TW201704900A - Component concentration measuring apparatus for developing solution, component concentration measuring method, developing solution managing apparatus and developing solution managing method supplies replenishing solution to the developing solution - Google Patents

Abstract

This disclosure provides a component concentration measuring apparatus for developing solution to measure the concentration of carbon dioxide in an alkaline developing solution, and a developing solution managing apparatus that manages the concentration of carbon dioxide in the alkaline developing solution. The component concentration measuring apparatus for developing solution and the developing solution managing apparatus of the invention have density gages to measure the concentration of the developing solution. The density of the developing solution corresponds well with the concentration of carbon dioxide regardless of the concentration of alkaline and other components. The component concentration measuring apparatus calculates the concentration of carbon dioxide based on the corresponding relationship between the density of the developing solution and the concentration of carbon dioxide. The developing solution managing apparatus makes use of the corresponding relationship between the density of the developing solution and the concentration of carbon dioxide, based on the measured density of the developing solution or the calculated concentration of carbon dioxide, to supply a replenishing solution to the developing solution in such a way that the concentration of carbon dioxide of the developing solution is set to be a predetermined management value or to be lower than the predetermined management value, in order to manage the concentration of carbon dioxide of the developing solution.

Description

Component concentration measuring device for developer, component concentration measuring method, developing solution management device, and developer management method

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

In a developing process of photolithography for fine wiring processing in a semiconductor, a liquid crystal panel, or the like, an alkaline developing solution is used for dissolving a chemical solution for forming a photoresist on a substrate (hereinafter, referred to as "Alkaline developer").

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

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

However, the alkaline developer easily absorbs carbon dioxide in the air to form carbonate. At this time, the alkaline component having development activity in the developer is consumed and reduced. Therefore, in order to maintain the development performance of the developing developer with high precision, it is necessary to carry out developer management in consideration of the influence of the carbon dioxide absorbed by the developer on the developing performance.

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

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

Prior technical literature Patent literature

Patent Document 1 Japanese Patent No. 2561778

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

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

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

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

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

In addition, regarding the concentration of carbon dioxide absorbed by the developer (hereinafter referred to as "absorbed carbon dioxide concentration"), it has not been known that the developer has a good characteristic value in a good relationship with the concentration of absorbed carbon dioxide, and it is difficult to measure absorption with high precision. Carbon dioxide concentration.

The present invention has been made in order to solve the above problems. An object of the present invention is to provide a component concentration measuring device for a developing solution capable of measuring a carbon dioxide concentration of a developing solution from a density value of a developing solution belonging to a multi-component system, and a component concentration measuring method, and a carbon dioxide capable of causing a developing solution The developer management device and the developer management method that manage the concentration to a predetermined management value or not to exceed a predetermined management value.

A component concentration measuring apparatus according to a first aspect of the present invention includes: a density meter; and a calculation means for density value and carbon dioxide concentration value of the developing solution based on a density value of the alkaline developing solution measured by a densitometer The correspondence between the two is calculated as the carbon dioxide concentration of the developer.

The component concentration measuring apparatus according to the first aspect described above includes a densitometer that measures a density value that has a good correlation with the carbon dioxide concentration of the developer. Therefore, the carbon dioxide absorbed by the developer can be calculated from the density value measured by the densitometer. concentration.

The component concentration measuring method according to the second aspect of the present invention measures the density of the alkaline developing solution, and calculates the aforementioned relationship between the density of the developing solution and the carbon dioxide concentration based on the measured density of the developing solution. The carbon dioxide concentration of the developer.

According to the component concentration measuring method of the second aspect described above, the density value which has a good correlation with the carbon dioxide concentration of the developer can be measured, and the absorbed carbon dioxide concentration of the developer can be calculated from the measured density value.

A developer management apparatus according to a third aspect of the present invention includes: a density meter; and a control means for using a density value of the developing solution and a carbon dioxide concentration value based on a density value of the alkaline developing solution measured by a densitometer The correspondence relationship between the carbon dioxide concentration of the developer is a predetermined management value or a predetermined management value or less, and a control signal is provided to the control valve provided in the flow path for supplying the replenishing liquid supplied to the developer.

According to the developer management apparatus of the third aspect, the amount of the replenishing liquid to be replenished is known from the density value of the developer measured by the densitometer by the density relationship between the density of the developer and the carbon dioxide concentration. The replenishing liquid is supplied and managed so that the absorbed carbon dioxide concentration of the developer becomes a predetermined management value or less than a predetermined management value.

The developer management method according to the fourth aspect of the present invention measures the density of the alkaline developing solution; and based on the measured density of the developing solution, the correspondence between the density of the developing solution and the carbon dioxide concentration is used. The replenishing liquid is supplied to the developer in such a manner that the carbon dioxide concentration of the developer becomes a predetermined management value or a predetermined management value or less.

According to the developer management method according to the fourth aspect, the amount of the replenishing liquid to be replenished is known from the density value of the measured developer by the density relationship between the density of the developer and the carbon dioxide concentration, so that development can be performed. The replenishing liquid is supplied and managed so that the absorbed carbon dioxide concentration of the liquid becomes a predetermined management value or a predetermined management value or less.

A developer management apparatus according to a fifth aspect of the present invention includes: a density meter; and an arithmetic control unit including an arithmetic unit and a control unit, wherein the calculation unit is based on a density of an alkaline developer measured by a densitometer The value is calculated from the correspondence relationship between the density value of the developer and the carbon dioxide concentration value, and the carbon dioxide concentration of the developer is calculated based on the carbon dioxide concentration of the developer calculated by the calculation unit so that the carbon dioxide concentration of the developer becomes predetermined. The management value is below the predetermined management value In this way, a control signal is issued to the control valve provided in the flow path for supplying the replenishing liquid supplied to the developer.

According to the developer management apparatus of the fifth aspect, the density meter for measuring the density value which has a good correlation with the carbon dioxide concentration of the developer, the carbon dioxide absorption coefficient of the developer can be calculated from the density value measured by the densitometer. The concentration can be managed by replenishing the replenishing liquid so that the absorbed carbon dioxide concentration of the developer becomes a predetermined management value or less than a predetermined management value.

A developer management apparatus according to a sixth aspect of the present invention includes: a density meter; and a calculation means based on a density value of a developing solution which is measured by a densitometer, and a density value and a carbon dioxide concentration value of the developer. The CO 2 concentration of the developer is calculated in accordance with the relationship between the two, and the control means is such that the carbon dioxide concentration of the developer calculated by the calculation means is such that the carbon dioxide concentration of the developer becomes a predetermined management value or a predetermined management value or less. A control signal is issued to the control valve provided in the flow path for supplying the replenishing liquid supplied to the developer.

According to the developer management apparatus of the sixth aspect, the density meter for measuring the density value which has a good correlation with the carbon dioxide concentration of the developer, the carbon dioxide absorption of the developer can be calculated from the density value measured by the densitometer. The concentration can be managed by supplying the replenishing liquid so that the concentration of the absorbed carbon dioxide of the developer becomes a predetermined management value or less than a predetermined management value.

A developer management method according to a seventh aspect of the present invention is for measuring a density of a developing developer which is alkaline; and a correspondence between a density of the developer and a concentration of carbon dioxide based on the measured density of the developer; In the relationship, the carbon dioxide concentration of the developer is calculated, and the replenishing liquid is supplied to the developer so that the calculated carbon dioxide concentration of the developer becomes a predetermined management value or less than a predetermined management value.

According to the developer management method of the seventh aspect, the density value which has a good correlation with the carbon dioxide concentration of the developer is measured, and the concentration of the absorbed carbon dioxide of the developer can be calculated from the density value, and the concentration of the absorbed carbon dioxide of the developer can be made. The supplemental liquid is managed to be a predetermined management value or a predetermined management value or less.

According to the present invention, it is possible to measure the concentration of absorbed carbon dioxide of a developer which is conventionally difficult to measure. In addition, it is possible to manage the supply of the replenishing liquid to the developing solution so that the carbon dioxide concentration of the developing solution becomes a predetermined management value or less than a predetermined management value based on the measured density value or the calculated absorbed carbon dioxide concentration value.

1‧‧‧Determination Department

2‧‧‧ Calculation Department

3‧‧‧Control Department

11‧‧‧density meter

12, 13‧‧‧Measurement means

14‧‧‧Sampling pump

15‧‧‧Sampling piping

16‧‧‧Exit side piping

21‧‧‧ calculus

22‧‧‧ Display means

23‧‧‧ Calculation Control Department (eg computer)

31‧‧‧Control block

41 to 43‧‧‧ control valve

44, 45, 46, 47‧ ‧ valves

51‧‧‧ sample room

52‧‧‧ thermometer

53‧‧‧Paltier components

54‧‧‧ thermostatic components

55‧‧‧Insulation

56‧‧‧ vibrator

61‧‧‧ developer storage tank

62‧‧‧Overflow trough

63‧‧‧liquid level meter

64‧‧‧Development room cover

65‧‧‧Roller conveyor

66‧‧‧Substrate

67‧‧‧Developing sprinkler

71‧‧‧Waste pump

72, 74‧‧‧ Circulating pump

73, 75‧‧‧ filter

80‧‧‧developer line

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

83‧‧‧Pure water pipeline

84‧‧‧Confluence pipeline

85‧‧‧Circulation line

86‧‧‧Nitrogen pipeline

91, 92‧‧‧Replenishment tank

A‧‧‧ component concentration measuring device

B‧‧‧Developing process equipment

C‧‧‧Replenishment Storage Department

D‧‧‧Circulating mixing mechanism

E‧‧‧ developer management device

Fig. 1 is a graph showing the relationship between the carbon dioxide concentration of the developer and the density.

Fig. 2 is a schematic view showing a device for measuring the concentration of a developer.

Fig. 3 is a schematic view showing a representative configuration of a vibrating densitometer.

Fig. 4 is a schematic view showing a development processing process of the developer management apparatus of the second embodiment.

Fig. 5 is a schematic view showing a development processing process of the developer management apparatus according to the third embodiment.

Fig. 6 is a schematic view showing a development processing process of the developer management apparatus of the fourth embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, the shape, the size, the size ratio, the relative arrangement, and the like of the apparatus and the like described in the following embodiments are not intended to limit the scope of the present invention, and are merely illustrative examples. Sexual illustration.

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

Further, in the following description, the concentration of the component such as the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration is a concentration calculated by the weight percent concentration (wt%). The "dissolved photoresist concentration" refers to a concentration at which the dissolved photoresist is converted into a resist amount; the "absorbed carbon dioxide concentration" refers to a concentration at which the absorbed carbon dioxide is converted into carbon dioxide.

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

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

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

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

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

The inventors of the present invention obtained the following findings after continuing research on the above points. That is, irrespective of the alkaline component concentration and the dissolved photoresist concentration of the developer, a relatively good correspondence (linear relationship) between the density value of the developer and the carbon dioxide concentration value can be obtained. Further, by using the correspondence (linear relationship), it is possible to measure the concentration of the absorbed carbon dioxide which has been difficult to measure in the past by measuring the density of the developer by a densitometer. Further, by using the correspondence relationship (linear relationship), it is possible to manage the carbon dioxide concentration of the developer by replenishing the replenishing liquid based on the measured density value or the calculated carbon dioxide concentration value.

The inventors of the present invention envisaged a management environment in which 2.38% of TMAH aqueous solution was carried out, and a TMAH aqueous solution having various changes in the concentration of the alkaline component, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration was prepared as a simulated developer sample. The inventor of the present invention has a basic composition of 2.38% TMAH aqueous solution as a developing solution, and has prepared an alkaline component. 11 calibration standard solutions with various changes in degree (TMAH concentration), dissolved photoresist concentration, and absorbed carbon dioxide concentration.

The inventors of the present invention conducted experiments in which the alkaline component concentration (TMAH concentration), the absorbed carbon dioxide concentration, and the density were measured for the simulated developer samples, and the relationship between the component concentration and the density was confirmed.

The manner in which the measurement was carried out was carried out by adjusting the temperature of the calibration standard solution to 25.0 °C. The temperature adjustment method is as follows: the bottle with the calibration standard solution is immersed in a constant temperature water bath with a temperature management at 25 ° C for a long time, and sampling is performed in this state, and the temperature controller is adjusted again immediately before the measurement is performed. Up to 25.0 ° C. For the density measurement, a density is measured using a densitometer using a natural vibration method, that is, a natural vibration frequency measured by applying vibration to a U-shaped tube flow cell. The unit of the measured density value is g/cm ³ .

Table 1 below shows the measurement results of the component concentration and density of each sample.

In view of the fact that the TMAH aqueous solution is strongly alkaline and easily absorbs carbon dioxide, the value of the component concentration in Table 1 is obtained by measuring each sample by a titration analysis method capable of accurately analyzing the basic component concentration (TMAH concentration) and the absorbed carbon dioxide concentration. Among them, the weight modulation value is used for the dissolved photoresist concentration.

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

Fig. 1 is a graph showing the concentration of absorbed carbon dioxide and the density of each sample shown in Table 1. This graph is a graph in which the carbon dioxide concentration (wt%) is plotted on the horizontal axis and the density (g/cm ³ ) is plotted on the vertical axis. The regression line is obtained by the least square method from each point drawn.

It can be understood from Fig. 1 that although there are various changes in the alkaline component concentration and the dissolved photoresist concentration of the developer, there is a good linear relationship between the concentration of the absorbed carbon dioxide and the density of the developer. According to the results of this experiment, the inventors of the present invention found that by using the correspondence relationship (linear relationship) between the carbon dioxide concentration and the density of the developer, it is possible to calculate the absorption carbon dioxide concentration of the developer by measuring the density of the developer. .

Therefore, it is possible to realize a component concentration measuring device for a developer using a densitometer that can measure the carbon dioxide concentration of the developer by the correlation (linear relationship) irrespective of the alkali component concentration (TMAH concentration) and the dissolved resist concentration.

Further, in the alkaline developing solution which is repeatedly used in the developing treatment process, the basic component concentration (TMAH concentration) and the dissolved resist concentration are usually managed by the developer management device. Compared to the above-described simulation of the sample, there is less factor that causes a linear relationship between the density of the developer and the concentration of carbon dioxide. Therefore, the component concentration measuring device capable of measuring the concentration of the absorbed carbon dioxide in the developing solution of the present invention can be suitably used as one member of the developer managing device that can monitor and manage the concentration of the absorbed carbon dioxide.

Further, the alkaline developing solution tends to increase the absorption of carbon dioxide. Therefore, by adding a replenishing liquid having a low carbon dioxide concentration (for example, a stock solution of a developing solution and a new liquid) to the replenishing liquid, the developing solution can be used. The absorbed carbon dioxide concentration is managed at a predetermined management value or managed below a predetermined management value.

Further, as shown in Fig. 1, the carbon dioxide concentration of the developer has a monotonously increasing correspondence relationship (linear relationship) with the density, so that the concentration of the absorbed carbon dioxide of the developer becomes a predetermined management value or becomes a predetermined management value or less. The density value of the developer is made to correspond to a predetermined management value or to a corresponding predetermined management value. Therefore, when the density value corresponding to the management value of the carbon dioxide concentration is used as the management value of the density, the density of the developer is measured, and the measured density value is managed as or smaller than the management value. By this, it is also possible to manage the developer in such a manner that the concentration of the absorbed carbon dioxide of the developer becomes a predetermined management value or a predetermined management value or less.

Here, the predetermined management value refers to a density value which is predetermined as an upper limit value of the concentration value of carbon dioxide of the developer which can develop the developing performance satisfactorily, or a density value corresponding to the density value. This is also true in the following description.

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

First embodiment

Fig. 2 is a schematic view showing a component concentration measuring device of the developing solution of the embodiment.

The component concentration measuring device A of the developing solution of the present embodiment includes the measuring unit 1 and the calculating unit 2.

The measurement unit 1 includes a density meter for measuring the density of the developer and another measurement means (11 to 13 in the figure) for measuring other characteristic values of the developer, and a sampling pump 14 A temperature bath (not shown) or the like for adjusting the temperature of the sampled liquid to a predetermined measurement temperature (for example, 25 ° C) before the measurement is performed.

When the component concentration measuring apparatus A only needs to measure the density, the measuring means 11 to 13 of the measuring unit 1 may be provided with a densitometer (for example, 11), and the measuring means (for example, 12, 13) for measuring other characteristic values are not required. However, as a component concentration measuring device for an alkaline developing solution, it is not only necessary to measure the concentration of carbon dioxide, but it is also often necessary to measure the concentration of the alkaline component and the concentration of the photoresist dissolved in the developing solution. Therefore, in the second drawing, measurement means 11, 12, and 13 including other measurement means necessary for measuring the concentration of the alkaline component and the concentration of the dissolved photoresist are described. Among them One is a densitometer. In the following description of the component concentration measuring apparatus A, the measuring means 11 among the measuring means 11 to 13 of Fig. 2 is used as the density meter.

The calculation unit 2 includes a calculation block 21 for calculating a carbon dioxide concentration value from the measured density value. In the calculation block 21, the correspondence relationship between the density of the developer and the carbon dioxide concentration has been previously input (for example, the linear relationship as shown in Fig. 1). The calculation block 21 has a function of obtaining a corresponding carbon dioxide concentration value from the measured density value of the developer. Further, the calculation unit 2 preferably includes a display means 22 for displaying the calculated carbon dioxide concentration. Further, the component concentration measuring device A is connected to the tank for storing the developer through the sampling pipe 15.

The component concentration measuring method performed by the component concentration measuring apparatus A of the present embodiment will be described. The developer is transported to the measurement unit 1 by the sampling pump 14. The developer supplied to the measuring unit 1 is first adjusted to a predetermined measurement temperature (for example, 25 ° C) in a constant temperature bath. The temperature-adjusted developer is supplied to the densitometer 11 and other measuring means 12, 13. The density meter 11 measures the density of the developer. The other measuring means 12 and 13 also measure the characteristic values of the developing solution. The developer after the measurement is discharged from the outlet side pipe 16 to the outside of the component concentration measuring device A.

The densitometer 11 and the other measuring means 12 and 13 are connected to the calculation block 21 of the calculation unit 2 via a signal line. The density value of the developer measured by the densitometer 11 and the measurement data of the characteristic value of the developer measured by the other measuring means 12 and 13 are transmitted to the calculation block 21 via the signal line.

The calculation block 21, which receives the measurement data of the density value of the developer and other characteristic values, calculates the component concentration of the developer based on the measurement data. The carbon dioxide concentration of the developer is calculated by a correspondence relationship between the density of the developer and the carbon dioxide concentration (for example, as shown in the linear relationship of Fig. 1). That is, from the correspondence relationship between the density of the developer and the carbon dioxide concentration, a carbon dioxide concentration value corresponding to the measured density value of the developer is obtained, and this value is a measured value of the carbon dioxide concentration of the developer.

In this way, the component concentration measuring device A of the developing solution of the present embodiment can measure the carbon dioxide concentration of the developing solution from the relationship between the density of the developing solution and the carbon dioxide concentration based on the measured value of the density of the developing solution.

In the component concentration measuring apparatus A of the present embodiment, as shown in FIG. 2, the measuring unit 1 and the calculating unit 2 may be configured independently of each other. In the case of the independent configuration, the measurement data measured by the density meter 11 of the measurement unit 1 and the other measurement means 12 and 13 may be transferred to the calculation block 21 of the calculation unit 2 by a signal line or the like. The measurement data can also be sent via wireless signals.

The component concentration measuring device A and the measuring unit 1 of the present embodiment may be directly connected or bypassed to be connected to the storage tank so as to be capable of sampling the developer from the storage tank in which the developer is stored. A circulation line of the development processing process of the developer is recycled.

In addition, in the second drawing, the measurement means 11 to 13 including the densitometer are connected in series, but each measurement is performed. The means of connection is not limited to this. They may be connected in parallel, or they may be independently provided with a chemical solution transport path for measurement. Regarding the order of measurement of the densitometer and other measuring means, there is no particular order. The measurement may be carried out in an optimal order as appropriate in accordance with the characteristics of each measuring means.

The sampling pump 14 among the configurations of the measuring unit 1 shown in Fig. 2 is not necessarily required. When it is directly connected to the circulation line, it is not necessary to provide the sampling pump 14 in the measurement unit 1. Further, when the developer is sampled from the storage tank, the sampling pump 14 may not be provided in the measurement unit 1. On the other hand, although not shown, it is preferable to arrange the thermostat for adjusting the developing solution to a predetermined measurement temperature before the measurement means.

The calculation block 21 of the calculation unit 2 has a function of calculating the carbon dioxide concentration from the measured value of the density, and may have a function of calculating other component concentrations such as the alkaline component concentration and the dissolved photoresist concentration of the developer. In this way, a component concentration measuring device capable of measuring the alkali component concentration, the dissolved photoresist concentration, and the carbon dioxide concentration of the developer can be realized.

In the density meter 11 of the component concentration measuring apparatus A of the present embodiment, a float type densitometer using buoyancy, a differential pressure densitometer using a pressure difference between two points of different heights in a liquid, and a gamma ray can be used. Various densitometers such as gamma ray densitometers. It is preferable to use a vibrating densitometer that detects the natural vibration frequency of a pipe filled with a liquid to obtain a density.

Fig. 3 schematically shows a representative configuration of a vibrating densitometer.

The measurement unit of the vibrating densitometer includes a sample chamber 51 bent in a U shape, a thermostat block 54 surrounding the sample chamber 51, and a heat insulating material 55 disposed on the outer periphery of the thermostat unit 54. The thermostat unit 54 is provided with a Peltier device 53 for adjusting the temperature of the sample. In the sample chamber 51, a vibrator 56 is provided at the tip end of the curved portion, and a driving portion that drives the vibrator 56 to vibrate and a detecting portion that detects the vibration frequency of the vibrator 56 are disposed close to the vibrator 56.

The sample chamber 51 of the excited vibration vibrates at a natural vibration frequency associated with the mass of the liquid inside. By detecting the natural frequency, the mass of the liquid in the sample chamber 51 can be known. Therefore, the density of the liquid is measured from the internal volume of the sample chamber 51.

The vibrating densitometer is characterized in that it can perform measurement with high sensitivity and stability, and can perform measurement continuously. The vibrating densitometer can be measured under good temperature conditions and temperature stability by means of a thermometer, a temperature adjusting means, and a heat insulating means. Further, the vibrating densitometer can measure the density of the sample by transporting the liquid of the sample to the sample chamber. When measuring the density, it is not necessary to add a reagent, and there is no waste liquid.

The method of installing the various measuring means 11 to 13 in the component concentration measuring device of the developing solution of the present embodiment, in particular, the method of setting the densitometer, is not limited to the one shown in Fig. 2 .

The density meter has various measurement principles and measurement methods, and each has a suitable setting method. When the density meter is a float type density meter or a differential pressure type density meter, it is preferable to set the density meter so that the float portion and the probe portion of the densitometer are immersed in the storage tank of the developer. When adopted The gamma ray density meter is capable of directly setting the densitometer to the line through which the developer flows. When the vibrating density timer is used, as shown in Fig. 2, by connecting the storage tank and the densitometer through the sampling line, the developer can be sampled and continuously measured.

The vibrating densitometer is capable of measuring the density by transporting the developer to the sample chamber, and is therefore suitable for continuous and online use. Further, it is suitable for stably controlling measurement conditions such as liquid temperature, and it is possible to perform stable and highly sensitive measurement. The vibrating densitometer for the process can also be measured with an accuracy of about 0.001 (g/cm ³ ). According to the linear relationship of Fig. 1, the component concentration measuring device of the present embodiment can achieve about 0.15 (wt%). The degree of measurement of carbon dioxide accuracy. As long as the alkaline component concentration and the dissolved photoresist concentration of the developer are managed, the linear relationship between the density and the carbon dioxide concentration is further improved, and the measurement accuracy of the densitometer is also expected to increase, so the component concentration measuring device is also improved. It is expected that the carbon dioxide concentration can be measured with higher precision.

In the component concentration measuring device of the developing solution of the present embodiment, it is possible to use a member for managing the concentration of carbon dioxide as the developing solution management device by measuring the concentration of carbon dioxide in the developing solution. The control is performed by supplying the replenishing liquid to the developing solution so that the carbon dioxide concentration of the developing solution measured by the component concentration measuring device is equal to or lower than a predetermined management value or a predetermined management value. In combination with the component concentration measuring device of the present embodiment, it is possible to configure a developer management device capable of managing the concentration of carbon dioxide.

Further, by using the component concentration measuring device of the developing solution of the present embodiment, the measured carbon dioxide concentration of the developing solution is compared with the allowable value of the carbon dioxide concentration of the developing solution, and when the allowable value is exceeded, a signal or flicker is emitted. A warning light or a buzzer or the like can also constitute a component concentration monitoring device for the developer.

Second embodiment

Fig. 4 is a developing solution for managing the carbon dioxide concentration of the developing solution by using the relationship between the density of the developing solution and the carbon dioxide concentration by the density value of the developing solution measured by the densitometer, by replenishing the replenishing liquid to the developing solution. Schematic diagram of the management device. For convenience of explanation, the developer management device E is connected to the developing process device B, and is illustrated together with the developing process device B, the replenishing liquid storage portion C, and the circulating stirring mechanism D.

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

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

Next, the developer management device E of the present embodiment will be described. The developer management device E of the present embodiment is a developer management device that measures the density of the developer by a densitometer and uses the relationship between the density of the developer and the concentration of carbon dioxide (for example, the linear relationship in FIG. 1). The replenishing liquid is supplied to the developing solution based on the measured density value so that the carbon dioxide concentration of the developing solution becomes a predetermined management value or less than a predetermined management value.

The developer management device E includes the measurement unit 1 , the calculation unit 2 , and the control unit 3 , and is connected to the developer storage tank 61 through the sampling pipe 15 and the outlet side pipe 16 . The measurement unit 1, the calculation unit 2, and the control unit 3 are connected via a signal line.

The measuring unit 1 includes a sampling pump 14, a density meter 11, and measuring means 12 and 13 for measuring other characteristic values of the developing solution. The measuring means 12 and 13 are used, for example, to measure the alkaline component concentration and the dissolved photoresist concentration of the developer. The densitometer 11 and the measuring means 12 and 13 are connected in series to the rear stage of the sampling pump 14. The measuring unit 1 is preferably a combination A temperature adjustment means (not shown) for stabilizing the sampled developer to a predetermined temperature in order to improve the measurement accuracy. At this time, the temperature adjustment means is preferably disposed before the measuring means. The sampling pipe 15 is connected to the sampling pump 14 of the measuring unit 1, and the outlet side pipe 16 is connected to a pipe at the end of the measuring means.

The calculation unit 2 includes, for example, a calculation block 21 for calculating the concentration of the alkaline component of the developer and the concentration of the dissolved photoresist. The calculation block 21 is connected to the measurement means 12 and 13 provided in the measurement unit 1 via a signal line. When the developer management device E only needs to have a function of measuring the density of the developer to control the concentration of the carbon dioxide, the measurement means 12 and 13 and the calculation unit 2 are not required.

The control unit 3 is connected to the densitometer 11 of the measuring unit 1 via a signal line. Further, the control unit 3 is connected to the control valves 41 to 43 provided in the flow path for supplying the replenishing liquid to the developing solution via signal lines. In Fig. 4, although the control valves 41 to 43 are shown as internal members of the developer management device E, the control valves 41 to 43 are not necessarily required members of the developer management device E of the present embodiment. The control unit 3 controls the operations of the control valves 41 to 43 so as to be able to communicate with the control valves 41 to 43 so that the replenishing liquid can be supplied to the developing solution. The control valves 41 to 43 may also be present outside the developer management device E.

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

The developer sampled from the developer storage tank 61 is sent to the measurement unit 1 to adjust the temperature. The developing solution was transported to the density meter 11 after temperature adjustment, and the density value was measured. The density measurement data is transmitted to the control unit 3.

The control unit 3 sets a management value of the density corresponding to the management value of the carbon dioxide concentration determined according to the correspondence relationship between the density of the developer and the carbon dioxide concentration (for example, the linear relationship as shown in FIG. 1). The control unit 3 controls the density of the developer obtained from the measurement unit 1 as follows.

When the management is performed such that the carbon dioxide concentration of the developer becomes a predetermined management value, the following management is performed. In other words, the replenishing liquid is supplied to the developing solution so that the density value of the measured developing solution becomes a management value of the density corresponding to the management value of the carbon dioxide concentration. If the concentration is not managed, the developer tends to absorb carbon dioxide to increase the concentration of carbon dioxide. Therefore, the replenishing liquid may be supplied as a replenishing liquid which serves to dilute the concentration of carbon dioxide in the developing solution.

When the management is performed such that the carbon dioxide concentration of the developer is equal to or less than a predetermined management value, the following management is performed. In other words, since the correspondence between the density of the developer and the carbon dioxide concentration is monotonously increasing as shown in Fig. 1, the density value of the measured developer is set to a density corresponding to the management value of the carbon dioxide concentration. The replenishing solution is supplied to the developer in the following manner. The replenishing replenishing liquid may be supplied as a replenishing liquid which produces a function of diluting the carbon dioxide concentration of the developing solution.

Here, the "predetermined management value" refers to a management value that is known in advance as a carbon dioxide concentration value when the developer develops optimum developing performance. For example, when the liquid chemical property of the developer is evaluated by the line width and the residual film thickness obtained by the development treatment, the line width and the residual film thickness can be made. The carbon dioxide concentration value of the developer which is the optimum value desired. This is also true in the following description.

In the management of the carbon dioxide concentration of the developer, for example, in the case where the developer uses a 2.38% TMAH aqueous solution, the carbon dioxide concentration of the developer is preferably managed to be 0.40 (wt%) or less. More preferably managed below 0.25 (wt%).

In addition, in the developer management device E, the measurement means 12 and 13 for measuring the characteristic value of the developer necessary for this purpose are usually provided by measuring the concentration of the alkaline component and the concentration of the dissolved photoresist. The characteristic values of the developer measured by the measuring means 12 and 13 are transmitted to the calculation unit 2. The calculation unit 2 calculates the basic component concentration and the dissolved photoresist concentration from the measured characteristic values of the developer, and transmits the result to the control unit 3. The control unit 3 manages the alkaline component concentration and the dissolved photoresist concentration of the developer in an optimum state based on the measurement result or the calculation result.

The replenishing liquid supplied to the developing solution is, for example, a stock solution of a developing solution, a new liquid, pure water, or the like. These replenishing liquids are used to dilute the carbon dioxide concentration of the developing solution. These replenishing liquids are also supplied for managing the alkaline component concentration and the dissolved photoresist concentration of the developing solution.

The replenishing liquid is stored in the replenishing liquid storage tanks 91 and 92 of the replenishing liquid storage unit C. The replenishing liquid storage tanks 91 and 92 are connected to a nitrogen gas line 86 including valves 46 and 47, and are pressurized by nitrogen gas supplied through the piping. Further, the replenishing liquid storage tanks 91 and 92 are connected to the replenishing liquid pipes 81 and 82, respectively, and the replenishing liquid is transported through the valves 44 and 45 in the normally open state. The replenishing liquid pipes 81 and 82 and the pure water pipe 83 are provided with control valves 41 to 43, and the control valves 41 to 43 are controlled by the control unit 3 System opening and closing. By the operation of the control valves 41 to 43, the replenishing liquid stored in the replenishing liquid storage tanks 91, 92 and the pure water are conveyed. Then, the replenishing liquid is merged with the circulation stirring mechanism D through the joining line 84, and is supplied to the developing solution storage tank 61 to be stirred.

When the replenishing liquid stored in the replenishing liquid storage tanks 91, 92 is reduced by replenishment, the internal pressure thereof is lowered, and the supply amount becomes unstable. Therefore, the valves 46, 47 are appropriately opened in response to the decrease in the replenishing liquid. Nitrogen gas is supplied to maintain the internal pressure of the replenishing liquid storage tanks 91 and 92. When the replenishing liquid storage tanks 91, 92 are empty, the valves 44, 45 are closed, the new replenishing liquid storage tank filled with the replenishing liquid is replaced, or the empty replenishing liquid storage tanks 91, 92 are refilled. Prepared supplement solution.

The control of the control valves 41 to 43 is performed, for example, as follows. As long as the flow rate that is circulated when the control valve is opened is adjusted, the replenishing liquid to be replenished can be replenished by managing the time to open the control valve. The control unit 3 issues a control signal for causing the control valve to open for a predetermined time to the control valve so that the replenishing liquid to be replenished flows in accordance with the measured value and the management value of the density.

Regarding the manner of control, various control methods used to control the control amount in accordance with the target value can be employed. Specifically, it is preferably proportional control (P control) (P: proportional), integral control (I control) (I: integral), differential control (D control) (D: derivative), and the control methods are performed. Combined control (PI control, etc.). Better for PID control.

According to the developer management apparatus of the present embodiment, the replenishing liquid is supplied to the developer so that the carbon dioxide concentration of the developer becomes a predetermined management value or less than a predetermined management value, and the carbon dioxide concentration of the developer can be managed.

Third embodiment

Fig. 5 is a graph showing the carbon dioxide concentration from the relationship between the density of the developer and the carbon dioxide concentration based on the density value of the developer measured by the densitometer, and replenishing the replenishing solution to the development based on the calculated carbon dioxide concentration of the developer. A schematic diagram of a developer management device for managing the carbon dioxide concentration of the developer. For convenience of explanation, the developer management device E is connected to the developing process device B, and is illustrated together with the developing process device B, the replenishing liquid storage portion C, and the circulating stirring mechanism D.

The developer management device according to the present embodiment is a developer management device that calculates a carbon dioxide concentration calculation unit from a measured value of the density of the developer and a control unit that controls the carbon dioxide concentration of the developer. For example, the internal function of a computer is implemented.

The developer management device E of the present embodiment includes the measurement unit 1 and the calculation control unit 23. The measuring unit 1 includes a densitometer 11 and other measuring means 12 and 13. The calculation control unit 23 includes a calculation block 21 and a control block 31.

In the measurement unit 1, the density value of the sampled developer is measured by the density meter 11. The measured density value is transmitted via the signal line It is sent to the calculation control unit 23. The other details of the measuring unit 1 are the same as those of the second embodiment, and therefore will not be described.

The calculation control unit 23 that receives the measured value of the density of the developer is calculated in the calculation block 21, and calculates the phase from the measured value of the density based on the correspondence relationship between the density of the developer and the carbon dioxide concentration (for example, the linear relationship in FIG. 1). Corresponding developer carbon dioxide concentration. The calculated carbon dioxide concentration is transmitted to the control block 31 as a measured value of the carbon dioxide concentration of the developer.

For the calculation function, the calculation control unit 23 may include, for example, a calculation block for calculating the alkaline component concentration and the dissolved photoresist concentration of the developer.

The control block 31 issues control signals to the control valves 41 to 43 in accordance with the measured carbon dioxide concentration so that the carbon dioxide concentration of the developer becomes a predetermined management value or a predetermined management value or less. The developer tends to absorb carbon dioxide and its concentration tends to increase. Therefore, the control system is carried out by replenishing a replenishing liquid having a function of diluting the carbon dioxide concentration. The details of the control are the same as those in the second embodiment, and therefore will be omitted.

In the control function, the calculation control unit 23 may include, for example, a control block for controlling the concentration of the alkaline component of the developer and the concentration of the dissolved photoresist.

As described above, the developer management device E according to the present embodiment can manage the concentration of the absorbed carbon dioxide of the alkaline developer to be a predetermined management value or less.

Fourth embodiment

Fig. 6 is a graph showing the carbon dioxide concentration from the relationship between the density of the developer and the carbon dioxide concentration based on the density value of the developer measured by the densitometer, and replenishing the replenishing solution to the development based on the calculated carbon dioxide concentration of the developer. A schematic diagram of a developer management device for managing the carbon dioxide concentration of the developer. For convenience of explanation, the developer management device E is connected to the developing process device B, and is illustrated together with the developing process device B, the replenishing liquid storage portion C, and the circulating stirring mechanism D.

The developer management device according to the present embodiment is a developer management device in which the calculation means for calculating the carbon dioxide concentration from the measured value of the density of the developer and the control means for controlling the carbon dioxide concentration of the developer are independently configured.

The developer management device E of the present embodiment includes a measurement unit 1, an arithmetic unit 2, and a control unit 3. The measuring unit 1 includes a densitometer 11 and other measuring means 12 and 13. The calculation unit 2 includes a calculation block 21 for calculating the carbon dioxide concentration of the developer based on the measured value of the density and the correspondence relationship between the density and the carbon dioxide concentration (for example, the linear relationship in FIG. 1). The control unit 3 includes a control block 31 for supplying the replenishing liquid to the developing solution to control the carbon dioxide concentration of the developing solution to a predetermined management value or less than a predetermined management value, based on the calculated carbon dioxide concentration.

In the measurement unit 1, the density value of the sampled developer is measured by the density meter 11. The measured density value is transmitted via the signal line Send to the calculation unit 2. The other details of the measuring unit 1 are the same as those of the second embodiment, and therefore will not be described.

The calculation unit 2 that receives the measured value of the density of the developer is calculated in the calculation block 21, and the corresponding relationship between the density of the developer and the carbon dioxide concentration (for example, the linear relationship in FIG. 1) is calculated from the measured value of the density. The concentration of carbon dioxide in the developer. The calculated carbon dioxide concentration is transmitted to the control unit 3 as a measured value of the carbon dioxide concentration of the developer.

For the calculation function, the calculation unit 2 may include, for example, a calculation block for calculating the alkali component concentration and the dissolved photoresist concentration of the developer.

The control unit 3 issues control signals to the control valves 41 to 43 in such a manner that the carbon dioxide concentration of the developer becomes a predetermined management value or a predetermined management value or less based on the measured carbon dioxide concentration. The developer tends to absorb carbon dioxide and its concentration tends to increase. Therefore, the control system is carried out by replenishing a replenishing liquid having a function of diluting the carbon dioxide concentration. The details of the control are the same as those in the second embodiment, and therefore will be omitted.

For the control function, the control unit 3 may include, for example, a control block for controlling the concentration of the alkaline component of the developer and the concentration of the dissolved photoresist.

As described above, the developer management device E according to the present embodiment can manage the concentration of the absorbed carbon dioxide of the alkaline developer to be a predetermined management value or less.

Next, a modification of the developer management device E of the present embodiment will be described.

In the fourth to sixth figures, the measuring unit 1 of the developer management device is a developer management device that is integrally formed with the calculation unit 2 and the control unit 3. However, the developer management device E of the present embodiment does not This is limited to this. It is also possible to configure the measuring unit 1 independently.

Each of the measuring means 11 to 13 including the densitometer has an optimum setting method corresponding to the respective measuring principle, and therefore, for example, the measuring portion 1 can be connected to the developing solution line 80 in an inline manner, or It is possible to arrange the measurement probe to be immersed in the developer storage tank 61. Each of the measuring means 11 to 13 can also be individually provided. The developer management device E of the present embodiment can be realized in such a manner that the measurement means 11 to 13 can communicate with each other by the calculation unit 2 and the control unit 3 to transmit and receive measurement data.

Similarly, in the fourth to sixth figures, the developer management device E in which the measuring means 11 to 13 such as the density meter are connected in series is shown, but the developer management device E of the present embodiment is Not limited to this. Each of the measuring means 11 to 13 may be connected in parallel or may be independently piped. In accordance with the measurement principle adopted by each measurement means, if it is necessary to add a reagent, each measurement means may be provided with a pipe for adding a reagent; if there is a waste liquid, each measurement means may be provided with waste. The pipeline for the liquid. The developer management device E of the present embodiment can be realized even if the respective measurement means are not connected in series.

The calculation unit 2 of the developer management device E of the present embodiment has a correspondence relationship between the density of the developer and the carbon dioxide concentration (for example, a linear relationship as shown in FIG. 1), and calculates carbon dioxide based on the measured value of the density of the developer. In addition to the calculation function of the concentration, other calculation functions are also available. For example, it is also possible to provide a calculation function for calculating the concentration of other components such as the alkaline component concentration and the dissolved photoresist concentration of the developer.

The control unit 3 of the developer management device E of the present embodiment is provided with control for supplying the replenishing liquid to the developer so that the carbon dioxide concentration of the developer becomes a predetermined management value or less than a predetermined management value. In addition to the functions, other control functions are also available. For example, it is also possible to provide a control function for controlling the concentration of the other component such as the alkaline component concentration and the dissolved photoresist concentration of the developer to be a predetermined management value or within a management range equal to or lower than a predetermined management value. The control required for this purpose is controlled by the addition of the replenishing liquid to the developing solution, and the regeneration of the developing liquid by the appropriate treatment and the regeneration of the regeneration by filtering the impurities by means of a filter or the like. Various types of control constituted by control of developer recovery.

In the fourth to sixth figures, the developing solution management device E is configured such that the control valves 41 to 43 provided in the flow path for supplying the replenishing liquid supplied to the developing solution become internal components of the developing solution management device E. The liquid supply pipes 81 and 82 and the pure water pipe 83 are connected to each other. However, the developer management device E of the present embodiment is not limited thereto. The developer management device may be provided with the control valves 41 to 43 in the form of no internal member, or may be connected to the lines 81 to 83 for replenishing the replenishing liquid to the developer.

The control unit 3 in the developer management device E of the present embodiment and the control valves 41 to 43 provided in the line for supplying the replenishing liquid are configured such that the control valves 41 to 43 are received by the developer management device. The control signals sent from the control unit 3 of E may be in a controlled manner to communicate with each other. Even if the control valve is not constituted as an internal member of the developer management device E, the developer management device E of the present embodiment can be realized.

The control unit 3 of the developer management device E may not be integrally formed with the measurement unit 1 and the calculation unit 2, or may be configured independently. The measurement unit 1, the calculation unit 2, and the control unit 3 may each be in the form of an individual device. The developer management device E of the present embodiment can be realized by connecting the measurement data, the calculation result, the control signal, and the like to each other via a signal line or the like.

The function of controlling the carbon dioxide concentration of the control unit 3 and the function of controlling other components such as the alkaline component concentration and the dissolved photoresist concentration are preferably achieved by a common control means, but may be realized by an independent control means. The replenishing liquid used for the control, the piping for supplying the replenishing liquid, the control valve, and the like may be individually arranged according to the target component of the developing developer to be controlled, but it is preferable to use them together if they can be used together.

The developer management device of the present invention, while permitting various modifications as described above, is provided with a densitometer, and uses a correspondence relationship between the density of the developer and the carbon dioxide concentration (for example, the linear relationship as shown in FIG. 1). The density value of the developer measured by the densitometer or the carbon dioxide concentration of the developer calculated from the density value of the developer measured by the densitometer so that the carbon dioxide concentration of the developer becomes The replenishing liquid is supplied to the developing solution to control the predetermined management value or less than the predetermined management value.

As described above, according to the developer management apparatus of the present invention, the concentration of the absorbed carbon dioxide of the alkaline developer can be managed to be below a predetermined management value or a predetermined management value. Therefore, according to the developer management device of the present embodiment, the carbon dioxide concentration of the alkaline developer can be maintained in a state in which the optimum developing performance is exhibited, and the desired line width and residual film thickness can be realized.

In the developer management device of the present invention, the alkaline component concentration and the dissolved photoresist concentration of the alkaline developer can be further managed, and the concentration of each component of the alkaline developer is managed in a predetermined state. Therefore, according to the developer management device of the present invention, the development performance of the management of the alkaline developer can be maintained with higher precision than the conventional developer management technique which cannot manage the concentration of carbon dioxide. Therefore, the developing speed at the time of developing the photoresist is stabilized at a constant speed, and the line width and the residual film thickness formed by the development processing are set to be constant, so that the quality of the product is improved, and it is expected to contribute to realization of finer and higher density integrated. .

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

1‧‧‧Determination Department

2‧‧‧ Calculation Department

3‧‧‧Control Department

11‧‧‧density meter

12, 13‧‧‧Measurement means

14‧‧‧Sampling pump

15‧‧‧Sampling piping

16‧‧‧Exit side piping

21‧‧‧ calculus

31‧‧‧Control block

41 to 43‧‧‧ control valve

44, 45, 46, 47‧ ‧ valves

61‧‧‧ developer storage tank

62‧‧‧Overflow trough

63‧‧‧liquid level meter

64‧‧‧Development room cover

65‧‧‧Roller conveyor

66‧‧‧Substrate

67‧‧‧Developing sprinkler

71‧‧‧Waste pump

72, 74‧‧‧ Circulating pump

73, 75‧‧‧ filter

80‧‧‧developer line

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

83‧‧‧Pure water pipeline

84‧‧‧Confluence pipeline

85‧‧‧Circulation line

86‧‧‧Nitrogen pipeline

91, 92‧‧‧Replenishment tank

B‧‧‧Developing process equipment

C‧‧‧Replenishment Storage Department

D‧‧‧Circulating mixing mechanism

E‧‧‧ developer management device

Claims (7)

A component concentration measuring device for a developing solution includes: a density meter; and a calculation means for density value and carbon dioxide concentration value of the developing solution based on a density value of an alkaline developing solution measured by the density meter The relationship between the carbon dioxide concentrations of the developer was calculated. A method for measuring a component concentration of a developer is a method of measuring a density of a developer having an alkalinity; and calculating a developer from a correspondence relationship between a density of the developer and a concentration of carbon dioxide based on the measured density of the developer; The concentration of carbon dioxide. A developer management apparatus comprising: a densitometer; and a control means for using a density value of an alkaline developing solution measured by the densitometer between the density value of the developing solution and a carbon dioxide concentration value Correspondingly, a control signal is issued to the control valve provided in the flow path for supplying the replenishing liquid supplied to the developing solution so that the carbon dioxide concentration of the developing solution becomes a predetermined management value or less than a predetermined management value. A developer management method for measuring a density of an alkaline developing solution; and using a correspondence relationship between a density of the developing solution and a carbon dioxide concentration according to the measured density of the developing solution to cause carbon dioxide of the developing solution The replenishing liquid is supplied to the developing solution in such a manner that the concentration becomes a predetermined management value or becomes a predetermined management value or less. A developer management apparatus includes: a density meter; and an arithmetic control unit including an arithmetic unit and a control unit, wherein the calculation unit is based on a density value of an alkaline developer measured by the density meter Calculating the carbon dioxide concentration of the developer in accordance with the relationship between the density value of the developer and the carbon dioxide concentration value, the control unit is configured to adjust the carbon dioxide concentration of the developer according to the calculation unit to increase the carbon dioxide concentration of the developer. A control signal is provided to the control valve provided in the flow path for supplying the replenishing liquid supplied to the developer by setting the predetermined management value or lower than the predetermined management value. A developer management apparatus comprising: a density meter; and a calculation means for correlating a density value of the developing solution from a density value of the developing solution based on a density value of the alkaline developing solution measured by the density meter; a relationship between the carbon dioxide concentration of the developer and the control means, wherein the carbon dioxide concentration of the developer calculated by the calculation means is such that the carbon dioxide concentration of the developer becomes a predetermined management value or a predetermined management value or less The method sends a control signal to a control valve provided to convey a flow path for replenishing the replenishing liquid to the developer. A developer management method for measuring a density of a developing solution which is alkaline; and calculating a carbon dioxide concentration of the developer from a correspondence relationship between a density of the developer and a concentration of carbon dioxide based on the measured density of the developer; ; The replenishing liquid is supplied to the developer so that the calculated carbon dioxide concentration of the developer becomes a predetermined management value or less than a predetermined management value.