbed carbon dioxide concentration, the dissolved photoresist concentration and the developing performance, and are not limited to the respective values.

As described above, it is understood that the conductivity capable of exhibiting the developing performance varies depending on the absorbed carbon dioxide concentration and the dissolved photoresist concentration. As described above, in the development liquid management, in the developer containing the absorbed carbon dioxide and the dissolved photoresist, the conductivity is used as the control value, the absorbed carbon dioxide concentration and the dissolved photoresist concentration are measured, and the conductivity The predetermined developing performance can be exerted.

That is, the conductivity data (matrix) having the conductivity value of the developer, which has been confirmed to have a predetermined developing performance, is stored for each concentration region specified with the concentration of the dissolved photoresist of the developer and the concentration of the absorbed carbon dioxide as an index, (Matrix), it becomes possible to manage the developing solution which can exhibit predetermined developing performance.

In addition, the inventors have studied extensively on the developer liquid management. As a result, it has been found that a portion of the carbonate or resist salinity developer is liberated and contributes to the development operation, and a developer Management can be realized by managing the alkaline component concentration value of the developer and that the management value of the alkaline component concentration is variously varied depending on the absorbed carbon dioxide concentration and the absorbance correlated with the dissolved photoresist concentration I got knowledge.

Therefore, the inventor has considered the case where the aqueous solution of TMAH is to be managed as a developing solution, and assuming that the concentration of the alkali component measured on the basis of the conductivity of the developing solution exhibiting alkalinity, the absorbance having a correlation with the dissolved photoresist concentration of the developing solution, The relationship between the desired developing performance for the photoresist and the concentration of the alkaline component in the developing solution was obtained by varying the carbon dioxide concentration.

A developer sample of aqueous TMAH solution was prepared by changing the absorbed carbon dioxide concentration between 0.0 and 1.3 (wt%) and changing the absorbance correlated with the dissolved photoresist concentration to between 0.0 and 1.3 (abs). The inventors conducted experiments for measuring the alkali component concentration, the absorbed carbon dioxide concentration, and the absorbance of the developer and confirming the correlation with the developing performance, the alkali component concentration, the absorbed carbon dioxide concentration, and the absorbance of these samples. A matrix (combination table) in which the absorbed carbon dioxide concentrations were arranged as one item in the longitudinal or transverse direction, and the absorbance was set as another item in the horizontal or vertical direction was prepared. For each combination of the absorbed carbon dioxide concentration and the absorbance, the concentration of the alkali component in the developer, which satisfies the desired developing performance for the photoresist, was calculated and written in the respective columns to complete the matrix.

Here, the predetermined developing performance means the developing performance of the developing solution when the line width of the wiring pattern on the substrate and the thickness of the residual film to be realized in the developing process are realized.

Representative measurement results of absorbed carbon dioxide concentration, absorbance, and alkali component concentration of each sample are shown. When the absorbed carbon dioxide concentration was 0.0 (wt%) and the absorbance was 0.0 (abs) (so-called fresh solution), the alkali component concentration of the developer capable of exhibiting a predetermined developing performance was 2.380 (wt%).

When the absorbed carbon dioxide concentration is 0.0 (wt%) and the absorbance is 0.8abs, the alkali component concentration of the developer capable of exhibiting a predetermined developing performance is 2.379 (wt%). When the absorbance is 1.3abs, The concentration was 2.378 (wt%).

When the absorbance is 0.0 (abs) and the absorbed carbon dioxide concentration is 0.6 (wt%), the alkali component concentration of the developer is 2.381 (wt%) and the absorbed carbon dioxide concentration is 1.3 The component concentration was 2.388 (wt%).

When the absorbed carbon dioxide concentration is 0.6 wt% and the absorbance is 0.7abs, the alkali component concentration of the developer is 2.381 (wt%). When the absorbance is 1.3abs, the alkali component concentration of the developer is 2.380 wt% ).

When the absorbed carbon dioxide concentration is 1.3 wt% and the absorbance is 0.7abs, the alkali component concentration of the developer is 2.388 (wt%). When the absorbance is 1.3abs, the alkaline component concentration of the developer is 2.388 wt% ).

In the experiment described above, when the absorbed carbon dioxide concentration increases in a certain concentration region, the control value of the alkali component concentration tends to become larger, and when the absorbance increases, the control value of the alkali component concentration tends to decrease.

In the above experiment, the alkali component concentration of the developer of each sample can be obtained by measuring the conductivity with an electric conductivity meter. Specifically, a correlation (for example, a linear relationship) between the alkali component concentration and the conductivity value of a fresh solution of a TMAH aqueous solution (TMAH aqueous solution before development) is prepared in advance as a calibration curve. Based on this calibration curve, the alkali component concentration can be obtained from the conductivity value.

The absorbed carbon dioxide concentration was measured by titration method. Titration is neutralization titration using hydrochloric acid as titration reagent. As an titration apparatus, an automatic titration apparatus GT-200 manufactured by Mitsubishi Chemical Corporation was used. Absorption spectrophotometer was used for measurement of absorbance.

The above-described alkali component concentration, absorbed carbon dioxide concentration, and absorbance are for finding the relationship between the alkali component concentration, the absorbed carbon dioxide concentration, the absorbance and the developing performance, and are not limited to the respective values.

As described above, it can be understood that the concentration of the alkali component capable of exhibiting the developing performance varies depending on the absorbed carbon dioxide concentration and the absorbance. As described above, in the developer containing the absorbed carbon dioxide and the dissolved photoresist, the concentration of the alkali component is used as the control value of the developer, the absorbed carbon dioxide concentration and the absorbance are measured, and based on the measurement results By varying the control value of the alkali component concentration, it is possible to exhibit a predetermined developing performance.

That is, for each concentration region specified with the absorbance of the developer and the absorbed carbon dioxide concentration as indexes, an alkali component concentration data (matrix) having an alkali component concentration value of the developer that has been confirmed to have a predetermined developing performance is stored, By using the component concentration data (matrix), predetermined developing performance can be exerted.

Next, specific embodiments will be described with reference to the drawings.

[First Embodiment]

1 is a schematic diagram of a developing process for describing the developer managing apparatus D of the present embodiment. The developer managing apparatus D of the present invention is shown together with the developing process facility A, the replenishing liquid storage section B, the circulating stirring mechanism C, and the like.

First, the developing process facility A will be briefly described.

The developing apparatus A mainly comprises a developer reservoir 61, an overflow tank 62, a developing chamber hood 64, a roller conveyor 65, a developer shower nozzle 67, and the like. The developing solution is stored in the developer storage tank 61. The developing solution is supplemented with the replenishing solution to control composition. The developer storage tank 61 is provided with a level gauge 63 and an overflow tank 62, and manages the increase of the liquid amount by replenishing the replenishment liquid. The developer reservoir 61 and the developer shower nozzle 67 are connected to each other by a developer pipe 80. The developer stored in the developer storage tank 61 is sent to the developer shower nozzle 67 through the filter 73 by the circulation pump 72 provided in the developer pipe 80. [ The roller conveyor 65 is provided above the developer reservoir 61 and conveys the substrate 66 on which the photoresist film has been formed. The developing solution is dropped from the developer shower nozzle 67. The substrate 66 conveyed by the roller conveyor 65 is immersed in the developing solution by passing through the developer to be dropped. Thereafter, the developer is collected in the developer reservoir 61 and stored again. Thus, the developer is circulated and used repeatedly in the development process. In some cases, a treatment for preventing the carbon dioxide in the air from being absorbed in the developing chamber of the small-size glass substrate is performed by filling the nitrogen gas. Further, the deteriorated developer is discharged (drained) by operating the waste liquid pump 71.

The circulating stirring mechanism C will be described. The circulating stirring mechanism C is mainly for circulating and stirring the developer stored in the developer storage tank 61.

The bottom of the developer reservoir 61 and the side of the developer reservoir 61 are connected by a circulation conduit 85 provided with a circulation pump 74 and a filter 75 in the middle. When the circulation pump 74 is operated, the developer stored in the developer storage tank 61 circulates through the circulation duct 85. The developer returns from the side of the developer reservoir 61 through the circulation duct 85 to the developer reservoir 61 and stirs the stored developer.

When the replenishment liquid flows into the circulation duct 85 through the confluent pipeline 84, the introduced replenishment liquid is supplied into the developer storage tank 61 while being mixed with the circulating developer in the circulation duct 85.

Next, the developer management apparatus D of the present embodiment will be described. The developer management device D of the present embodiment has a conductivity value of a developer that has been confirmed to have a predetermined developing performance for each concentration region specified with the concentration of the dissolved photoresist and the absorbed carbon dioxide concentration of the developer exhibiting alkalinity as an index The electric conductivity of the concentration area specified by the measured value of the dissolved photoresist concentration of the developer and the measured value of the absorbed carbon dioxide concentration is set as the control target value and the developer is supplied with the replenishment liquid A developing solution supply device for supplying developer solution to the developing solution.

The developer management device D includes a measurement unit 1 and a control unit 21. [ The developer management apparatus D is connected to the developer reservoir 61 by the sampling pipe 15 and the outlet pipe 16. [

The measuring unit 1 includes a sampling pump 14, a conductivity meter 11, a first concentration measuring unit 12 for measuring the dissolved photoresist concentration, and a second concentration measuring unit 12 for measuring the concentration of absorbed carbon dioxide (13). The conductivity meter 11, the first concentration measuring means 12 and the second concentration measuring means 13 are connected in series to the rear end of the sampling pump 14. The measuring section 1 is preferably provided with temperature adjusting means (not shown) for stabilizing the sampled developer to a predetermined temperature in order to improve the measurement accuracy. At this time, it is preferable that the temperature adjusting means is provided in front of the measuring means. The sampling pipe 15 is connected to the sampling pump 14 of the measuring section 1 of the developer management apparatus D and the outlet pipe 16 is connected to the pipe at the end of the measuring means.

1, the conductivity meter 11, the first concentration measuring means 12 and the second concentration measuring means 13 are connected in series. However, the conductivity meter 11, the first concentration The connection of the measuring means 12 and the second concentration measuring means 13 is not limited to this. But may be a parallel connection, and each of them may be independently provided with a liquid delivery path. The order of the conductivity meter 11, the first concentration measuring means 12, and the second concentration measuring means 13 is not specifically referred to. It may be measured in an optimum order according to the characteristics of each measurement means.

The control means 21 includes a data storage section 23 and a control section 31. The data storage section 23 stores a conductivity value having a conductivity value of the developer to be used which has been previously confirmed to have a predetermined developing performance for each concentration area specified with the concentration of the dissolved photoresist and the concentration of absorbed carbon dioxide of the developing agent exhibiting alkalinity as an index Data is stored.

The control means 21 is connected to the conductivity meter 11 of the measuring section 1, the first concentration measuring means 12 and the second concentration measuring means 13 by a signal line. The conductivity value measured by the measuring unit 1, the dissolved photoresist concentration value, and the absorbed carbon dioxide concentration value are sent to the control means 21. [

The control section 31 of the control means 21 is connected to the control valves 41 to 43 provided in the pipeline for feeding the replenishing liquid to the developer by signal lines. 1, the control valves 41 to 43 are shown as internal components of the developer management apparatus D, but the control valves 41 to 43 are essential components of the developer management apparatus D of the present embodiment It does not mean anything. The control section 31 may be connected to the control valves 41 to 43 so as to control the operation of the control valves 41 to 43 and supply the replenishing liquid to the developer. The control valves 41 to 43 may be located outside the developer management apparatus D. [

The developer management apparatus D according to the embodiment further includes the display means 22. The display means 22 can display at least one of the conductivity value of the developer, the alkali component concentration value, the dissolved photoresist concentration value, and the absorbed carbon dioxide concentration value, at least one of the conductivity value and the alkali component concentration value.

The display means 22 may be a display monitor electrically connected to the developer management apparatus D or may be a touch panel type computer mounted on the developer management apparatus D. [ In the case of the touch panel type computer, the control means and the display means (the control portion and the data storage portion) are formed integrally.

Next, the operation of the developer management apparatus D of the present embodiment will be described.

The developer sampled from the developer storage tank 61 is fed into the measuring section 1 and the temperature is adjusted. The developer is then sent to the conductivity meter 11, the first concentration measuring means 12 and the second concentration measuring means 13 to measure the conductivity, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration. Each measurement data is sent to the control means 21.

The control unit 31 is provided with a control unit 31 for controlling the concentration of the developing solution in the developing solution to be applied to the developing solution in accordance with the conductivity value of the conductivity data having the conductivity value of the developing solution previously determined to have a predetermined developing performance for each concentration area specified with the concentration of dissolved photoresist and the concentration of absorbed carbon dioxide, And a management value of conductivity is set. The control section 31 performs the following control according to the measurement data received from the measurement section 1.

The control unit 31 determines the concentration of the dissolved photoresist and the measured absorbance among the conductivity data stored in the data storage unit 23 based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration received from the measuring unit 1 The conductivity value of the concentration region specified by the carbon dioxide concentration is obtained. The obtained conductivity value is set as the control target value of the conductivity of the developer.

The control unit 31 compares the measured conductivity received from the measuring unit 1 with the conductivity set as the control target value, and performs the following management according to the comparison result. That is, when the conductivity set as the control target value is equal to the measured conductivity, a replenishing liquid is basically not added to the developer. When the conductivity set as the control target value is larger than the measured conductivity, a replenishing liquid acting to raise the conductivity of the developer may be supplied. Further, when the conductivity set as the control target value is smaller than the measured conductivity, a replenishing liquid acting to lower the conductivity of the developer may be supplied.

Examples of the replenishment liquid replenished to the developing solution include a stock solution, a fresh solution, and pure water.

The replenishment liquid is stored in the replenishment liquid storage tanks 91, 92 of the replenishment liquid storage portion (B). The replenishing liquid storage tanks 91 and 92 are connected to a nitrogen gas pipeline 86 having valves 46 and 47 and are pressurized by the nitrogen gas supplied through this pipeline. The replenishing liquid reservoirs 91 and 92 are connected to the replenishing liquid channels 81 and 82, respectively, and the replenishing liquid is fed through the valves 44 and 45, which are normally open. The replenishing liquid channels 81 and 82 and the pure water channel 83 are provided with control valves 41 to 43 and the control valves 41 to 43 are controlled by the control unit 31 to be controlled. By the operation of the control valve, the replenishing liquid stored in the replenishing liquid storage tanks 91 and 92 is pressure-fed, and pure water is also fed. Thereafter, the replenishing liquid passes through the confluent pipeline 84, merges with the circulation agitating mechanism C, is supplied to the developer storage tank 61, and is stirred.

When the replenishment liquid stored in the replenishment liquid storage tanks 91 and 92 is reduced by the replenishment, the internal pressure is lowered and the supplied amount becomes unstable. Therefore, So that the internal pressures of the replenishment liquid storage tanks 91 and 92 are maintained. When the replenishment liquid storage tanks 91 and 92 are empty, the valves 44 and 45 are closed and replaced with a new replenishment solution storage tank filled with the replenishing solution, or the separately supplied replenishing solution is charged back into the empty replenishing solution storage tank.

The control of the control valves 41 to 43 is performed, for example, as follows. When the flow rate when the control valve is opened is adjusted, the replenishment amount of the liquid amount to be replenished can be distributed by managing the time when the control valve is opened. The control unit 31 controls the control valve to open the control valve for a predetermined time so that the replenishing liquid of the liquid amount to be supplied flows, based on the measured conductivity received from the measuring unit 1 and the conductivity set as the control target value Signal.

As the control method, various control methods used for controlling the control amount to the target value can be adopted. In particular, Proportional-Integral (P control), Proportional-Integral (Integral Control), Differential Control (Differential Control) Control) is preferable. More preferably, PID control (Proportional-Integral-Differential Control) is suitable.

As described above, according to the developer managing apparatus D according to the present embodiment, even if the developer has any dissolved photoresist concentration and absorbed carbon dioxide concentration, by managing the developer with the conductivity in the developer, It is possible to maintain the desired developing performance and realize the developing process capable of maintaining the desired line width and the residual film thickness of the wiring pattern on the substrate.

Further, according to the developer managing apparatus D of the present embodiment, by setting the control target management value using the conductivity data of the conductivity value of the developer whose developing performance has been confirmed in advance, the concentration of the dissolved photoresist in the developing liquid is 0.0 to 0.40 (wt.%) (corresponding to 0.0 to 1.3 (abs)) and the absorbed carbon dioxide concentration is 0.0 to 1.3 (wt%). That is, even when the concentration of the dissolved photoresist in the developing solution is 0.25 (wt%) or more (corresponding to 0.8 (abs)) and the absorbed carbon dioxide concentration is 0.6 (wt% The developer can be used without a waste solution, and it becomes possible to reduce the amount of waste solution of the developer.

In the above, examples in which the conductivity, the absorbed carbon dioxide concentration, the dissolved photoresist concentration, and the conductivity data are used have been described. The developer can be managed using the alkali component concentration data, the absorbed carbon dioxide concentration, the absorbance correlated with the dissolved photoresist concentration, and the alkali component concentration data without limiting thereto. In this case, the display means 22 displays at least an alkali component concentration value, an absorbance value correlated with the dissolved photoresist concentration, and an alkali component concentration value among the absorbed carbon dioxide concentration values.

[Second Embodiment]

Fig. 2 is a schematic diagram of a developing process for explaining the developer management device D of the present embodiment. The developer managing apparatus D of the present invention is shown together with the developing process facility A, the replenishing liquid storage section B, the circulating stirring mechanism C, and the like. The same components as those of the first embodiment are denoted by the same reference numerals and the description thereof may be omitted.

The measurement section 1 of the developer management apparatus D is configured to measure the conductivity value of the developing agent in a manner that the characteristic value of the developing solution correlated with the dissolved photoresist concentration of the developing solution and the characteristic value of the developing solution correlated with the absorbed carbon dioxide concentration of the developing solution And a plurality of measuring apparatuses for measuring. For example, the first characteristic value measuring means 12A for measuring the characteristic value of a developing solution correlated with the dissolved photoresist concentration is provided with a light absorbance photometer for measuring the absorbance at, for example,? = 560 nm. The second characteristic value measuring means (13A) for measuring the characteristic value of the developing liquid correlated with the absorbed carbon dioxide concentration is provided with a density meter for measuring the density of the developing liquid.

Here, the characteristic value of the developer having the "correlation" means that the characteristic value is related to the concentration of the component, and the characteristic value changes as the component concentration changes. For example, the characteristic value a of the developer having at least correlation with the component concentration A among the component concentrations of the developer is such that when the characteristic value a is obtained by a function having the component concentration as a variable, at least the component concentration A . Although the characteristic value a may be a function of only the component concentration A, a multivariate analysis method (for example, a multiple regression analysis method) is usually used when a multivariable function is used in addition to the component concentration A, Significance of adoption is great.

The control unit 21 includes a data storage unit 23, a control unit 31, and an arithmetic unit 32. The calculating unit 32 calculates a measured value of the dissolved photoresist concentration of the developer and a measured value of the absorbed carbon dioxide concentration from the plurality of characteristic values of the developer measured by the measuring unit 1 by multivariate analysis.

In the present embodiment, the developer sampled from the developer storage tank 61 is fed into the measuring section 1 and the temperature is adjusted. The developer is then sent to the conductivity meter 11, the first characteristic value measuring means 12A and the second characteristic value measuring means 13A to measure conductivity, absorbance and density. Each measurement data is sent to the control means 21.

The calculating unit 32 calculates the measured value of the dissolved photoresist concentration of the developer and the measured value of the absorbed carbon dioxide concentration from the absorbance and the density measured by the measuring unit 1 by multivariate analysis. At this time, the measurement value of the dissolved photoresist concentration and the measured value of the absorbed carbon dioxide concentration may be calculated from the conductivity, the absorbance, and the density by a multivariate analysis.

Based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration calculated by the calculation section 32, the control section 31 calculates the concentration of the dissolved dissolved photoresist and the measured absorbed carbon dioxide concentration in the electric conductivity data stored in the data storage section 23 The conductivity value of the concentration region specified by the concentration is obtained. The obtained conductivity value is set as the control target value of the conductivity of the developer.

Other configurations, operations, and the like are the same as those of the first embodiment and therefore will not be described.

Next, a method of calculating the measured value of the dissolved photoresist concentration and the absorbed carbon dioxide concentration from a plurality of characteristic values of the developer by the multivariate analysis will be described.

The inventors have found that the use of a multivariate analysis method (for example, a multiple regression analysis method) as an operation method can calculate the concentration of each component of the developer precisely as compared with the case of using the conventional method, And the concentration can be measured. (Concentration of dissolved photoresist and concentration of absorbed carbon dioxide) of the developer calculated by a multivariate analysis method (for example, a multiple regression method) is used, the dissolved photoresist concentration and the absorbed carbon dioxide concentration It is possible to easily obtain the desired conductivity value from the conductivity data having the conductivity value.

Assuming that the 2.38% TMAH aqueous solution was to be managed, a TMAH aqueous solution having various concentrations of alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration was prepared as a simulated developer sample. The inventors conducted an experiment for obtaining the component concentrations thereof by the multiple regression analysis method from various characteristic values measured for these developer samples. Hereinafter, a general calculation method by the multiple regression analysis method will be described, and thereafter, a method of calculating the component concentration of the developer using the multiple regression analysis method based on the experiment performed by the inventor will be described.

Multiple regression analysis consists of two steps: calibration and prediction. In the multiple regression analysis of the n-component system, m calibration standard solutions shall be prepared. The concentration of the jth component present in the i-th solution is denoted by C _ij . Here, i = 1 to m and j = 1 to n. with respect to m pieces of the standard solution, respectively, p of characteristic value is measured (for example, absorbance Toka property values such as conductivity of an arbitrary _{wavelength) A ik (k = 1~p)} . The density data and the characteristic data can be collectively represented by the matrix type (C, A).

[Equation 1]

The matrix for associating these matrices is called a calibration matrix, and is represented here as a symbol S (S _kj ; k = 1 to p, j = 1 to n).

&Quot; (2) "

The contents of C and A (A in A) can be calculated by matrix calculation from the conductivity, the absorbance and the density, regardless of whether homogeneous or heterogeneous measured values are mixed. This is the corrective step. In this case, p> = n and m> = np must be satisfied. Since each element of S is unknown, it is preferable that m > np. In this case, the least squares operation is performed as follows.

&Quot; (3) "

Here, superscript T means transpose matrix and superscript -1 means retrograde column.

_{A; (j = 1~n Cu j)} ; p characteristic of the measurement, and their value Au (Au _{k k} = 1~p) for a sample solution having a concentration of said unknown if the concentration is multiplied by the S Cu to obtain it Can be obtained.

&Quot; (4) "

This is a prediction step.

The inventors regarded the used alkaline developer (2.38% TMAH aqueous solution) as a multi-component system (n = 3) composed of three components of alkali component, dissolved photoresist and absorbed carbon dioxide, (p = 3), that is, an electric conductivity value of the developer, an absorbance value at a specific wavelength, and a density value. The inventors prepared eleven calibration standard solutions (m = 11, p (t)) in which a 2.38% TMAH aqueous solution was varied as the basic composition of the developing solution to variously change the alkali component concentration (TMAH concentration), the dissolved photoresist concentration and the absorbed carbon dioxide concentration > = n and m > np).

For the 11 calibration standard solutions, the conductivity value, the absorbance value at the wavelength? = 560 nm, and the density value were measured as characteristic values of the developing solution, and the concentration of each component was measured by a Multiple Linear Regression- Inverse Least Squares (MLR-ILS).

The measurement was performed by adjusting the temperature of the calibration standard solution to 25.0 캜. For the temperature adjustment, a bottle containing a calibration standard solution is immersed in a constant temperature water bath maintained at about 25 캜 for a long time and sampled at a temperature of 25 캜 by a temperature controller immediately before measurement. The conductivity meter used its own conductivity meter. And the conductivity was measured using a conductivity cell manufactured by Shimadzu Corporation, which was subjected to platinum black treatment. In the conductivity meter, the cell constant of the conductivity flow cell identified by a separate calibration operation is input. The absorption spectrophotometer was also used. A light source part having a wavelength? = 560 nm, a light measuring part and a glass flow cell. For the density measurement, a density meter employing a natural vibration method was used to obtain the density from the natural frequency measured by exciting the U-shaped flow cell. The units of measured conductivity value, absorbance value and density value are mS / cm, Abs., G / cm < ^{3 &} gt ;, respectively.

The calculation is based on the assumption that one of the 11 calibration standards is regarded as an unknown sample and the calibration matrix is obtained from the remaining 10 standards and the concentration of the unknown sample is calculated to obtain a known value Or a weight preparation value) (a one-out-of-the-way check method; leave-one-out method).

Table 1 shows the results of MLR-ILS calculation.

[Table 1]

In the MLR-ILS calculation, in consideration of the fact that the aqueous solution of TMAH absorbs carbon dioxide in strong alkalinity and is liable to be deteriorated, the concentration matrix used for the calculation is determined by an appropriate analytical method capable of accurately analyzing the alkali component concentration and the absorbed carbon dioxide concentration The calibration standard solution was measured separately. However, regarding the concentration of the dissolved photoresist, a weight preparation value was used.

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

The concentration matrix is shown in Table 2 below.

[Table 2]

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

[Table 3]

Table 4 shows the calibration matrix.

[Table 4]

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

[Table 5]

As shown in Table 5, the TMAH concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration obtained by the multiple regression analysis were all determined based on the TMAH concentration, the absorbed carbon dioxide concentration, and the dissolved photoresist concentration, Both are fairly close values.

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

The multivariate analysis method (for example, the multiple regression method) is effective for calculating the concentration of a plurality of components. A plurality of characteristic values a, b, c, ... of the developer , And the component concentrations A, B, C, ... are measured from the measured values by multivariate analysis (for example, regression analysis). Can be obtained. At this time, as to the component concentration to be obtained, at least one of the characteristic values correlated with at least the component concentration needs to be measured and used for the calculation.

Also, the component concentration is a measure indicating the relative amount of the component with respect to the whole. The component concentration of the mixed solution in which the component increases or decreases over time, such as a developer to be repeatedly used, is not determined solely by the component, but is usually a function of the concentration of the other components. Therefore, in many cases, it is difficult to display the relationship between the characteristic value of the developing solution and the component concentration in a plane graph. In such a case, in the calculation method using a calibration curve or the like, the component concentration can not be calculated from the developer characteristic value.

However, according to the multivariate analysis method (for example, the multiple regression analysis method), when a set of measured values of a plurality of characteristic values correlated with the concentration of a component to be calculated is prepared, do. In the conventional knowledge, it is possible to obtain a remarkable effect that the component concentration can be measured by measuring the characteristic value even at a glance of the component concentration, which is difficult to measure, by the component concentration measurement by the multivariate analysis method (for example, the multiple regression analysis method).

As described above, according to the computation method of the present invention, the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration of the developer can be appropriately determined according to the characteristic values of the developer (for example, conductivity, absorbance at a specific wavelength, Can be calculated on the basis of the measured values. According to the calculation method of the present invention, the concentration of each component can be calculated with high accuracy as compared with the conventional method.

In addition, since the multivariate analysis method (for example, the regression method) is used in the present invention, a characteristic value of a developing solution which is not linearly related to the concentration of a specific component of the developing solution can be employed in calculation for calculating the component concentration of the developing solution .

Further, according to the present invention, it is not necessary to prepare a large number of samples and preliminary measurement in order to enable high precision measurement, which is necessary in the invention of Patent Document 2. (As in the above-mentioned experiment example, It is sufficient to prepare and measure the number of samples p (for example, p = 11 samples) satisfying m > = np with the number of characteristic values to be measured p = The number of samples is further reduced.)

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

In the present embodiment, the absorbance at? = 560 nm is exemplified as a characteristic value of the developer having a correlation with the concentration of the dissolved photoresist in the developer, but the present invention is not limited thereto. It is also possible to use the absorbance at another specific wavelength, that is, the visible light, more preferably a specific wavelength in the wavelength range of 360 to 600 nm, and more preferably the absorbance at the wavelength? = 480 nm. This is because the absorbance at a specific wavelength included in these wavelength regions is in a relatively good correspondence with the dissolved resist concentration.

In addition, although the density is shown as a characteristic value of a developer having correlation with the absorbed carbon dioxide concentration of the developer, the present invention is not limited thereto. As the characteristic value of the developing solution correlated with the concentration of the dissolved photoresist of the developing solution and the concentration of the absorbed carbon dioxide, the characteristic value that can be adopted for the characteristic value measured in combination with the conductivity of the developing solution includes, for example, Ultrasound propagation velocity, refractive index, proper end point, pH and the like.

[Third embodiment]

3 is a schematic diagram of a developing process for describing the developer managing apparatus D of the present embodiment. The developer managing apparatus D of the present invention is shown together with the developing process facility A, the replenishing liquid storage section B, the circulating stirring mechanism C, and the like. The same components as those of the first embodiment and the second embodiment are denoted by the same reference numerals and the description thereof may be omitted.

The developer managing apparatus D of the present embodiment includes a measuring section 1, a control section 21 and an arithmetic section 36. [ In the present embodiment, unlike the second embodiment, the control means 21 and the arithmetic means 36 for performing arithmetic operations are constituted by separate devices.

The measuring section 1 is provided with a conductivity meter 11, a first characteristic value measuring means 12A and a second characteristic value measuring means 13A. The calculation means 36 calculates the measured value of the dissolved photoresist concentration of the developer by the multivariate analysis from the absorbance and the density measured by the first characteristic value measuring means 12A and the second characteristic value measuring means 13A And a measured value of the absorbed carbon dioxide concentration. At this time, the measured value of the dissolved photoresist concentration and the absorbed carbon dioxide concentration can be calculated from the conductivity, absorbance, and density by multivariate analysis.

Based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration calculated by the calculation means, the control unit 31 compares the measured dissolved photoresist concentration and the measured absorbed carbon dioxide concentration among the conductivity data stored in the data storage unit 23 To obtain the conductivity value of the concentration region specified by the conductivity value. The obtained conductivity value is set as the control target value of the conductivity of the developer.

Other configurations, operations, and the like are the same as those of the second embodiment, and therefore are omitted.

[Fourth Embodiment]

4 is a schematic diagram of a developing process for describing the developer managing apparatus D of the present embodiment. The developer managing apparatus D of the present invention is shown together with the developing process facility A, the replenishing liquid storage section B, the circulating stirring mechanism C, and the like. The same constituent elements as those of the first embodiment, the second embodiment and the third embodiment are denoted by the same reference numerals and the description thereof may be omitted.

The measuring unit 1 of the present embodiment includes a conductivity meter 11, a first concentration measuring unit 12, and a density meter 13B. The control unit 21 includes a data storage unit 23 and an operation unit 33. [ The calculating unit 33 calculates the absorbed carbon dioxide concentration of the developer from the density of the developer measured by the density meter 13B based on the corresponding relationship between the absorbed carbon dioxide concentration and the density of the developer.

The control unit 31 determines whether or not the concentration of the dissolved photoresist measured in the measuring unit 1 and the measured absorbed carbon dioxide concentration in the calculating unit 33 The conductivity value of the concentration region specified by the dissolved photoresist concentration and the measured absorbed carbon dioxide concentration is obtained. The obtained conductivity value is set as the control target value of the conductivity of the developer.

Other configurations, operations, and the like are the same as those of the first embodiment and therefore will not be described.

The relationship between the density value of the developing solution and the absorbed carbon dioxide concentration value will be described. As a result of continuing exemplary research, the inventors obtained the following findings. That is, a relatively good correspondence relationship (linear relationship) can be obtained between the density value of the developer and the absorbed carbon dioxide concentration value regardless of the concentration of the alkaline component of the developer or the concentration of the dissolved photoresist. In addition, when this correspondence relationship (linear relationship) is used, it is possible to measure the absorbed carbon dioxide concentration, which was difficult conventionally, by measuring the density of the developer with the density meter.

The inventors used eleven calibration standard solutions used for the calculation of the component concentration of the developing solution employing the multivariate analysis method as a simulated developer sample and compared them with the alkaline component concentration (TMAH concentration), the dissolved photoresist concentration, the absorbed carbon dioxide concentration, The density was measured to confirm the correlation between the component concentration and the density.

Table 6 below shows measurement results of the component concentration and density of each sample. Table 6 is a table in which the density measurement value (wt%) in Table 5 is compared with the density (g / cm ³ ) in Table ³ .

[Table 6]

Fig. 5 shows graphs of the absorbed carbon dioxide concentration and density of each sample shown in Table 6. Fig. This graph is a graph plotting the value of each sample with the concentration (g / cm ³ ) on the ordinate along the abscissa with the absorbed carbon dioxide concentration (wt%). From each plotted point, a regression line was obtained by the least squares method.

It can be understood from Fig. 5 that the absorbed carbon dioxide concentration of the developer has a good linear relationship with the density of the developer although the concentration of the alkaline component and the concentration of the dissolved photoresist varies. According to the results of this experiment, it is possible to calculate the absorbed carbon dioxide concentration of the developer by measuring the density of the developer using the correspondence (linear relationship) between the absorbed carbon dioxide concentration and the density of the developer. It is.

Therefore, the absorbed carbon dioxide concentration of the developer can be measured by using the density meter based on the corresponding relationship (linear relationship) regardless of the alkali component concentration (TMAH concentration) or the dissolved resist concentration.

The calculation unit 33 can easily measure the absorbed carbon dioxide concentration of the developer by using the relationship between the density of the developer and the absorbed carbon dioxide concentration.

[Fifth Embodiment]

6 is a schematic diagram of a developing process for describing the developer managing apparatus D of the present embodiment. The developer managing apparatus D of the present invention is shown together with the developing process facility A, the replenishing liquid storage section B, the circulating stirring mechanism C, and the like. The same components as those of the first embodiment and the second embodiment are denoted by the same reference numerals and the description thereof may be omitted.

The developer managing apparatus D of the present embodiment includes a measuring section 1, a control section 21, and an arithmetic section 37. In the present embodiment, unlike the fourth embodiment, the control means 21 and the arithmetic means 37 for performing the arithmetic operation are constituted by separate devices. The measurement unit 1 of the present embodiment includes a conductivity meter 11, a first concentration measurement unit 12, and a density meter 13B. The calculating means 37 calculates the absorbed carbon dioxide concentration of the developer from the density of the developer measured by the density meter 13B based on the corresponding relationship between the absorbed carbon dioxide concentration and the density of the developer.

The control unit 31 selects the conductivity data stored in the data storage unit 23 based on the dissolved photoresist concentration measured by the measuring unit 1 and the absorbed carbon dioxide concentration calculated by the calculating unit 37 And the conductivity value of the concentration region specified by the measured absorption carbon dioxide concentration is obtained. The obtained conductivity value is set as the control target value of the conductivity of the developer.

Other configurations, operations, and the like are the same as those of the fourth embodiment, and therefore will not be described.

As described above, according to the developer management device (D) of the present embodiment, even if the developer has any dissolved photoresist concentration and absorbed carbon dioxide concentration, since the active ingredient in the developing effect in the developer is kept constant, It is possible to realize a developing process capable of maintaining a desired line width and a residual film thickness of the wiring pattern on the substrate.

Next, modified examples of the developer management device D of the present embodiment will be described.

1 to 4 and 6, the measuring section 1 of the developer managing apparatus D shows the developer managing apparatus D constituted integrally with the controlling means 21 and the calculating means 36 and 37 , The developer management apparatus D of the present embodiment is not limited to this. The measurement unit 1 may be configured as a separate unit.

The measuring section 1 can be connected in-line to the developer piping 80 or the measuring probe 1 can be connected to the developer reservoir 61 with the measuring probe 1, Or may be provided so as to be immersed. The first conductivity measuring instrument 11, the first concentration measuring means 12, the first characteristic value measuring means 12A, the second concentration measuring means 13, the second characteristic value measuring means 13A and the density meter 13B, May be provided separately from each other. The developer managing apparatus D of this embodiment can be realized when each of the measuring means is connected to each other so as to exchange measurement data with the controlling means 21 and the calculating means 36 and 37.

According to the measuring principle employed by each measuring means, when reagent addition is required, each measuring means may have a pipe for it, or, if a waste liquid is required, each measuring means may have a conduit for it. The developer managing apparatus D of the present embodiment can be realized even if each measuring means is not connected in series.

1 to 4 and 6 show the case where the developer control device D is used for the replenishment liquid D such that the control valves 41 to 43 provided in the pipeline for feeding the replenishment liquid to be supplied to the developer become the internal components of the developer control device D, The conduits 81 and 82 and the conduit 83 for pure water are shown. However, the developer management apparatus D of the present embodiment is not limited to this. The developer management apparatus need not have the control valves 41 to 43 as internal components, and may not be connected to the conduits 81 to 83 for replenishing the developer with the replenishing liquid.

The control means 21 in the developer managing apparatus D of the present embodiment and the control valves 41 to 43 provided in the pipeline for replenishing the replenishing liquid are arranged so that the control valves 41 to 43 are connected to the developer management apparatus D to be controlled by receiving the control signal generated by the control means 21 of the control unit 21, Even if the control valve is not an internal component of the developer management apparatus D, the developer management apparatus D of the present embodiment can be realized.

[Sixth Embodiment]

7 is a schematic diagram for explaining the developer management device D of the present embodiment. The developer management apparatus D of the present embodiment has the same configuration as that of the first embodiment. The same components as those in the first to fifth embodiments are denoted by the same reference numerals and the description thereof may be omitted.

As shown in Fig. 7, the display means 22 of the sixth embodiment is characterized in that at least a conductivity value and an alkali component concentration value among the conductivity value of the developer, the alkali component concentration value, the dissolved photoresist concentration value and the absorbed carbon dioxide concentration value Either one of them can be graphically displayed with the measurement time or elapsed time from the start of measurement as an index.

Further, in the present embodiment, the display means 22 performs the switching of the graph display of the characteristic value and the component concentration by the switching button BT which is the display switching means set on the screen of the display means 22 .

Also in the first to fifth embodiments, the display means 22 of the sixth embodiment can be applied. Although the developer managing apparatus of the present invention allows various kinds of modifications as described above, it is preferable that the developer managing apparatus of the present invention further comprises: a developer concentration determining unit that determines, based on the concentration of dissolved photoresist and the concentration of absorbed carbon dioxide in the developer, And the conductivity value of the conductivity data of the concentration region specified by the measured value of the dissolved photoresist concentration of the developer and the measured value of the absorbed carbon dioxide concentration is set as the control target value and the conductivity of the developer Is replenished to the control target value.

INDUSTRIAL APPLICABILITY As described above, according to the developer managing method and the developer managing apparatus of the present invention, even if the developer has any dissolved photoresist concentration and absorbed carbon dioxide concentration, the active component in the developing operation in the developer is kept constant, It is possible to realize a developing process capable of maintaining a desired line width and a residual film thickness of the wiring pattern on the substrate.

As a preferable embodiment of the developer management apparatus, since the dissolved photoresist concentration and the absorbed carbon dioxide concentration are calculated by the multivariate analysis method, the dissolved photoresist concentration and the absorbed carbon dioxide concentration can be obtained with high precision. Based on the dissolved photoresist concentration and the absorbed carbon dioxide concentration, the target conductivity value can be obtained from the conductivity data.

Further, as a preferable aspect of the developer management apparatus, the absorbed carbon dioxide concentration of the developer is calculated from the density of the developer measured by the density meter based on the correspondence between the concentration of absorbed carbon dioxide and the density of the developer. Thus, the absorbed carbon dioxide concentration of the developing solution can be obtained more easily. Based on the absorbed carbon dioxide concentration and the separately obtained dissolved photoresist concentration, the target conductivity value can be obtained from the conductivity data.

A ... Development process equipment, B ... Refill solution reservoir, C ... Circulating stirring device, D ... Developer management device, 1 ... Measuring section, 11 ... Conductivity meter, 12 ... First concentration measuring means, 12A ... First characteristic value measuring means, 13 ... Second concentration measuring means, 13A ... Second characteristic value measuring means, 13B ... Density meter, 14 ... Sampling pump, 15 ... Sampling piping, 16 ... Exit side piping, 21 ... Control means (for example, a computer), 22 ... Display means, 23 ... A data storage unit 31, A control unit 32, 33, Operation unit, 36, 37 ... Computing means, 41 to 43 ... Control valve, 44, 45, 46, 47 ... Valve, 61 ... Developer reservoir, 62 ... Overflow tank, 63 ... Level gauge, 64 ... Developing room hood, 65 ... Roller conveyor, 66 ... Substrate, 67 ... Developer nozzle, 71 ... Waste liquid pump, 72, 74 ... Circulation pumps, 73, 75 ... Filter, 80 ... Development pipeline, 81, 82 ... Pipes for replenishment liquids (developer liquid and / or new liquid), 83 ... Pure water pipeline, 84 ... Confluence channel, 85 ... Circulation duct, 86 ... Pipes for nitrogen gas, 91, 92 ... The replenishment liquid (developer stock solution and / or fresh solution)

Claims (11)

Data in which conductivity data having a conductivity value of the developer, which has been confirmed to have a predetermined developing performance beforehand for each concentration region specified with the concentration of the dissolved photoresist and the absorbed carbon dioxide concentration of the developer showing alkalinity repeatedly used as indexes A storage unit,
The conductivity value stored in the data storage unit of the concentration region specified by the measured value of the dissolved photoresist concentration of the developer and the measured value of the absorbed carbon dioxide concentration is set as the control target value and the conductivity of the developer is set to the control target value A control unit for issuing a control signal to a control valve provided in a pipeline for feeding a replenishing liquid replenished to the developer,
And control means
Display means for displaying at least one of a conductivity value, an alkali component concentration value, a dissolved photoresist concentration value and an absorbed carbon dioxide concentration value obtained from the developer, at least one of a conductivity value and an alkali component concentration value,
And a developing device for developing the developer. The method according to claim 1,
Further comprising display switching means for switching an object to be displayed displayed on the display means. Data in which conductivity data having a conductivity value of the developer, which has been confirmed to have a predetermined developing performance beforehand for each concentration region specified with the concentration of the dissolved photoresist and the absorbed carbon dioxide concentration of the developer showing alkalinity repeatedly used as indexes A storage unit,
The conductivity value stored in the data storage unit of the concentration region specified by the measured value of the dissolved photoresist concentration of the developer and the measured value of the absorbed carbon dioxide concentration is set as the control target value and the conductivity of the developer is set to the control target value A control unit for issuing a control signal to a control valve provided in a conduit for feeding a replenishing liquid replenished to the developer,
And control means
At least either the conductivity value or the alkali component concentration value among the conductivity value, the alkali component concentration value, the dissolved photoresist concentration value and the absorbed carbon dioxide concentration value obtained from the developer is measured with the measurement time or the elapsed time from the start of measurement as a graph Display means for displaying,
And a developing device for developing the developer. The method of claim 3,
Further comprising display switching means for switching an object to be displayed displayed on the display means. 5. The method according to any one of claims 1 to 4,
A plurality of measurement devices for measuring a plurality of characteristic values of the developer including a characteristic value of the developer correlated with the concentration of the dissolved photoresist of the developer and a characteristic value of the developer correlated with the absorbed carbon dioxide concentration of the developer Further,
Wherein,
A calculation unit for calculating a measured value of the dissolved photoresist concentration and a measured value of the absorbed carbon dioxide concentration of the developer from the plurality of characteristic values of the developer measured by the plurality of measuring apparatuses by a multivariate analysis method,
Further comprising: 5. The method according to any one of claims 1 to 4,
A plurality of measurement devices for measuring a plurality of characteristic values of the developer including a characteristic value of the developer correlated with a dissolved photoresist concentration of the developer and a characteristic value of the developer correlated with an absorbed carbon dioxide concentration of the developer; ,
Calculating means for calculating a measured value of the dissolved photoresist concentration of the developer and a measured value of the absorbed carbon dioxide concentration from a plurality of characteristic values of the developer measured by the plurality of measuring apparatuses by using a multivariate analysis method,
Further comprising: 5. The method according to any one of claims 1 to 4,
Density meter,
Wherein,
An operation unit for calculating the absorbed carbon dioxide concentration value of the developer from the density value of the developer measured by the density meter based on the corresponding relationship between the absorbed carbon dioxide concentration and the density of the developer,
Further comprising: 5. The method according to any one of claims 1 to 4,
Density meter,
Calculating means for calculating an absorbed carbon dioxide concentration value of the developer from the density value of the developer measured by the density meter based on the correspondence between the absorbed carbon dioxide concentration and the density of the developer;
Further comprising: Having an alkali component concentration value of the developer which has been previously confirmed to have a predetermined developing performance for each concentration region specified with the absorbance and the absorbed carbon dioxide concentration correlated with the dissolved photoresist concentration of the developing solution exhibiting alkalinity repeatedly used as an index A data storage unit for storing alkali component concentration data;
The alkali component concentration value stored in the data storage section of the concentration area specified by the measured absorbance of the developer and the absorbed carbon dioxide concentration is set as the control target value and the alkali component concentration of the alkali component concentration of the developer is determined to be the control target value A control unit for issuing a control signal to a control valve provided in a pipe for feeding a replenishing liquid to be supplied to the developer,
And control means
Display means for displaying at least the alkali component concentration value among the alkali component concentration value obtained from the developer, the absorbance value correlated with the dissolved photoresist concentration, and the absorbed carbon dioxide concentration value,
And a developing device for developing the developer. Having an alkali component concentration value of the developer which has been previously confirmed to have a predetermined developing performance for each concentration region specified with the absorbance and the absorbed carbon dioxide concentration correlated with the dissolved photoresist concentration of the developing solution exhibiting alkalinity repeatedly used as an index A data storage unit for storing alkali component concentration data;
The alkali component concentration value stored in the data storage section of the concentration area specified by the measured absorbance of the developer and the absorbed carbon dioxide concentration is set as the control target value and the alkali component concentration of the alkali component concentration of the developer is determined to be the control target value A control unit for issuing a control signal to a control valve provided in a pipe for feeding a replenishing liquid to be supplied to the developer,
And control means
At least the alkali component concentration value among the alkali component concentration value obtained from the developer, the absorbance value correlated with the dissolved photoresist concentration, and the absorbed carbon dioxide concentration value is displayed as a graph using the measurement time or the elapsed time from the start of measurement as an index Display means for displaying,
And a developing device for developing the developer. 11. The method according to claim 9 or 10,
Further comprising display switching means for switching an object to be displayed displayed on the display means.

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