JP2018120897A - Device for monitoring concentration of developer, and developer management device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device for monitoring the concentration of a developer, which measures the concentration of carbon dioxide absorbed in a developer showing alkalinity, and a developer management device for managing the concentration of absorbed carbon dioxide in a developer showing alkalinity.SOLUTION: A concentration monitoring device calculates the concentration of absorbed carbon dioxide based on a measurement value of the density of a developer, from correspondence between the density and the concentration of absorbed carbon dioxide. Warning means warns when the concentration of absorbed carbon dioxide in the developer calculated by computing means is out of a preliminarily set management range. The developer management device manages the concentration of absorbed carbon dioxide in a developer by replenishing the developer with a replenisher using the correspondence between the density of the developer and the concentration of absorbed carbon dioxide, based on the measured density of the developer or the calculated concentration of absorbed carbon dioxide, so as control the concentration of absorbed carbon dioxide in the developer to a predetermined management value or lower than the management value.SELECTED DRAWING: Figure 6

Description

  The present invention relates to an alkaline developer monitoring apparatus and a developer management apparatus used for developing a photoresist film in a development process of a circuit board in a semiconductor or a liquid crystal panel.

  In the development process of photolithography that realizes fine wiring processing in a semiconductor, a liquid crystal panel, etc., as a chemical solution that dissolves the photoresist formed on the substrate, an alkaline developer (hereinafter referred to as “alkaline developer”) is used. .) Is used.

  In the manufacturing process of semiconductors and liquid crystal panel substrates, in recent years, the enlargement of wafers and glass substrates, the miniaturization of wiring processing, and the high integration have been promoted. Under these circumstances, it is necessary to measure and maintain the developer by measuring the concentration of the main component of the alkaline developer with higher accuracy in order to realize finer wiring processing and higher integration of large substrates. It has become.

  As described in Patent Document 1, the measurement of the conventional alkaline developer component concentration is good between the alkali component concentration (hereinafter referred to as “alkaline component concentration”) and the electrical conductivity of the alkaline developer. A linear relationship is obtained, and a good linear relationship is obtained between the concentration of the photoresist dissolved in the alkaline developer (hereinafter referred to as “dissolved photoresist concentration”) and the absorbance. It was a thing.

  However, alkaline developers tend to absorb carbon dioxide in the air and generate carbonates. At this time, the alkali component having development activity in the developer is consumed and reduced. Therefore, in order to maintain and manage the developing performance of the developing solution with high accuracy, it is necessary to manage the developing solution in consideration of the influence of carbon dioxide absorbed by the developing solution on the developing performance.

  In order to solve such a problem, Patent Document 2 discloses the ultrasonic propagation velocity, conductivity and conductivity at alkali concentration, carbonate concentration and dissolved resin concentration by measuring the ultrasonic propagation velocity, conductivity and absorbance of the developer. The alkali concentration, carbonate concentration and dissolved resin concentration of the developer are detected based on a previously created relationship (matrix) between the absorbance and the absorbance, and the measured alkali concentration, carbonate concentration and dissolved resin concentration of the developer, Control the supply of the developer stock solution based on the pre-created relationship between the alkali concentration, carbonate concentration and dissolved resin concentration that can exhibit the dissolving ability so that the CD value (line width) becomes a constant value. A developer preparation device for adjusting the alkali concentration is disclosed.

  Patent Document 3 discloses a carbonate-based salt concentration measuring device that measures the refractive index, conductivity, and absorbance of a developer, and obtains the carbonate-based salt concentration in the developer from the measured values, and the carbonic acid salt. An alkaline developer management system including a system salt concentration measuring device and a control unit that controls a carbonate salt concentration in a developer is disclosed.

Japanese Patent No. 2561578 JP 2008-283162 A JP 2011-128455 A

  However, the ultrasonic wave propagation velocity value and refractive index value of the alkaline developer are characteristic values indicating the properties of the whole of the multi-component alkaline developer. Such characteristic values indicating the properties of the entire liquid generally do not correlate only with the concentration of a specific component contained in the liquid. Such characteristic values indicating the properties of the entire liquid generally have a correlation with each of the concentrations of various components contained in the liquid. Therefore, when the component concentration of the developer is calculated from the measured value of the characteristic value indicating the properties of the entire liquid, it is assumed that a certain characteristic value correlates with only a specific component concentration (for example, has a linear relationship). If the influence of the component on the characteristic value is ignored, the concentration of the specific component cannot be calculated with sufficient accuracy.

  On the other hand, when calculating the concentration of each component from the measured value of the characteristic value of the developer assuming that the characteristic value of the developer is a function of the concentration of various components contained in the developer, a plurality of characteristic values must be measured. Therefore, it is necessary to employ an appropriate calculation method for calculating the concentration of each component from the measured values of these characteristic values. However, it is very difficult to appropriately select a characteristic value to be measured and find an appropriate calculation method that can accurately calculate the concentration of each component from the measured value of the characteristic value. For this reason, there is a problem that the concentration of each component cannot be calculated with sufficient accuracy unless the measured characteristic value and calculation method are appropriate.

  Furthermore, in multicomponent liquids, the concentration of one component is generally not independent of the concentration of another component. In a multi-component liquid, there is a correlation that when the concentration of a certain component changes, the concentration of other components also changes at the same time. This makes it more difficult to calculate the component concentration with high accuracy and to manage the developer with high accuracy.

  In addition, with respect to the concentration of carbon dioxide absorbed in the developer (hereinafter referred to as “absorbed carbon dioxide concentration”), an appropriate characteristic value of the developer showing a good correlation with this is not known. It was difficult to accurately measure the absorbed carbon dioxide concentration. Also, monitoring the change in the concentration of absorbed carbon dioxide in the developer is important in managing the developer.

  The present invention has been made to solve the above-described problems. The present invention relates to a concentration monitoring device capable of measuring the absorbed carbon dioxide concentration of a developing solution from the density value of the developing solution, which is a multi-component system, and monitoring a change in the concentration of absorbed carbon dioxide, and a predetermined carbon dioxide concentration of the developing solution It is an object of the present invention to provide a developing solution management apparatus that can manage such that the control value is such that the predetermined control value is not exceeded.

  The developer concentration monitoring apparatus according to the present invention includes a density meter and a correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration based on the density value of the developer indicating alkalinity measured by the density meter. Calculating means for calculating the absorbed carbon dioxide concentration of the developer, and an alarm for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculating means is out of a preset management range. Means.

  According to the present invention, since the density meter that measures the density value having a good correspondence with the absorbed carbon dioxide concentration of the developer is provided, the absorbed carbon dioxide concentration of the developer is determined from the density value measured by the density meter. The concentration of the developer can be monitored by an alarm from the alarm means.

  In the concentration monitoring device, as the alarm means, an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning light that lights or blinks light, a display device that displays a warning, and switching between opening and closing of contacts At least one of the relay terminals.

  The developer management apparatus of the present invention uses a correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration based on the density meter and the density value of the developer showing the alkalinity measured by the density meter. Then, a control signal is issued to a control valve provided in a conduit for feeding a replenisher to be replenished to the developer so that the absorbed carbon dioxide concentration of the developer becomes a predetermined management value or less than a management value. The control unit and the density measured by the densimeter from a density range corresponding to a preset management range of the absorbed carbon dioxide concentration, which is determined by a correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration. Alarm means for issuing an alarm when the density value of the developer is deviated.

  According to the present invention, the amount of the replenisher to be replenished can be determined from the density value of the developer measured by the densimeter from the correspondence between the density of the developer and the absorbed carbon dioxide concentration. The replenisher can be replenished and managed so that the concentration becomes a predetermined control value or less than the control value, and the concentration of the developer can be monitored by an alarm by an alarm means.

  The developer management device of the present invention is based on the density relationship between the density of the developer and the absorbed carbon dioxide concentration, based on the density meter and the density value of the developer indicating alkalinity measured by the density meter. An arithmetic unit that calculates the absorbed carbon dioxide concentration of the developer, and the absorbed carbon dioxide concentration of the developer based on the absorbed carbon dioxide concentration of the developer calculated by the arithmetic unit is a predetermined management value or management value A control unit that emits a control signal to a control valve provided in a conduit for feeding a replenisher to be replenished to the developer so as to be calculated by the control unit; Alarm means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer is out of a preset management range.

  According to the present invention, since the density meter that measures the density value having a good correspondence with the absorbed carbon dioxide concentration of the developer is provided, the absorbed carbon dioxide concentration of the developer is determined from the density value measured by the density meter. It can be calculated, and the concentration of absorbed carbon dioxide in the developer can be managed by replenishing the replenisher so that it is less than or equal to the predetermined control value. it can.

  The developer management device of the present invention is based on the density relationship between the density of the developer and the absorbed carbon dioxide concentration, based on the density meter and the density value of the developer indicating alkalinity measured by the density meter. Based on the calculation means for calculating the absorbed carbon dioxide concentration of the developer and the absorption carbon dioxide concentration of the developer calculated by the calculation means, the absorbed carbon dioxide concentration of the developer is a predetermined management value or management value. Control means for issuing a control signal to a control valve provided in a conduit for supplying a replenisher to be replenished to the developer, and the absorbed carbon dioxide of the developer calculated by the calculator Alarm means for issuing an alarm when the concentration value falls outside a preset management range.

  According to the present invention, since the density meter that measures the density value having a good correspondence with the absorbed carbon dioxide concentration of the developer is provided, the absorbed carbon dioxide concentration of the developer is determined from the density value measured by the density meter. It can be calculated, and the concentration of absorbed carbon dioxide in the developer can be managed by replenishing the replenisher so that it is less than or equal to the predetermined control value. it can.

  In the developer management device, as the alarm means, an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning light that lights or blinks light, a display device that displays a warning, and opening and closing of contacts At least one of the relay terminals to be switched is provided.

  According to the present invention, it is possible to measure the absorbed carbon dioxide concentration of a developing solution, which has conventionally been difficult to measure, and to monitor the concentration of the developing solution. Further, based on the measured density value or the calculated absorbed carbon dioxide concentration value, the developer is supplied with a replenisher and managed so that the absorbed carbon dioxide concentration of the developer is equal to or lower than a predetermined management value. be able to.

It is a graph which shows the relationship between the absorbed carbon dioxide density | concentration of a developing solution, and a density. It is a schematic diagram of a developer concentration monitoring device. It is a schematic diagram of the typical structure of a vibration type density meter. It is a schematic diagram of the image development process including the developing solution management apparatus of 2nd embodiment. It is a schematic diagram of the image development process including the developing solution management apparatus of 3rd embodiment. It is a schematic diagram of the image development process including the developing solution management apparatus of 4th embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with appropriate reference to the drawings. However, the shapes, sizes, dimensional ratios, relative arrangements, etc. of the devices described in these embodiments are only those shown within the scope of the present invention unless otherwise specified. It is not limited. It is only schematically shown as an example for explanation.

  In the following description, as a specific example of the developer, a 2.38% tetramethylammonium hydroxide aqueous solution (hereinafter, tetramethylammonium hydroxide is referred to as TMAH) that is mainly used in the manufacturing process of semiconductors and liquid crystal panel substrates. Will be described as appropriate. However, the developer to which the present invention is applied is not limited to this. Examples of other developers to which the developer concentration monitoring device and developer management device of the present invention can be applied include aqueous solutions of inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, and trimethyl. An aqueous solution of an organic compound such as monoethanolammonium hydroxide (choline) can be mentioned.

  In the following description, component concentrations such as alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration are concentrations based on weight percentage concentration (wt%). “Dissolved photoresist concentration” refers to the concentration when the dissolved photoresist is converted as the amount of photoresist, and “absorbed carbon dioxide concentration” refers to when the absorbed carbon dioxide is converted as the amount of carbon dioxide. The concentration of

  In the development process, development is performed by the developer dissolving unnecessary portions of the photoresist film after the exposure process. The photoresist dissolved in the developer generates a photoresist salt with the alkali component of the developer. For this reason, unless the developer is appropriately managed, as the development process proceeds, the developer deteriorates due to consumption of an alkaline component having development activity, and the development performance deteriorates. At the same time, the dissolved photoresist is accumulated in the developer as a photoresist salt with an alkali component.

  The photoresist dissolved in the developer exhibits a surface activity in the developer. For this reason, the photoresist dissolved in the developer improves the wettability of the photoresist film subjected to the development process with respect to the developer and improves the familiarity between the developer and the photoresist film. Therefore, with a developer containing a moderate amount of photoresist, the developer spreads well in fine concave portions of the photoresist film, and the development processing of the photoresist film having fine irregularities can be performed satisfactorily.

  Further, in recent development processing, with the increase in the size of the substrate, a large amount of the developer has been repeatedly used, so that the opportunity for the developer to be exposed to air is increasing. However, alkaline developers absorb carbon dioxide in the air when exposed to air. The absorbed carbon dioxide forms carbonate with the alkali component of the developer. For this reason, if the developer is not properly managed, the developer is consumed and reduced by the carbon dioxide in which the alkali component having development activity is absorbed. At the same time, the absorbed carbon dioxide is accumulated in the developer as a carbonate with an alkali component.

  The carbonate in the developer has a developing action because it shows alkalinity in the developer. For example, in the case of a 2.38% TMAH aqueous solution, development is possible if the carbon dioxide in the developer is about 0.4 wt% or less.

  Thus, unlike the conventional recognition that the photoresist dissolved in the developer and the absorbed carbon dioxide are unnecessary for the development process, the photoresist actually contributes to the developing performance of the developer. Therefore, it is not a developer management that completely eliminates dissolved photoresist and absorbed carbon dioxide, but a developer that maintains these at an optimum concentration while allowing them to be slightly dissolved in the developer. Management is required.

  Regarding these points, the inventor obtained the following knowledge as a result of continual research. That is, a relatively good correspondence (linear relationship) can be obtained between the density value of the developer and the absorbed carbon dioxide concentration value regardless of the alkali component concentration or dissolved photoresist concentration of the developer. . Further, if this correspondence (linear relationship) is used, it is possible to measure the absorbed carbon dioxide concentration, which has been difficult in the past, by measuring the density of the developer with a densitometer. Furthermore, if this correspondence relationship (linear relationship) is used, the absorbed carbon dioxide concentration of the developer can be managed by replenishment of the replenisher based on the measured density value or the calculated absorbed carbon dioxide concentration value.

  The inventor prepared a TMAH aqueous solution in which the alkali component concentration, the dissolved photoresist concentration, and the absorbed carbon dioxide concentration were variously changed as a simulated developer sample on the assumption that the 2.38% TMAH aqueous solution was managed. The inventor prepared 11 calibration standard solutions in which the alkali component concentration (TMAH concentration), dissolved photoresist concentration, and absorbed carbon dioxide concentration were variously changed with a 2.38% TMAH aqueous solution as the basic composition of the developer. .

  The inventor measured the alkali component concentration (TMAH concentration), the absorbed carbon dioxide concentration, and the density of these simulated developer samples, and conducted an experiment to confirm the correlation between the component concentration and the density.

The measurement was performed by adjusting the temperature of the calibration standard solution to 25.0 ° C. To adjust the temperature, immerse the bottle containing the calibration standard solution in a constant temperature water bath whose temperature is controlled at around 25 ° C. for a long time, sample from here, and set the temperature controller to 25.0 ° C. again immediately before the measurement. This is the method. For the density measurement, a density meter employing a natural vibration method for obtaining a density from a natural frequency measured by exciting a U-shaped flow cell was used. 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 deteriorates by absorbing carbon dioxide, the component concentrations in Table 1 are determined by titration analysis that can accurately analyze the alkali component concentration (TMAH concentration) and the absorbed carbon dioxide concentration. Separately measured values were used. However, the weight preparation value was used for the dissolved photoresist concentration.

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

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

  From FIG. 1, it can be understood that there is a good linear relationship between the absorbed carbon dioxide concentration of the developer and the density of the developer even though the alkali component concentration and the dissolved photoresist concentration are various. From this experimental result, using the correspondence relationship (linear relationship) between the absorbed carbon dioxide concentration and density of the developer, the absorbed carbon dioxide concentration of the developer can be calculated by measuring the density of the developer. The inventor has found that this is possible.

  Therefore, regardless of the alkali component concentration (TMAH concentration) or the dissolved photoresist concentration, the developer concentration monitoring device using the density meter that can measure the absorbed carbon dioxide concentration of the developer by this correspondence relationship (linear relationship). Can be realized.

  Further, in an alkaline developer repeatedly used in the development processing step, the alkali component concentration (TMAH concentration) and the dissolved photoresist concentration are usually managed by a developer management apparatus. There are fewer factors that degrade the linearity between developer density and absorbed carbon dioxide concentration compared to the experiments in the simulated sample. Therefore, the concentration monitoring device capable of measuring the absorbed carbon dioxide concentration of the developer according to the present invention can be suitably used as a component of the developer management device that can further monitor and manage the absorbed carbon dioxide concentration.

  Further, since the alkaline developer tends to increase the absorbed carbon dioxide, replenishing a replenisher solution having a low absorbed carbon dioxide concentration (for example, a developer stock solution or a new solution) as a replenisher solution allows the developer to absorb absorbed carbon dioxide. The carbon concentration can be managed to a predetermined management value, or can be managed to be lower than the predetermined management value.

  Further, as shown in FIG. 1, since the absorbed carbon dioxide concentration and density of the developer have a monotonically increasing correspondence (linear relationship), the absorbed carbon dioxide concentration of the developer is equal to or lower than a predetermined management value. Doing so is equivalent to making the density value of the developer equal to or lower than the corresponding predetermined management value. Therefore, if the density value corresponding to the management value of the absorbed carbon dioxide concentration is set as the density management value, the density of the developer is measured, and the measured density value is managed so as to be equal to or less than the management value. By doing so, the developer can be managed so that the absorbed carbon dioxide concentration of the developer becomes a predetermined control value or a control value or less.

  Here, the predetermined control value is a concentration value that has been confirmed in advance as the upper limit of the concentration value of carbon dioxide in the developing solution that allows the developing solution to exhibit good developing performance, or a density value corresponding thereto. That's it. The same applies to the following description.

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

[First embodiment]
FIG. 2 is a schematic diagram of the developer concentration monitoring apparatus according to the present embodiment.

  The developer concentration monitoring apparatus A of the present embodiment includes a measurement unit 1, a calculation unit 2, and an alarm unit WD.

  The measuring unit 1 includes a density meter for measuring the density of the developing solution, other measuring means for measuring other characteristic values of the developing solution (11 to 13 in the figure), a sampling pump 14, and the sampled developing solution. A thermostat (not shown) for adjusting the temperature to a predetermined measurement temperature (for example, 25 ° C.) before measurement is provided.

  When the concentration monitoring device A only needs to measure the density, the measuring means 11 to 13 of the measuring unit 1 only need to be provided with a density meter (for example, 11), and measure other characteristic values. Means (for example, 12, 13) are unnecessary. However, as a concentration monitoring device for an alkaline developer, not only the absorbed carbon dioxide concentration but also the concentration of an alkaline component and the concentration of a photoresist dissolved in the developer are often measured. Therefore, FIG. 2 shows measuring means 11, 12, and 13 including other measuring means necessary for measuring the alkali component concentration, the dissolved photoresist concentration, and the like. One of these is the density meter. In the following description of the concentration monitoring apparatus A, the measuring means 11 of the measuring means 11 to 13 in FIG.

  The calculation unit 2 includes a calculation block 21 that calculates an absorbed carbon dioxide concentration value from the measured density value. In the calculation block 21, a correspondence relationship (for example, a linear relationship as shown in FIG. 1) between the density of the developer and the absorbed carbon dioxide concentration is input in advance. The calculation block 21 has a function of obtaining a corresponding absorbed carbon dioxide concentration value from the measured density value of the developer. Moreover, it is desirable that the calculation unit 2 includes a display unit 22 for displaying the calculated absorbed carbon dioxide concentration. The concentration monitoring apparatus A is connected to a tank in which the developer is stored by the sampling pipe 15.

  A method for measuring absorbed carbon dioxide by the concentration monitoring apparatus A of the present embodiment will be described. The developer is fed into the measuring unit 1 by the sampling pump 14. The developer sent to the measurement unit 1 is first adjusted to a predetermined measurement temperature (for example, 25 ° C.) in a constant temperature bath. The temperature-adjusted developer is sent to the density meter 11 and other measuring means 12 and 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 developer. The developer after the measurement is discharged out of the concentration monitoring apparatus A from the outlet side pipe 16.

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

  Receiving the measurement data of the density value of the developer and other characteristic values, the calculation block 21 calculates the component concentration of the developer based on the measurement data. The absorbed carbon dioxide concentration of the developer is calculated using a correspondence relationship (for example, a linear relationship as shown in FIG. 1) between the density of the developer and the absorbed carbon dioxide concentration. That is, an absorption carbon dioxide concentration value corresponding to the measured density value of the developing solution is obtained from the correspondence relationship between the density of the developing solution and the absorbed carbon dioxide concentration, and this is measured for the absorption carbon dioxide concentration of the developing solution. Value.

  In this way, the developer concentration monitoring apparatus A of the present embodiment, based on the measured value of the density of the developer, determines the absorbed carbon dioxide of the developer from the correspondence between the density of the developer and the absorbed carbon dioxide concentration. The concentration can be measured.

  As shown in FIG. 2, the concentration monitoring apparatus A of the present embodiment may be configured as a separate unit in addition to the case where the measurement unit 1 and the calculation unit 2 are configured as an integrated device. In the case of being configured separately, the measurement data measured by the density meter 11 of the measurement unit 1 and other measurement means 12 and 13 is transmitted by a signal line or the like so that the measurement data is transferred to the calculation block 21 of the calculation unit 2. It only has to be connected. Measurement data may be transmitted and received wirelessly.

  The concentration monitoring apparatus A and its measurement unit 1 of the present embodiment circulates and uses the developer in addition to the case where it is connected to the reservoir so that the developer can be sampled from the reservoir in which the developer is stored. It may be connected directly or bypassed to the circulation line of the development processing step.

  Moreover, in FIG. 2, although the aspect by which each measuring means 11-13 including a density meter was connected in series was illustrated, the connection of each measuring means is not limited to this. A parallel connection may be used, or each may be independently provided with a liquid supply path for measurement. The order of measurement with the density meter and other measuring means is not particularly limited. What is necessary is just to measure in the optimal order suitably according to the characteristic of each measuring means.

  Of the configuration of the measurement unit 1 shown in FIG. 2, the sampling pump 14 is not always necessary. When directly connected to the circulation line, it is not necessary to provide the sampling pump 14 in the measurement unit 1. Even 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 desirable that a constant temperature bath for adjusting the developer to a predetermined measurement temperature is provided immediately before the measurement means.

  In addition to the function of calculating the absorbed carbon dioxide concentration from the measured density value, the calculation block 21 of the calculation unit 2 has a function of calculating other component concentrations such as the alkali component concentration and dissolved photoresist concentration of the developer. May be. By doing so, it is possible to realize a concentration monitoring device capable of measuring the alkali component concentration, dissolved photoresist concentration, and absorbed carbon dioxide concentration of the developer.

  The concentration monitoring apparatus A according to the present embodiment includes an alarm unit WD. The warning unit WD can issue an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the calculation unit 2 which is an aspect of the calculation unit is out of a preset management range.

  For example, the management range is stored in the calculation unit 2 in advance, and the calculation unit 2 determines whether the absorbed carbon dioxide concentration value is outside the management range. The information can be transmitted from the calculation unit 2 to the alarm means WD, and an alarm can be issued to the alarm means WD based on the information.

  In addition, the management range is stored in advance in the warning unit WD, information on the component concentration is received from the calculation unit 2, and the warning unit WD determines whether the absorbed carbon dioxide concentration value is within the management range. Based on this determination, a warning can be issued to the warning means WD.

  As long as the alarm unit WD can issue an alarm, the management range storage unit and the determination unit are not particularly limited.

  As the alarm means WD, preferably, an external output signal terminal for transmitting an alarm signal, an alarm device for generating an alarm sound, a warning light for lighting or blinking light, a display device for displaying a warning, and a relay terminal for switching the contact open / close , At least one of the above.

  When the alarm means WD is an external output signal terminal that transmits an alarm signal, the external output signal terminal is connected to a device (not shown). When the device receives an alarm signal from the external output signal terminal, the device can perform a predetermined operation. For example, if the system includes a concentration monitoring device, the system can be stopped.

  When the alarm means WD is an alarm device that emits an alarm sound, or an alarm lamp that lights or blinks light, an operator near the concentration monitoring device can be alerted. The operator can check the state of the concentration monitoring device and take appropriate measures.

  When the warning means WD is a display device that displays a warning, the operator can be similarly alerted. In addition, when the display device is electrically connected to the calculation unit 2 by wire or wirelessly, it is possible to alert an operator away from the concentration monitoring device.

  When the alarm means WD is a relay terminal that switches between opening and closing of the contact, the device connected to the relay terminal can be switched ON and OFF, and the device can be caused to perform a predetermined operation.

  As the density meter 11 of the concentration monitoring apparatus A of the present embodiment, a float type density meter using buoyancy, a differential pressure type density meter using a pressure difference between two points having different heights in liquid, and a gamma ray transmittance Various density meters such as a gamma ray density meter used can be adopted. More preferably, it is desirable to employ a vibratory density meter that obtains the density by detecting the natural frequency of the line filled with liquid.

  FIG. 3 schematically shows a typical configuration of the vibration type density meter.

  The measurement unit of the vibration type densitometer includes a sample cell 51 bent in a U shape, a thermostatic block 54 surrounding the sample cell 51, and a heat insulating material 55 on the outer periphery thereof. A constant temperature block 54 is provided with a Peltier element 53 for adjusting the temperature of the sample. The sample cell 51 is provided with a vibrator 56 at the tip of the bent portion, and a drive section for exciting the vibrator 56 and a detection section for detecting the vibration frequency of the vibrator 56 are disposed in the vicinity of the vibrator 56. ing.

  The excited sample cell 51 vibrates at a natural frequency related to the mass of the liquid inside. By detecting the natural frequency, the mass of the liquid in the sample cell 51 can be known, so the density of the liquid is measured from the internal volume of the sample cell 51.

  The vibration type density meter is characterized by high sensitivity and stable measurement, and continuous measurement. The vibration type density meter can be measured under a favorable temperature condition and temperature stability by a thermometer, a temperature adjusting means, and a heat insulating means. In addition, the vibration type density meter can measure the density of the sample only by feeding the sample liquid to the sample cell. When measuring density, there is no need to add reagents and no waste liquid.

  In the developer concentration monitoring apparatus of the present embodiment, the various measuring means 11 to 13, particularly the way of installing the density meter, is not limited to the mode shown in FIG. 2.

  There are various measurement principles and measurement methods for density meters, and there are installation methods suitable for each. When adopting a float type density meter or a differential pressure type density meter as the density meter, it is preferable to install the density meter so that the float part and the probe part of the density meter are immersed in the storage tank of the developer. When a gamma ray density meter is employed, the density meter can be directly installed in the pipeline through which the developer flows. When the vibration type density meter is employed, as shown in FIG. 2, if the storage tank and the density meter are connected by a sampling pipe, the developer can be sampled and continuously measured.

The vibration-type density meter is suitable for continuous and online use because the density can be measured simply by feeding the developer to the sample cell. In addition, it is suitable for stably managing the measurement conditions such as the liquid temperature, so that stable and highly sensitive measurement can be performed. Even a vibration density meter for a process can be measured with an accuracy of about 0.001 (g / cm ³ ), and according to the linear relationship of FIG. The measurement accuracy of carbon dioxide of about wt%) can be achieved. If the alkali component concentration and dissolved photoresist concentration in the developer are controlled, the linearity between the density and absorbed carbon dioxide concentration will be better, and the measurement accuracy of the density meter can be expected to improve. It is expected that the absorbed carbon dioxide concentration of the concentration monitoring device can be measured with higher accuracy.

  The developer concentration monitoring apparatus of the present embodiment can be used as a component of a developer management apparatus for managing the absorbed carbon dioxide concentration by utilizing the ability to measure the absorbed carbon dioxide concentration of the developer. . Control means for supplying a replenisher to the developer and controlling the developer so that the absorbed carbon dioxide concentration of the developer is equal to or lower than a predetermined management value based on the absorbed carbon dioxide concentration measured by the concentration monitoring device. By combining with the concentration monitoring apparatus of this embodiment, a developer management apparatus capable of managing the absorbed carbon dioxide concentration can be configured.

[Second Embodiment]
FIG. 4 shows the development solution by replenishing the developer with the replenisher using the correspondence between the density of the developer and the absorbed carbon dioxide concentration based on the density value of the developer measured by the density meter. It is a schematic diagram of the developing solution management apparatus which manages the carbon dioxide concentration of. For convenience of explanation, the developing solution management apparatus E is illustrated together with the developing process facility B, the replenisher storing part C, and the circulation stirring mechanism D in a mode connected to the developing process facility B.

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

  The development process facility B mainly includes a developer storage tank 61, an overflow tank 62, a development chamber hood 64, a roller conveyor 65, a developer shower nozzle 67, and the like. A developer is stored in the developer storage tank 61. The composition of the developer is managed by replenishing the replenisher. The developer storage tank 61 includes a liquid level gauge 63 and an overflow tank 62, and manages an increase in the amount of liquid caused by replenishing the replenisher. The developer reservoir 61 and the developer shower nozzle 67 are connected by a developer conduit 80. The developer stored in the developer storage tank 61 is sent to the developer shower nozzle 67 via the filter 73 by a circulation pump 72 provided in the developer conduit 80. The roller conveyor 65 is provided above the developer storage tank 61 and conveys a substrate 66 on which a photoresist film is formed. The developer is dropped from the developer shower nozzle 67. The substrate 66 conveyed by the roller conveyor 65 is immersed in the developer by passing through the dropped developer. Thereafter, the developer is collected in the developer storage tank 61 and stored again. As described above, the developer is circulated and used repeatedly in the development process. Note that the developing chamber in a small glass substrate may be subjected to a treatment that does not absorb carbon dioxide in the air, for example, by being filled with nitrogen gas.

  Next, the developer management apparatus E of this embodiment will be described. The developer management apparatus E according to the present embodiment measures the density of the developer with a densitometer, and uses the correspondence between the developer density and the absorbed carbon dioxide concentration (for example, a linear relationship as shown in FIG. 1) to develop the developer. This is a developing solution management apparatus that replenishes the developing solution with the replenisher based on the measured density value so that the absorbed carbon dioxide concentration of the solution is equal to or less than a predetermined management value.

  The developer management apparatus E includes a measurement unit 1, a calculation unit 2, a control unit 3, and an alarm unit WD, and is connected to the developer storage tank 61 by a sampling pipe 15 and an outlet side pipe 16. The measurement unit 1, the calculation unit 2, and the control unit 3 are connected by 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 developer. The measuring means 12 and 13 are for measuring, for example, the alkali component concentration and the dissolved photoresist concentration of the developer. The density meter 11 and the measuring means 12 and 13 are connected in series to the subsequent stage of the sampling pump 14. The measurement unit 1 preferably further includes a temperature adjusting means (not shown) that stabilizes the sampled developer at a predetermined temperature in order to increase the measurement accuracy. At this time, the temperature adjusting means is preferably provided immediately 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 a calculation block 21 for calculating, for example, the alkali component concentration and the dissolved photoresist concentration of the developer. The calculation block 21 is connected to measurement means 12 and 13 provided in the measurement unit 1 by signal lines. When the developer management device E only needs to have a function of controlling the absorbed carbon dioxide concentration by measuring the density of the developer, the measuring means 12 and 13 and the calculation unit 2 are not necessary.

  The control unit 3 is connected to the density meter 11 of the measurement unit 1 by a signal line. In addition, the control unit 3 is connected to control valves 41 to 43 provided in a conduit for sending the replenisher to the developer by a signal line. In FIG. 4, the control valves 41 to 43 are illustrated as internal parts of the developer management apparatus E, but the control valves 41 to 43 are not necessarily essential parts of the developer management apparatus E of the present embodiment. . The control unit 3 only needs to communicate with the control valves 41 to 43 so as to control the operation of the control valves 41 to 43 so that the replenisher can be supplied to the developer. The control valves 41 to 43 may exist outside the developer management apparatus E.

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

  The developer sampled from the developer reservoir 61 is fed into the measuring unit 1 and the temperature is adjusted. The developer is then sent to the density meter 11 and the density value is measured. The density measurement data is sent to the control unit 3.

  The control unit 3 has a density management value corresponding to the management value of the absorbed carbon dioxide concentration determined based on the correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration (for example, a linear relationship as shown in FIG. 1). Is set. The control unit 3 performs control as follows according to the measured density value of the developer received from the measurement unit 1.

  When managing the absorbed carbon dioxide concentration of the developer so as to be a predetermined control value, the following management is performed. In other words, the replenisher is supplied to the developer so that the measured density value of the developer becomes a management value of density corresponding to the management value of the absorbed carbon dioxide concentration. If the concentration is not controlled, the developer absorbs carbon dioxide and the absorbed carbon dioxide concentration tends to increase. Therefore, the replenisher to be replenished is a replenisher that acts to reduce the absorbed carbon dioxide concentration of the developer. Just replenish.

  When managing the absorbed carbon dioxide concentration of the developer so as to be a predetermined control value or less, the following management is performed. That is, since the correspondence between the density of the developing solution and the absorbed carbon dioxide concentration is a monotonically increasing relationship as shown in FIG. 1, the measured density value of the developing solution corresponds to the management value of the absorbed carbon dioxide concentration. The replenisher is replenished to the developer so as to be less than the control value. The replenisher to be replenished may be a replenisher that acts to reduce the absorbed carbon dioxide concentration of the developer.

  Here, the “predetermined management value” is a management value known in advance as the absorbed carbon dioxide concentration value when the developer exhibits an optimum developing performance. For example, when the liquid performance of the developer is evaluated by the line width or remaining film thickness obtained by the development process, the absorbed carbon dioxide concentration value of the developer can be set to a desired optimum value. The same applies to the following description.

  As the management of the absorbed carbon dioxide concentration of the developer, for example, when a 2.38% TMAH aqueous solution is used as the developer, the absorbed carbon dioxide concentration of the developer is preferably controlled to 0.40 (wt%) or less. . More preferably, it is good to manage to 0.25 (wt%) or less.

  Since the developer management apparatus E normally measures and manages the alkali component concentration and the dissolved photoresist concentration, the developer management apparatus E includes measuring means 12 and 13 for measuring the characteristic values of the developer necessary for this purpose. The developer characteristic values measured by the measuring means 12 and 13 are sent to the calculation unit 2. The calculation unit 2 calculates the alkali component concentration and the dissolved photoresist concentration from the measured characteristic values of the developer, and sends the results to the control unit 3. The control unit 3 manages the alkali component concentration and the dissolved photoresist concentration of the developer in an optimum state based on the measurement result or the calculation result.

  Examples of the replenisher to be replenished to the developer include a stock solution of the developer, a new solution, and pure water. These replenishers are for diluting the absorbed carbon dioxide concentration of the developer. These replenishers are also replenished to manage the alkali component concentration and dissolved photoresist concentration of the developer.

  The replenisher is stored in the replenisher reservoirs 91 and 92 of the replenisher reservoir C. The replenisher storage tanks 91 and 92 are connected to a nitrogen gas pipe 86 having valves 46 and 47, and are pressurized by nitrogen gas supplied through the pipe. Also, replenisher reservoirs 91 and 92 are connected to replenisher conduits 81 and 82, respectively, and replenisher is fed through valves 44 and 45 that are normally open. The replenisher lines 81 and 82 and the pure water line 83 are provided with control valves 41 to 43, and the control valves 41 to 43 are controlled to be opened and closed by the control unit 3. By operating the control valve, the replenisher stored in the replenisher reservoirs 91 and 92 is pumped and pure water is transported. Thereafter, the replenisher is joined to the circulation stirring mechanism D via the joining conduit 84, and is supplied to the developer storage tank 61 and stirred.

  When the replenisher stored in the replenisher reservoirs 91 and 92 decreases due to replenishment, the internal pressure decreases and the supply amount becomes unstable. Therefore, the valves 46 and 47 are opened as appropriate according to the decrease of the replenisher. Gas is supplied and maintained so that the internal pressure of the replenisher storage tanks 91 and 92 is maintained. When the replenisher reservoirs 91 and 92 are emptied, the valves 44 and 45 are closed and replaced with a new replenisher reservoir filled with the replenisher, or the separately procured replenisher is emptied. The replenisher storage tanks 91 and 92 are filled again.

  Control of the control valves 41-43 is performed as follows, for example. If the flow rate flowing when the control valve is opened is adjusted, the amount of replenisher to be replenished can be replenished by managing the time during which the control valve is open. Based on the measured value and the management value of the density, the control unit 3 issues a control signal to the control valve so as to open the control valve for a predetermined time so that the replenisher of the amount to be replenished flows.

  As the control method, various control methods used for control for adjusting the control amount to the target value can be adopted. In particular, proportional control (P control), integral control (I control), differential control (D control), and a combination of these (PI control, etc.) are preferable. More preferably, PID control is suitable.

  As described above, the developer management apparatus according to this embodiment supplies the replenisher to the developer so that the absorbed carbon dioxide concentration of the developer is equal to or lower than the predetermined management value, and the absorbed carbon dioxide of the developer. Concentration can be controlled.

  Further, an alarm can be issued when the absorbed carbon dioxide concentration is out of the management range by the alarm means WD.

[Third embodiment]
FIG. 5 shows the calculation of the absorbed carbon dioxide concentration from the corresponding relationship between the density of the developer and the carbon dioxide concentration based on the density value of the developer measured by the density meter, and the calculated absorption dioxide of the developer. FIG. 3 is a schematic diagram of a developer management device that manages the carbon dioxide concentration of a developer by supplying a replenisher to the developer based on the carbon concentration. For convenience of explanation, the developing solution management apparatus E is illustrated together with the developing process facility B, the replenisher storing part C, and the circulation stirring mechanism D in a mode connected to the developing process facility B.

  In the developer management apparatus of the present embodiment, a calculation unit that calculates an absorbed carbon dioxide concentration from a measured value of the density of the developer and a control unit that controls the absorbed carbon dioxide concentration of the developer are integrated calculation control means ( For example, it is a developing solution management apparatus realized as an internal function of a computer.

  The developer management apparatus E of the present embodiment includes a measuring unit 1, an arithmetic control unit 23, and an alarm unit WD. The measuring unit 1 includes a density meter 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 sent to the arithmetic control unit 23 through a signal line. In addition, since the details of the measurement unit 1 are the same as those in the second embodiment, a description thereof will be omitted.

  Receiving the measured value of the density of the developing solution, the calculation control unit 23 measures the density in the calculation block 21 based on the correspondence between the density of the developing solution and the absorbed carbon dioxide concentration (for example, the linear relationship in FIG. 1). The absorbed carbon dioxide concentration of the corresponding developer is calculated from the value. The calculated absorbed carbon dioxide concentration is sent to the control block 31 as a measured value of the absorbed carbon dioxide concentration of the developer.

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

  Based on the measured absorbed carbon dioxide concentration, the control block 31 issues a control signal to the control valves 41 to 43 so that the absorbed carbon dioxide concentration of the developer becomes a predetermined management value or a management value or less. Since the developer tends to absorb carbon dioxide and increase its concentration, control is performed by replenishing a replenisher that has the effect of reducing the absorbed carbon dioxide concentration. The details of the control are the same as in the description of the second embodiment, and will be omitted.

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

  As described above, according to the developer management apparatus E of the present embodiment, the absorbed carbon dioxide concentration of the alkaline developer can be managed so as to be a predetermined management value or lower than the management value. Further, an alarm can be issued when the absorbed carbon dioxide concentration is out of the management range by the alarm means WD.

[Fourth embodiment]
FIG. 6 shows the calculation of absorption carbon dioxide concentration based on the relationship between developer density and absorption carbon dioxide concentration based on the density value of the developer measured by the density meter. It is a schematic diagram of a developer management device that manages the absorbed carbon dioxide concentration of a developer by replenishing the developer with a replenisher based on the carbon dioxide concentration. For convenience of explanation, the developing solution management apparatus E is illustrated together with the developing process facility B, the replenisher storing part C, and the circulation stirring mechanism D in a mode connected to the developing process facility B.

  In the developer management apparatus of the present embodiment, the calculation means for calculating the absorbed carbon dioxide concentration from the measured value of the developer density and the control means for controlling the absorbed carbon dioxide concentration of the developer are configured separately. This is a developer management apparatus of the type.

  The developer management apparatus E of the present embodiment includes a measurement unit 1, a calculation unit 2, a control unit 3, and a warning unit WD. The measuring unit 1 includes a density meter 11 and other measuring means 12 and 13. The calculation unit 2 includes a calculation block 21 that calculates the absorbed carbon dioxide concentration in the developer based on the correspondence between the density and the absorbed carbon dioxide concentration (for example, the linear relationship in FIG. 1) from the measured density value. Based on the calculated absorbed carbon dioxide concentration, the control unit 3 replenishes the developer with a replenisher so as to control the absorbed carbon dioxide concentration of the developer to be a predetermined management value or less than the management value. A control block 31 is provided.

  In the measurement unit 1, the density value of the sampled developer is measured by the density meter 11. The measured density value is sent to the calculation unit 2 through a signal line. In addition, since the details of the measurement unit 1 are the same as those in the second embodiment, a description thereof will be omitted.

  Receiving the measured value of the density of the developing solution, the calculation unit 2 receives the measured value of the density in the calculation block 21 based on the correspondence between the density of the developing solution and the absorbed carbon dioxide concentration (for example, the linear relationship of FIG. To calculate the absorbed carbon dioxide concentration of the corresponding developer. The calculated absorbed carbon dioxide concentration is sent to the control unit 3 as a measured value of the absorbed carbon dioxide concentration of the developer.

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

  Based on the measured absorbed carbon dioxide concentration, the control unit 3 issues a control signal to the control valves 41 to 43 so that the absorbed carbon dioxide concentration of the developer becomes a predetermined management value or a management value or less. Since the developer tends to absorb carbon dioxide and increase its concentration, control is performed by replenishing a replenisher that has the effect of reducing the absorbed carbon dioxide concentration. The details of the control are the same as in the description of the second embodiment, and will be omitted.

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

  As described above, according to the developer management apparatus E of the present embodiment, the absorbed carbon dioxide concentration of the alkaline developer can be managed so as to be a predetermined management value or lower than the management value. Further, an alarm can be issued when the carbon dioxide concentration is out of the management range by the alarm means WD.

  Next, a modified example of the developer management apparatus E of the present embodiment will be described.

  4 to 6, the measuring unit 1 of the developing solution management apparatus depicts the developing solution management apparatus configured integrally with the calculation unit 2 and the control unit 3, but the developing solution management apparatus E according to the present embodiment is illustrated here. It is not limited. The measurement part 1 can also be made into a separate structure.

  Since each measuring means 11-13 including the density meter has an optimum installation method according to the measurement principle employed, for example, the measuring unit 1 is connected inline to the developer pipe 80, or a developer storage tank. Alternatively, the measurement probe 61 may be installed so as to be immersed in 61. Each measuring means 11-13 may be installed separately, respectively. The developing solution management apparatus E of the present embodiment can be realized as long as the measuring units 11 to 13 communicate with each other so that the measurement data can be exchanged with the calculation unit 2 and the control unit 3.

  Similarly, in FIGS. 4 to 6, the developer management apparatus E in a form in which the density meter and other measuring units 11 to 13 are connected in series is illustrated, but the developer management apparatus E of the present embodiment is not limited to this. . Each measuring means 11 to 13 may be connected in parallel or may be independently piped. Depending on the measurement principle adopted by each measuring means, if reagent addition is necessary, each measuring means may be provided with a pipe for that purpose, and if a waste liquid is required, each measuring means has a pipe line for that purpose. May be provided. Even if the measuring units are not connected in series, the developer management apparatus E of the present embodiment can be realized.

  The calculation unit 2 of the developer management apparatus E according to the present embodiment uses the correspondence relationship between the developer density and the absorbed carbon dioxide concentration (for example, a linear relationship as shown in FIG. 1) to obtain a measured value of the developer density. In addition to the calculation function for calculating the carbon dioxide concentration based on this, another calculation function may be provided. For example, an arithmetic function for calculating other component concentrations such as an alkali component concentration of a developing solution and a dissolved photoresist concentration may be provided.

  The control unit 3 of the developer management apparatus E of the present embodiment has a control function for replenishing the developer with a replenisher so as to control the carbon dioxide concentration of the developer to a predetermined management value or lower than the management value. In addition, other control functions may be provided. For example, a control function may be provided for controlling other component concentrations such as the alkali component concentration and dissolved photoresist concentration of the developer so as to be within a management range below a predetermined management value or management value. For this purpose, in addition to replenishing the developer with a replenisher, a control for draining the developer as appropriate is added, and a control for returning the regenerated developer that has been regenerated by filtering impurities through a filter, etc. Various controls can be performed.

  4 to 6, the developer management device E replenishes so that the control valves 41 to 43 provided in the conduits for supplying the replenisher to be replenished to the developer are internal components of the developer management device E. Although the aspect connected with the liquid pipe lines 81 and 82 and the pure water pipe line 83 was drawn, the developing solution management apparatus E of this embodiment is not limited to this. The developer management apparatus may not include the control valves 41 to 43 as internal components, and may not be connected to the conduits 81 to 83 for supplying the replenisher to the developer.

  The control unit 3 in the developer management apparatus E of the present embodiment and the control valves 41 to 43 provided in the pipelines for replenishing the replenisher are controlled by the control valves 41 to 43 of the developer management apparatus E. It suffices if the control signals issued by 3 are received and controlled so as to communicate with each other. Even if the control valve is not an internal component of the developer management apparatus E, the developer management apparatus E of this embodiment can be realized.

  The control unit 3 of the developer management apparatus E may not be configured integrally with the measurement unit 1 and the calculation unit 2 or may be a separate body. The measurement unit 1, the calculation unit 2, and the control unit 3 may exist as separate devices. If the measurement data, the calculation result, the control signal, and the like are communicated with each other via a signal line or the like, the developer management apparatus E of the present embodiment can be realized.

  The function of controlling the absorbed carbon dioxide concentration of the control unit 3 and the function of controlling other components such as the alkali component concentration and the dissolved photoresist concentration are preferably realized by a common control means. It may be realized by means. The replenisher used for the control, the pipeline for supplying it, and the control valve may be prepared separately for each target component of the developer to be controlled, but are common if they can be used in common. It is preferable.

  The developer management apparatus of the present invention is provided with a density meter in spite of the various modifications as described above, and a correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration (for example, Using the linear relationship as shown in FIG. 1, the absorbed carbon dioxide of the developer based on the density value of the developer measured by the density meter or calculated from the density value of the developer measured by the density meter Based on the concentration value, control is performed by replenishing the developer with a replenisher so that the absorbed carbon dioxide concentration of the developer becomes a predetermined management value or lower than the management value.

  As described above, according to the developer management apparatus of the present invention, the absorbed carbon dioxide concentration of the alkaline developer can be managed to a predetermined management value or less than the management value. Therefore, the developer management apparatus of the present embodiment can maintain the alkaline developer in a state of absorbed carbon dioxide concentration that exhibits optimum development performance, and can realize a desired line width and remaining film thickness. .

  When the developer management apparatus of the present invention can further manage the alkaline component concentration and dissolved photoresist concentration of the alkaline developer, the concentration of each component of the alkaline developer is managed in a predetermined state. Therefore, compared to the conventional developer management in which the absorbed carbon dioxide concentration cannot be managed, according to the developer management apparatus of the present invention, the development performance of the alkaline developer can be maintained and managed so as to be more accurate and constant. . Therefore, the development speed when developing the photoresist is stabilized, the line width and the remaining film thickness by the development process are made constant, the product quality is improved, and further miniaturization and higher integration are realized. Expected to contribute.

  Furthermore, according to the developer management device of the present invention, the developer is automatically maintained at the optimum development performance at all times, so that the product yield is improved and the replacement work of the developer becomes unnecessary, and the running cost and the waste liquid cost are reduced. It is expected to contribute to the reduction of

DESCRIPTION OF SYMBOLS A ... Concentration monitoring apparatus, B ... Development process equipment, C ... Replenisher storage part, D ... Circulating stirring mechanism, E ... Developer management apparatus 1 ... Measurement part 11 ... Density meter 12, 13, ... Measuring means, 14 ... Sampling Pump 15, sampling pipe 16, outlet side pipe 2 arithmetic unit 21 arithmetic block 22 display means 23 arithmetic control unit (for example, computer)
3 ... Control unit 31 ... Control blocks 41-43 ... Control valve, 44, 45, 46, 47 ... Valve,
DESCRIPTION OF SYMBOLS 51 ... Sample cell, 52 ... Thermometer, 53 ... Peltier device, 54 ... Constant temperature block, 55 ... Thermal insulation, 56 ... Vibrator, 61 ... Developer storage tank, 62 ... Overflow tank, 63 ... Liquid level gauge, 64 ... Development chamber hood, 65 ... roller conveyor, 66 ... substrate, 67 ... developer shower nozzle, 71 ... waste liquid pump, 72, 74 ... circulation pump, 73, 75 ... filter, 80 ... developer line, 81, 82 ... replenishment Liquid (developer stock solution and / or new liquid) pipe, 83... Pure water pipe, 84. Merge pipe, 85. Circulation pipe, 86. Nitrogen gas pipe, 91 and 92. WD ... Alarm means

Claims (6)

A density meter;
Calculation means for calculating the absorbed carbon dioxide concentration of the developer from the correspondence between the density of the developer and the absorbed carbon dioxide concentration, based on the density value of the developer showing alkalinity measured by the density meter When,
Alarm means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the arithmetic means is out of a preset management range;
A developer concentration monitoring apparatus comprising:   As the alarm means, an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning light that lights or blinks light, a display device that displays a warning, and a relay terminal that switches between opening and closing of contacts, The developer concentration monitoring apparatus according to claim 1, comprising at least one of the following. A density meter;
Based on the density value of the developer indicating alkalinity measured by the densimeter, the absorbed carbon dioxide concentration of the developer is determined to be a predetermined value using the correspondence relationship between the density of the developer and the absorbed carbon dioxide concentration. Control means for issuing a control signal to a control valve provided in a conduit for feeding a replenisher to be replenished to the developer so as to be a management value or a management value or less;
The density of the developer measured by the density meter from a density range corresponding to a preset management range of the absorbed carbon dioxide concentration, which is determined by the correspondence between the density of the developer and the absorbed carbon dioxide concentration. An alarm means for issuing an alarm when the value deviates,
A developer management apparatus comprising: A density meter;
Based on the density value of the developing solution showing alkalinity measured by the densimeter, an arithmetic unit for calculating the carbon dioxide concentration of the developing solution from the correspondence between the density of the developing solution and the absorbed carbon dioxide concentration; Based on the absorbed carbon dioxide concentration of the developer calculated by the arithmetic unit, the replenishment replenished to the developer so that the absorbed carbon dioxide concentration of the developer is equal to or lower than a predetermined management value. A control unit that emits a control signal to a control valve provided in a pipeline for feeding the liquid, and an arithmetic control means comprising:
Alarm means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the arithmetic unit is out of a preset management range;
A developer management apparatus comprising: A density meter;
Calculation means for calculating the absorbed carbon dioxide concentration of the developer from the correspondence between the density of the developer and the absorbed carbon dioxide concentration, based on the density value of the developer showing alkalinity measured by the density meter When,
Based on the absorbed carbon dioxide concentration of the developer calculated by the computing means, a replenisher solution replenished to the developer so that the absorbed carbon dioxide concentration of the developer becomes a predetermined management value or a management value or less. Control means for issuing a control signal to a control valve provided in a pipe line for feeding liquid;
Alarm means for issuing an alarm when the absorbed carbon dioxide concentration value of the developer calculated by the arithmetic means is out of a preset management range;
A developer management apparatus comprising:   As the alarm means, an external output signal terminal that transmits an alarm signal, an alarm device that emits an alarm sound, a warning light that lights or blinks light, a display device that displays a warning, and a relay terminal that switches between opening and closing of contacts, The developer management apparatus according to claim 3, comprising at least one of the following.

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