JPH03215735A - Automatic liquid controller - Google Patents

Abstract

PURPOSE:To analyze an extremely small amount of processing liquid by setting the number of times of sampling optionally and increasing/decreasing a sampling amount freely. CONSTITUTION:A control means 103 is provided with the number of times of setting function which can set the number of times of sampling of the processing liquid by a sampling means 100 optionally. The sampling amount of the processing liquid to be fed to reaction cells 25 and 26 can be increased/ decreased freely by increasing/decreasing the number of times of sampling and a fine amount of processing liquid can be analyzed by setting the sampling frequency large, as well. (A fine-amount analysis is available when the sampling amount, i.e. the number of times of sampling becomes large.) Further, a photocell 4 guides the processing liquid sent by a processing liquid supply path 1 into the cell and the processing liquid is irradiated with a light having constant wavelength to detect the degradation of the quality of the processing liquid with time from the measurement result of the absorbance of the processing liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to an automatic liquid management device that can automatically detect the amount of components and deterioration of a processing liquid.

"Prior Art" Conventionally, stripping solutions (processing solutions) used, for example, in semiconductor manufacturing processes, have been analyzed and managed using various methods. Management has been automated.

For example, in this type of automatic liquid management device, a stripping solution containing a mixture of sulfuric acid and hydrogen peroxide is sampled intermittently using a bomb and a valve, and then injected into a reaction cell in an analytical instrument, where the reaction takes place. Titration analysis is performed within the cell.

In such an analysis, a computer installed in the control unit analyzes the pump, . In addition to controlling the operation of equipment such as the hull, it calculates the sulfuric acid concentration and hydrogen peroxide concentration in the processing liquid based on the amount of the reagent titrated into the reaction cell, and outputs the calculation results to a CRT or printer. was.

``Problems to be Solved by the Invention'' By the way, the above-mentioned automatic liquid management device has two problems: (1) the amount of sampled processing liquid is set to a constant value, making it impossible to perform trace analysis; the operation of the equipment,
The processing status of the liquid cannot be determined. (3) The amount of each drop dropped by the titration device is constant, so if the amount is set small, the dripping time will be longer, and if it is set larger, analysis errors may occur. Each had the problem of growing larger.

This invention was made in view of the above-mentioned circumstances, and (-) the number of sampling times can be freely set, the sampling (total) amount can be freely increased or decreased, and trace analysis is also possible. (2) It is possible to directly grasp the operating status of the device, and (3) It is possible to perform titration efficiently and shorten the dripping time. For the purpose of providing.

"Means for Solving the Problem" In order to achieve the above object, the first invention provides a sampling means for sampling a processing liquid, and determining the amount of active ingredient in the sampled processing liquid from a potential change and titration. An automatic liquid management device comprising a titration means, a control means for controlling each of the means, and an input means for giving various commands to the control means, the apparatus comprising: The control means, based on the command from the input means, .
A number setting function is provided for arbitrarily setting the number of times the processing liquid is sampled by the sampling means.

In the second invention, there is provided a sampling means for sampling the treatment liquid, a titration means for determining the amount of active ingredient in the sampled treatment liquid from a potential change and titration, a control means for controlling each of the above-mentioned means, and a control means for controlling the respective means. An output means for displaying the operating status and processing status of the device based on the control results is provided.

In the third invention, there is provided a sampling means for sampling the treatment liquid, a titration means for determining the amount of active ingredient in the sampled treatment liquid from a potential change and titration, a control means for controlling each of the above-mentioned means, and a control means for controlling the above-mentioned means. An automatic liquid management device comprising an input means for giving various commands to the control means, the control means being configured to control the amount of drip per drop by the titration means based on the commands from the input means, based on potential changes. A dripping amount setting function is provided to set the dripping amount so that it becomes small near the end point.

"Operation" According to the first invention, since the control means is provided with a number setting function for arbitrarily setting the number of sampling times of the processing liquid by the sampling means, the sampling (total) amount can be freely increased or decreased. I can do it.

According to the second invention, since the output means is provided for displaying the operating status of the apparatus based on the control result by the control means, the operating status of the apparatus can be determined by the operator referring to the output means. be understood directly.

According to the third invention, the control means is provided with a drip amount setting function for setting the drip amount per drop by the titration means to be smaller near the end point based on the potential change based on the command from the input means. Therefore, the titration by the titration means can be performed for a short period of time.

"Embodiment" An embodiment of the present invention will be described with reference to FIGS. 1(A) to 5.

First, the general structure of the entire automatic liquid management apparatus will be explained with reference to FIG. 1(A). In the figure, what is indicated by the symbol l is a processing liquid supply path through which the processing liquid is supplied.

The treatment liquid may include one containing components such as sulfuric acid and hydrogen peroxide that can be used to remove and dissolve the resin (such as Noporanok resin) on a silicon wafer for semiconductors.

In the middle of the processing liquid supply path 1, along the flow direction X of the processing liquid, there are a cooler 2 for cooling the processing liquid, a filter 3 for removing impurities such as undissolved substances, a photocell 4, and a solenoid valve 5.
are set up in sequence.

The photocell 4 guides the processing liquid sent through the processing liquid supply path 1 into a cell (not shown) and measures the absorbance of the processing liquid by irradiating the processing liquid with a light beam of a certain wavelength. Based on the measurement results, the degree of deterioration of the processing liquid over time is detected.

Note that the processing liquid passing through the photocell 4 is colored by dissolving the peeled resist.

Further, the six-way solenoid valve 5 is (1) usually arranged as shown by the solid line, and the processing liquid is transferred to a processing tank (not shown) through a loop 10 and paths 6 and 7, and to a train through paths 6 and 8. (2) When measuring the concentration of sulfuric acid and hydrogen peroxide in the processing liquid, the liquid is switched to the position shown by the dotted line, and while it is placed at the position shown by the solid line, it is temporarily stored in the loop 10. The treated solution is transferred to the pure water supply system 11 (
(to be described later) is pushed out by pure water sent through a reaction cell (to be described later).

Note that the lube 10 has a preset amount of processing liquid stored therein, that is, is used for quantitative determination.

Further, the one provided at the branching part of the paths 6 to 8 is a three-way solenoid valve 12 for guiding particularly dirty processing liquid to the drain tank 9, and the one provided in the middle of the path 6 is a bomb 13. A PH electrode 14 is provided in the middle of the path 8 to measure the PH of the processing liquid.

Further, the pure water supply system 1.1 includes a two-way solenoid valve I6 provided along the pure water supply route I5, an intermediate toranop l7,
It is composed of a bomb 18 and a relief valve 20 provided in a branched path 19 to maintain the supply pressure of the pure water below a certain value. In addition, this relief valve 20
The pure water discharged is guided to the drain tank 9.

On the other hand, the processing liquid that is temporarily stored in the loop 10 and then pushed out by the pure water flows through the paths 21 to 23 and the paths 21 to 23.
A three-way solenoid valve 24 provided at a branch part of 23 selectively guides the reaction cells 25 and 26.

Further, the reaction cells 25 and 26 include the paths 22 and 2.
Reagent supply systems 27 to 29 that supply reagents to the processing liquid supplied by 3, and redox electrodes 30 and 3l that measure the redox potential of the solution in the reaction cells 25 and 26 are provided. There is.

The reagent supply systems 27 to 29 include flasks 27A to 29A.
The reagents stored in the reaction cells 25 and 25 are passed through routes 27C to 29C by titration pumps 27B to 29B.
The oxidation-reduction electrodes 30 and 31 detect the oxidation-reduction potential of the processing solution when the reagent is dropped, and detect the sulfuric acid of the processing solution based on the change in the oxidation-reduction potential. , the hydrogen peroxide concentration can be calculated.

In other words, the point at which the redox potential jumps is the end point of the reaction, and the amount of reagent dripped at the end point of this reaction (data indicating this amount of drip is output from the titration pumps 27B to 29B to the control means 103, which will be described later). From this, the sulfuric acid and hydrogen peroxide concentrations of the treatment liquid are calculated.

As the reagents stored in the flasks 27A to 29A, suitable alkali standard solutions such as sodium hydroxide, standard solutions that cause redox reactions such as potassium permanganate solution, acidic standard solutions such as sulfuric acid, etc. It is.

On the other hand, in the lower part of the reaction cells 25 and 26, paths 32 to 34 are provided for discharging the processing liquid in the reaction cells 25 and 26 each time a measurement is completed. , filters 35 and 36, two-way solenoid valves 37 and 38 for discharging the solution from the reaction cells 25 and 26,
Drainage bombs 39 are sequentially provided. The solution discharged through the paths 32 to 34 is sent into the drain tank 9 described above.

In the above configuration, the configuration in the range shown by the reference numeral 100 in FIG.

Further, in FIG. 1(B), the reference numeral 103 is a control means, and this control means 103 includes an input means 104 such as a keyboard, and input means 104 for inputting the operating status and processing status of the apparatus.
Display panel l05 for RT display (for example, Fig. 1 (A)
A system diagram similar to that shown in the figure is shown, and a display panel (with lamps, etc.) is provided at locations corresponding to each component.

The control means 103 controls the following processing means (A) based on the input data of the input means 1040, and also controls the processing means (A) based on the control result of this processing means (A).
) The operating status and processing status are displayed on the display panel 105 based on the detection data of the detection means (B) obtained by controlling the system.

The processing means (A) includes a cooler 2, a six-way solenoid valve 5, a three-way solenoid valve 12, a pump 13, and a two-way solenoid valve 16.
, a three-way solenoid valve 24, titration pumps 27B to 29B, two-way solenoid valves 37 and 38, and a drain bomb 39, and the detection means (B) includes a photocell 4, a PH'l pole 14, a titration pump Bombs 27B to 29B, redox electrode 30.
There are 31 etc.

Next, the control contents of the automatic liquid management device stored in the control means 103 will be explained with reference to FIGS. 2 to 5.

FIG. 2 is a flowchart for determining whether various measurement conditions regarding titration are set. Note that "Step nJ" in the specification corresponds to [SP n l in the figure.

<Step l> Using the input means, the sampling amount (that is, the number of sampling times) of the processing liquid to be supplied to the reaction cells 25 and 26, the dripping amount per drop of the reagent dripped by the dripping pumps 27B to 29B (1a,; minute (as a numerical value), and set automatic or manual operation.

Step Knob 2> Determine whether the condition is set by Step Knob 1, and select YES.
If S, proceed to step 3.

Step 3> Determine whether it is an automatic analysis operation or a manual analysis operation, and proceed to Step 4 if it is an automatic analysis operation, and proceed to Step 5 if it is a manual analysis operation.

Step 4> Perform automatic analysis (see Figure 3) Kuste, Bu 5〉 Perform manual analysis.

Next, with reference to FIG. 3, the control details of the "automatic analysis" shown in step 4 will be explained.

<Step 6> Set the six-way solenoid valve 5 to the position shown by the solid line, and set the three-way solenoid valve 24
, the two-way solenoid valve 16 is set appropriately, and the bomb 18 is driven to supply pure water sent from the pure water supply system 11 into, for example, the reaction cell 25 to clean the inside thereof.

Note that the reaction cell 26 is also washed at the same time, and at this time the three-way solenoid valve 24 is switched.

During this period, the processing liquid supplied through the processing liquid supply path 1 is guided to the path 6 side via the lube 10 by driving the pump 13.

<Stenop 7> Set the two-way solenoid valve 37 to open state, and drain liquid bomb 39
is driven to discharge the cleaning liquid in the reaction cell 25 to the drain tank 9. Further, the inside of the reaction cell 26 is also cleaned in the same manner.

Step 8> Sampling (described later with reference to the flowchart in FIG. 4).

<Stenob 9> Titration analysis of the concentrations of sulfuric acid and hydrogen peroxide, which are active ingredients, contained in the treatment liquid (described later with reference to the flowchart in FIG. 5).

<Step 10> The same evacuation operation as shown in the steno knob 7 above is performed.

<Stenop 11> to <Step 12> These steps are the same as the above <Step 6> to <Step 7> and will therefore be omitted.

Next, the "sampling" shown in step 8 will be explained with reference to the flowchart of FIG. The "sampling" shown in FIG. 4 is based on the number setting function of the control means 103.

<Stenop 8A> Processing liquid is made to flow in the lube 10 (the six-way solenoid valve 5 is in the position indicated by the solid line; see the description of the steno knob 6).

<Step 8B> The six-way solenoid valve 5 is switched to the position shown by the dotted line.

<Step 8C> The processing liquid filled in the loop 10 is passed through the paths 21 and 23.
through the reaction cell 25.

<Step 8D> The number of samplings set in the steno knob I is
It is detected whether or not the number of samplings shown in steps 8A to 8C has been reached. If the number of samplings is less than the set number, the process proceeds to step 8E, and if it has been reached, the process proceeds to step 8F.

<Step gE> Switch the six-way solenoid valve 5 to the position shown by the solid line, and
Repeat steps 88-8C.

Step 8F> The stenops 8A~
When the sampling number indicated by 8C is reached, pure water is supplied into the reaction cell 25 following the processing liquid, and the redox electrode 3
Adjust so that the tip of 0 is located below the liquid level.

Note that the operation is similar to that described above when supplying the processing liquid into the reaction cell 26. At this time, the three-way solenoid valve 24 is switched, and the processing liquid is supplied to the reaction cell 26 through the paths 21 and 22.
You will be guided inside.

Next, the "analysis" shown in step 9 will be explained with reference to FIG. The "analysis" shown in FIG. 5 is based on the dropping amount setting function of the control means 103.

Kustenop 9A> The redox potential inside the reaction cell 25 is measured by the redox electrode 30, and the measured value is V. shall be.

Knob 9B> Titration bombs 28B and 29B are driven to drip the reagent into the reaction cell 25.

In addition, when supplying a fixed amount of the reagent, for example, the titration pump 28B is operated for a fixed period of time.

In addition, the titration pump 29B controls the titration amount by changing the potential, and at this time, the amount of dripping jl per 1a (=
a. ) is performed using a standard one, and when the titration approaches the end point, the amount of the drop is reduced to a small amount (see the explanation of Stesob 1). Step 9C> The redox potential inside the reaction cell 25 is measured by the redox electrode 30, and the measured value is defined as 1.

Kustenop 9D> The redox potential V, detected by Kustenop 9C is 1o00 [
■] Determine whether or not the above is true, and if YES, Stenobu 9J
If the answer is No, the process proceeds to step 9E.

Difference in redox potential 1v, -v. If l is 10[:V) or more and it is determined that the amount of change has become large, proceed to step 9F, and if l is less than 10[V) and it is determined that the amount of change remains small. Step 9■
Proceed to.

<Step 9F> The titration pumps 28B and 29B are driven to drip the reagent into the reaction cell 25.

Note that the dropping amount (1a,) per drop at this time is set to be smaller than the dropping amount described in step 9A since the end point of titration is near.

<Step 9G> The redox potential inside the reaction cell 25 is measured by the redox electrode 30, and the measured value is set as V.

<Step 9H> The redox potential V detected in step 9G is 1000 [
■] Determine whether or not the above is true, and if YES, step 9J
If the answer is No, the process returns to step 9F.

<Step 91> The redox potential ■1 detected using Stenobu 9C is ■.

shall be.

<Stenob 9J> As shown in Steps 9D and 9H, the amount of reagent dripped is calculated based on the output data of the titration pumps 27B to 29B when the redox potential V1.V is 1000 [V] or more. , From this, the sulfuric acid concentration and hydrogen peroxide concentration in the treatment liquid are calculated.

Here, the settings of (1), (2), and (1v, -vg) may be arbitrarily changed depending on the analysis conditions.

Kustenop 9K> The calculated value obtained in step 9J is output to the display panel 105 and displayed.

As explained in detail above, according to the automatic liquid management device shown in this embodiment, (1) the control means 103 is provided with a number setting function that can arbitrarily set the number of times the processing liquid is sampled by the sampling means 100; Therefore, by increasing or decreasing the number of samplings, the sampling (total) M of the processing liquid introduced into the reaction cells 25 and 26 can be freely increased or decreased.
In addition, by setting the sampling frequency to a large value, it is possible to analyze a small amount of processing liquid (sampling amount,
In other words, if the number of times is large, trace analysis becomes possible)
.

(2) Since a display panel 105 is provided that displays the operating status of the device based on the control results by the control means 103, the operator can directly check the operating status of the device by referring to the display panel 105. It is possible to understand. .

(3) Since the control means 103 is provided with a drip amount setting function that sets the amount of each drop by the titration means 101 to be smaller near the end point based on the potential change, the titration can be performed for a short time. It is possible to do this efficiently.

In addition, in this example, "sampling 1" shown in FIG.
, I made them perform the "analysis" shown in Figure 5 together, but
Either one is fine.

"Effects of the Invention" As explained in detail above, according to the first invention, the number of sampling times can be arbitrarily set and the (total) amount of sampling can be freely increased or decreased.
and setting the sampling number to a large value,
This makes it possible to analyze minute amounts of processing liquid.

According to the second invention, the operator can directly grasp the operating status of the apparatus by referring to the output means that displays the operating status of the apparatus.

According to the third invention, the amount of each drop dropped by the titration means can be set to be small near the end point based on the potential change, and titration can thereby be performed efficiently in a short time.

[Brief explanation of drawings]

1(A) to 5 show an embodiment of the present invention, FIG. 1(A) is an overall schematic configuration diagram, and FIG. 1(B) is an overall schematic configuration diagram.
1 is a diagram showing a control device, and FIGS. 2 to 5 are flowcharts showing control contents of the control device. 100... Sampling means 101... Titration means 102... Discharge means 103... Control means 104... Input means

Claims (3)

[Claims] (1) Sampling means for sampling the processing liquid;
An automatic liquid solution comprising a titration means for determining the amount of active ingredient in a sampled treatment liquid from a potential change and titration, a control means for controlling each of the above-mentioned means, and an input means for giving various commands to the control means. The automatic liquid management device, wherein the control means is provided with a number setting function that allows the sampling means to arbitrarily set the number of times the processing liquid is sampled based on a command from the input means. . (2) sampling means for sampling the processing liquid;
Titration means for determining the amount of active ingredient in the sampled treatment liquid from potential changes and titration; Control means for controlling each of the means; and Displaying the operating status of the device and the treatment status based on the control results of the control means. An automatic liquid management device characterized in that it is equipped with an output means. (3) sampling means for sampling the processing liquid;
An automatic liquid solution comprising a titration means for determining the amount of active ingredient in a sampled treatment liquid from a potential change and titration, a control means for controlling each of the above-mentioned means, and an input means for giving various commands to the control means. In the control device, the control means is provided with a drip amount setting function for setting the drip amount per drop by the titration means to be smaller near an end point based on a potential change based on a command from the input means. An automatic liquid management device characterized by: