JP6401580B2 - Analysis apparatus and analysis method - Google Patents

Description

  The present invention relates to an analysis apparatus and an analysis method.

  Conventionally, an analysis target liquid is separated into two liquids containing a relatively large amount of bubbles and a liquid containing a relatively small amount of bubbles by a bubble separator, and a desired analysis is performed on a liquid containing a relatively small amount of bubbles. Analytical methods / apparatuses are known that merge with a liquid containing a relatively large amount of bubbles after being performed.

JP 2006-113075 A

  However, the conventional method cannot sufficiently remove the influence of noise in the analysis result. The present invention has been made in view of the above problems, and an object thereof is to provide an analysis apparatus and an analysis method that can further improve measurement accuracy.

The secondary analysis apparatus according to the present invention includes a bubble separator that separates an inflowing liquid into a first liquid having a relatively small amount of bubbles and a second liquid having a relatively large amount of bubbles,
An analyzer for analyzing the first liquid separated by the bubble separator;
A dropping device for dropping the second liquid separated by the bubble separator;
A merging unit that merges the first liquid discharged from the analyzer and the second liquid discharged from the dropping unit;

The analysis method according to the present invention includes a step of separating a liquid into a first liquid having a relatively small amount of bubbles and a second liquid having a relatively large amount of bubbles,
Analyzing the first liquid;
Dropping the second liquid; and
A step of joining the second liquid after dropping with the first liquid after analysis.

  According to these inventions, since the defoamed liquid is analyzed, errors in analysis due to bubbles can be reduced. In addition, since the second liquid separated from the first liquid is added again after the second liquid is dropped, the second liquid does not form another current path different from the first liquid, and thus is formed by the second liquid. The influence of the current path on the analysis result can be suppressed.

  Here, the bubble separator may be a T-shaped tube having an upward tube, a downward tube, and a horizontal tube, the liquid flows in from the horizontal tube, and the first liquid is discharged from the downward tube. Then, the second liquid can be discharged from the upward cylinder. According to this, bubbles can be efficiently removed with a simple configuration.

  The analyzer may include a sensor that measures a current flowing in the liquid. According to this, the accuracy of the analysis result is particularly improved.

  ADVANTAGE OF THE INVENTION According to this invention, the analyzer which can improve a measurement precision more and the analysis method are provided.

FIG. 1 is a flowchart of an analyzer according to an embodiment of the present invention. 2A and 2B are circuit diagrams showing examples of the analyzer of FIG. FIG. 3 is a cross-sectional view showing an example of the bubble separator of FIG. FIG. 4 is an example of an analysis result according to the example. FIG. 5 is an example of an analysis result according to the comparative example.

  Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a flowchart of an analyzer 100 according to an embodiment of the present invention.

  The analyzer 100 analyzes the developer sampled from the developer utilization system S and returns it to the developer utilization system S.

  The developer utilization system S includes a developing unit S1, a developer collecting unit S2, and a developer regenerating unit S3. The developing section S1 dissolves the resist with a developer supplied from the developer regeneration section S3, for example, a TMAH (tetramethylammonium hydroxide) aqueous solution, and obtains a resist having a desired shape.

  The developer recovery unit S2 recovers and stores the developer used for development. The developer regeneration unit S3 removes the dissolved resist in the developer by precision filter processing or the like, adjusts the concentration, and regenerates the developer.

  The analyzer 100 mainly includes a bubble separator 10, an analyzer 20, a dropper 30, and a junction 40.

  The bubble separator 10 separates the developer supplied from the developer regeneration unit S3 of the developer utilization system S into a first liquid with relatively few bubbles and a second liquid with relatively many bubbles. The first liquid is supplied to the analyzer 20 and the second liquid is supplied to the dropping unit 30.

  Specifically, the bubble separator 10 of the present embodiment is a T-shaped tube having an upward cylinder 10C, a downward cylinder 10B, and a horizontal cylinder 10A. A developer regeneration unit S3 is connected to the horizontal cylinder 10A by a line L0 having a pump P. A line L1 that returns to the developer regeneration unit S3 via the analyzer 20 and the merge unit 40 is connected to the downward cylinder 10B. A line L2 having a valve V1 and a dropper 30 is connected to the upward cylinder 10C, and the line L2 is connected to the junction 40. The developer supplied from the developer regeneration unit S3 to the horizontal cylinder 10A is separated into a first liquid discharged from the downward cylinder 10B and a second liquid discharged from the upward cylinder 10C.

  The inner diameter of each cylinder is not particularly limited. For example, the inner diameter of the horizontal cylinder 10A can be 6.0 mm to 22.2 mm. The inner diameters of the downward cylinder 10B and the upward cylinder 10C can be 6.0 mm to 22.2 mm.

  The analyzer 20 measures the TMAH concentration in the first liquid. Specifically, the analyzer 20 determines the concentration based on a conductivity meter (sensor) 20S that measures the conductivity of the developer, and the correspondence relationship between the measured conductivity and a predetermined conductivity-TMAH concentration. And a computer unit 20C to acquire.

  The form of the conductivity meter 20S is not particularly limited. For example, as shown in FIG. 2A, the electromagnetic induction type conductivity meter includes a toroidal coil C1 having a winding W1 arranged in a container V to which a liquid is supplied, and a winding W1 of the toroidal coil C1. A power supply PS1 for applying an alternating current to the toroidal coil C2 having a winding W2 for detecting an induced current i applied to the liquid by the toroidal coil C1, and a detector D for detecting a voltage induced in the winding W2. . As shown in FIG. 2B, the AC two-electrode conductivity meter includes a pair of electrodes E1 and E2 disposed in the container V, a power source PS1 that applies an AC voltage between these electrodes, A detector D for detecting a current flowing between the electrodes is provided.

  Returning to FIG. 1, the dropping device 30 drops the second liquid. As shown in FIG. 3, the dropping device 30 mainly includes a container 32 and a dropping tube 34. The container 32 includes a slope portion 32S, a storage portion 32R, and a dropping tube insertion portion 32C. The dropping tube insertion portion 32C is formed above the slope portion 32S.

  A dripping pipe 34 is inserted into the dripping pipe insertion portion 32 </ b> C via a sealing material 36. The inner end of the dripping pipe 34 faces the slope portion 32S and is separated from the slope portion 32S. The outer end of the dropping pipe 34 is connected to the bubble separator 10 via a line L2.

  The inner diameter of the dripping pipe 34 is not particularly limited as long as the second liquid can be dropped, but may be, for example, 8.0 to 22.2 mm. Further, the distance between the dropping tube 34 and the slope portion 32S is only required to be a distance at which the second liquid can be dropped. For example, the shortest distance in the vertical direction between the lower end of the dropping tube 34 and the slope portion 32S is as follows. It can be 10 mm to 15 mm.

  The storage portion 32R is connected to the lower end of the slope portion 32S so that the developer dropped onto the slope portion 32S can be stored.

  The angle of inclination of the slope portion 32S may be any angle that allows the dropped developer to flow into the storage portion 32R. For example, the angle θ between the surface of the slope portion 32S and the horizontal plane is 1 to 90 °. Can do. In the case of 90 °, the slope portion 32S does not exist and is directly dropped onto the storage portion 32R.

  In the dripping pipe 34, the dripping pipe 34 and the slope portion 32S are preferably made of an electrically insulating material such as glass or resin, but can also be implemented with a metal material.

  The dropping speed may be in a range where the liquid can be dropped without continuously flowing down, and can be, for example, 30 to 120 drops / min.

  A line L2 is connected to the lower end of the reservoir 32R.

  Returning to FIG. 1, the junction 40 is provided on the downstream side of the analyzer 20 in the line L1. The merge unit 40 merges the developer discharged from the dropping device 30 and supplied via the line L2 with the developer flowing through the line L1. There is no restriction on the form of the junction.

  Next, a developer analysis method using such an analyzer 100 will be described.

  First, the developer is supplied from the developer regenerating unit S3 to the bubble separator 10 via the line L0 by the pump P. Bubbles are contained in the developer flowing through the line L0. In the bubble separator 10, as the developer branches into the first downward liquid and the second upward liquid, the bubbles in the developer are mostly contained in the upward second liquid due to the buoyancy. Therefore, the amount of bubbles in the first liquid is relatively smaller than that in the second liquid. In this way, the first liquid in which the amount of bubbles is reduced is supplied to the analyzer 20 via the line L1, and the analyzer 20 continuously measures the conductivity of the developer, and the obtained conductivity. Based on the above, the concentration of TMAH is obtained continuously. Thereafter, the first liquid returns to the developer regeneration unit S3 via the line L1.

  On the other hand, the second liquid is supplied to the dropping device 30 via the line L <b> 2 and dropped from the dropping pipe 34. The dropped developer is joined to the line L1 at the joining unit 40 via the line L2.

  The flow rate of the second liquid flowing through the line L2 can be adjusted by the valve V1. The flow rate of the second liquid flowing through the line L2 can be adjusted as appropriate as long as the developer does not continuously flow down with the dropping device 30. The flow rate of the second liquid is usually less than the flow rate of the first liquid.

  According to the present embodiment, since the liquid degassed by the bubble separator 10 is analyzed by the analyzer 20, analysis errors due to bubbles can be reduced. In addition, since the second liquid separated from the first liquid by the bubble separator 10 merges with the first liquid via the dropping device 30, the second liquid is transferred from the bubble separator 10 to the junction 40. It is electrically isolated, i.e. the second liquid does not form a current path. Therefore, an error caused in the conductivity meter due to the presence of the current paths of the line L1 and the line L2 in parallel between the bubble separator 10 and the junction 40 is suppressed. In particular, if there are two current paths, noise due to an electrical loop may occur. Further, since the second liquid generated in the bubble separator 10 is joined to the line L1, the waste of the developing liquid and the cost of waste liquid processing are reduced.

  The present invention is not limited to the above-described embodiment, and various modifications can be made. For example, in the above-described embodiment, the developer is used as the target liquid. However, the liquid can be applied to any liquid as long as it can be dropped. In particular, a liquid having conductivity, for example, an aqueous solution is preferable. Examples of the liquid are a resist stripping solution, a developing solution, an etching solution, and the like. These liquids can be aqueous solutions containing acid or alkali components.

  Moreover, in the said embodiment, although the analyzer 20 which has a conductivity meter and measures the density | concentration of TMAH is employ | adopted, if it is an analyzer which has a sensor which measures the electric current which flows in a liquid, various analyzers will be used. Can be adopted. For example, an analyzer having a conductivity meter and acquiring other concentrations and characteristics other than TMAH may be used, or an analyzer having a sensor other than the conductivity meter, such as a dielectric constant meter, may be used.

  Also, the analysis interval of the analyzer is not particularly limited, and the analysis interval may be continuous analysis of about several seconds, or intermittent analysis such as once a day.

  Moreover, in the said embodiment, although the dripping device which has a slope part and a dripping pipe is employ | adopted, it will not be limited to this as long as it is the mechanism which can dripping a liquid and can divide the conductive path of a liquid and can insulate. For example, it is not necessary to have a slope part, for example, it may replace with a dripping pipe | tube and may employ | adopt a spray nozzle and may drip mist-like liquid.

  Further, the gas-liquid separator is not limited to the T-shaped tube. For example, a cyclone type or a liquid is rotated by rotating the container to apply a centrifugal force to the liquid, and a liquid with many bubbles on the outside with respect to the rotation axis and a liquid with few bubbles on the inside with respect to the rotation axis. A separation device can be used.

  Further, the supply source of the line L0 is not limited to the developer regeneration section, and any supply source can be used.

  The analyzer can also include a temperature adjustment unit that maintains the temperature of the liquid supplied into the analyzer 20 within a certain range.

  Moreover, the position of the junction 40 may be after the analyzer 20, and for example, the developer utilization system S such as the developer regeneration unit S3 may be used as the junction.

(Example)
The TMAH concentration of the developer (2.38 wt% TMAH aqueous solution) was measured using the system and analyzer shown in FIG. Using an analyzer having a conductivity meter, the conductivity data was converted to TMAH concentration using predetermined calibration data.

  The inner diameter of the dropping tube of the dropping device was 8 mm, the dropping speed was about 60 drops / minute, and the angle θ of the slope was 7 °. The inner diameter of each cylinder of the bubble separator was 8 mm. As the developer utilization system S, an actual developing device was used. Since the developer having a predetermined concentration is circulated only in the analyzer without performing development in the developer utilizing system S, the concentration of the developer does not vary.

(Comparative example)
The same procedure as in the example was performed except that the developer discharged from the upward cylinder 10C was not supplied to the junction 40 via the line L2 without using the dropping unit 30.

  The results of Examples and Comparative Examples are shown in FIGS. 4 and 5, respectively. Noise was confirmed in the comparative example, but no noise was confirmed in the example.

  DESCRIPTION OF SYMBOLS 10 ... Bubble separator, 10A ... Horizontal cylinder, 10B ... Downward cylinder, 10C ... Upward cylinder, 20 ... Analyzer, 30 ... Dropper, 40 ... Merging part, 100 ... Analytical apparatus.

Claims (3)

A bubble separator that separates an inflowing liquid into a first liquid having a relatively small amount of bubbles and a second liquid having a relatively large amount of bubbles;
An analyzer for analyzing the first liquid separated by the bubble separator;
A dropping device for dropping the second liquid separated by the bubble separator;
E Bei confluence unit, for combining the second liquid discharged from the first fluid and the dropper discharged from the analyzer,
The analyzer includes an sensor that measures a current flowing in the liquid .   The bubble separator is a T-shaped tube having an upward tube, a downward tube, and a horizontal tube, the liquid flows in from the horizontal tube, the first liquid is discharged from the downward tube, and the second liquid The analyzer according to claim 1, wherein is discharged from the upward tube. Separating the liquid into a first liquid having a relatively small amount of bubbles and a second liquid having a relatively large amount of bubbles;
Analyzing the first liquid;
Dropping the second liquid; and
The second solution after dropping, the step of merging the first liquid after analysis, Bei give a,
The analysis method includes measuring an electric current flowing through the first liquid .

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