Patent Publication Number: US-2023142129-A1

Title: Dilute solution production apparatus

Description:
TECHNICAL FIELD 
     The present invention relates to a dilute solution production apparatus for producing a dilute solution of a substance such as a conductivity-imparting substance or an oxidation-reduction potential regulating substance by adding a small amount of a second liquid containing the substance to a first liquid such as ultrapure water. 
     RELATED ART 
     As a cleaning solution used for wafer processing in the electronic industry field, a solution obtained by adding a conductivity-imparting substance or an oxidation-reduction potential regulating substance to ultrapure water is used. 
     At that time, the conductivity-imparting substance or the oxidation-reduction potential regulating substance is added to the ultrapure water by a pump (Patent Documents 1 and 2). 
     In the case where the conductivity-imparting substance or the oxidation-reduction potential regulating substance is a substance that easily vaporizes, bubbles of the substance tend to accumulate in the pump. Particularly, a pump with an extremely low flow rate is vulnerable to clogging by bubbles, and when the bubbles accumulate, the pump becomes less able to discharge at a constant amount. 
     PRIOR-ART DOCUMENTS 
     Patent Documents 
     Patent Document 1: Japanese Patent Laid-open No. 2018-171610 
     Patent Document 2: Japanese Patent Laid-open No. 2018-206998 
     SUMMARY OF THE INVENTION 
     Problems to Be Solved by the Invention 
     The present invention aims to provide a dilute solution production apparatus in which a trace amount of a second liquid containing a conductivity-imparting substance or an oxidation-reduction potential regulating substance is added to a first liquid such as ultrapure water, and a dilute solution having a specified concentration can be stably produced. 
     Means for Solving the Problems 
     A dilute solution production apparatus according to a first invention produces a dilute solution of a second liquid containing at least one of a conductivity-imparting substance and an oxidation-reduction potential regulating substance by adding the second liquid to a first liquid. The dilute solution production apparatus is characterized by including: a first pipe through which the first liquid flows; a pump adding the second liquid into the first pipe via a second pipe; a degassing mechanism extending from the pump; a water quality detector composed of a conductivity meter, a resistivity meter, or an oxidation-reduction potential meter, provided downstream of a connection part in the first pipe with the second pipe; and a degassing mechanism control part operating the degassing mechanism when a water quality detection value of the water quality detector varies by a predetermined value or more. 
     A dilute solution production apparatus according to a second invention produces a dilute solution of a second liquid containing at least one of a conductivity-imparting substance and an oxidation-reduction potential regulating substance by adding the second liquid to a first liquid. The dilute solution production apparatus is characterized by including: a first pipe through which the first liquid flows; a pump adding the second liquid into the first pipe via a second pipe; a degassing mechanism extending from the pump; a flowmeter provided downstream of the pump in the second pipe; and a degassing mechanism control part operating the degassing mechanism when a detection value of the flowmeter varies by a predetermined value or more. 
     In one aspect of the present invention, a tank storing the second liquid is provided, and the second pipe is connected to the tank. The degassing mechanism includes a degassing pipe for guiding the second liquid mixed with a gas from the pump to the tank, and a valve provided in the degassing pipe. The control part controls opening and closing of the valve. 
     In the present invention, examples of the conductivity-imparting substance and the oxidation-reduction potential regulating substance include, but are not limited to, ammonia, carbon dioxide, hydrogen peroxide, and ozone. 
     Effects of the Invention 
     According to the dilute solution production apparatus of the present invention, in the case where a gas accumulates in the pump for adding the second liquid to the first liquid such as ultrapure water, a discharge amount of the pump decreases, or the conductivity, resistivity or oxidation-reduction potential of the dilute solution accordingly varies by a predetermined value or more from a stable value up to that point, the degassing mechanism is operated to degas the pump, and the discharge amount of the pump is restored. Accordingly, it is possible to stably supply a dilute solution having a specified concentration. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG.  1    is a configuration diagram of a dilute solution production apparatus according to an embodiment. 
         FIG.  2    is a configuration diagram of a dilute solution production apparatus according to another embodiment. 
         FIG.  3    is a configuration diagram of a dilute solution production apparatus according to a comparative example. 
     
    
    
     DESCRIPTION OF THE EMBODIMENTS 
     Embodiments are described below with reference to the drawings. 
       FIG.  1    shows an embodiment of a first invention. 
     Ultrapure water as a first liquid is supplied to a use point via a first pipe  1  having a flowmeter  2  and a valve  3 . In the middle of this operation, a second liquid in a tank  4  is added via a second pipe  5 , a pump  6  and a flow regulating valve  7 . A degassing pipe  8  is provided so as to return, to the tank  4 , the second liquid that contains a gas generated by the pump  6 . A degassing valve  9  is provided in the degassing pipe  8 . The degassing valve  9  may be provided in the middle of the degassing pipe  8 , or may be provided at an upstream end or a downstream end thereof. 
     A solution of the aforementioned conductivity-imparting substance or oxidation-reduction potential regulating substance is stored in the tank  4 . 
     A water quality sensor  11  as a water quality detector composed of a conductivity meter, a resistivity meter, or an oxidation-reduction potential meter (ORP meter) is provided downstream of a connection part (confluence part) in the first pipe  1  with the second pipe  5 . A detection signal of the water quality sensor  11  is input to a control device (in this embodiment, a programmable logic controller (PLC))  12 . The pump  6 , the flow regulating valve  7  and the degassing valve  9  are controlled by the control device  12 . 
     In the dilute solution production apparatus configured in this way, in a steady state, the ultrapure water flows in the first pipe  1  at a constant flow rate, the second liquid flows in the second pipe  5  at a constant flow rate, and a dilute solution to which the second liquid is added so as to obtain a specified concentration is supplied to the use point. 
     When a gas separated from the second liquid, such as ammonia, carbon dioxide, hydrogen peroxide, or ozone, or a gas such as air, accumulates in the pump  6 , a discharge amount of the pump  6  decreases, and a detection value of the sensor  11  varies by a predetermined value or more (for example, 5% or more) from a stable value (value according to a target value) up to that point. In such a case where a water quality variation is detected, the control valve  12  opens the degassing valve  9  for a predetermined time, returns the second liquid mixed with the gas from the pump  6  to the tank  4 , and returns the degassing valve  9  to a closed state after passage of the predetermined time. Accordingly, the discharge amount of the pump  6  returns to a steady-state amount, and ultrapure water containing the second liquid having the specified concentration is supplied to the use point. 
     In the above description, a case where a sensor detection value varies by 5% or more is described as an example. However, the present invention is not limited thereto. As a variation value of the sensor detection value, a value selected from a range of normally 1% to 10%, particularly 3% to 7%, may be adopted. The same applies to a flowmeter  13  according to an embodiment of a second invention to be described next. 
       FIG.  2    shows an embodiment of a second invention. In this embodiment, the flowmeter  13  is disposed downstream of the pump  6  in the second pipe  5  (in this embodiment, downstream of the flow regulating valve  7 ). A detection signal of the flowmeter  13  is input to the control device  12 . 
     In the case where a flow rate detected by the flowmeter  13  varies by 5% or more from a stable value up to that point, the control device  12  opens the degassing valve  9  for a predetermined time for degassing. Other configurations and effects are the same as in  FIG.  1   , and the same reference numerals indicate the same portions. 
     Also in this embodiment, ultrapure water containing the second liquid having a specified concentration is stably supplied to the use point. 
     EXAMPLES 
     Examples and comparative examples are described below. 
     Example 1 
     By use of the dilute solution production apparatus shown in  FIG.  1   , a 29% NH 3  solution was supplied from the tank  4  by the pump  6 , added to ultrapure water in the pipe  1  that passed at 60 L/min, and a solution having a conductivity of 3 μS/cm was prepared. The sensor  11  used was a conductivity meter. At the moment when the conductivity dropped by 5% from a set value, the degassing valve was opened for 5 seconds for degassing, and then the degassing valve  9  was closed to return to a normal state. This test was continued for 30 days during which the conductivity detected by the conductivity meter  11  never decreased by 10% or more from the set value. 
     Example 2 
     The operation was performed in the same manner as in Example 1 except that a 29% NH 3  solution was added so as to obtain a conductivity of 1500 μS/cm. This test was continued for 30 days during which the conductivity detected by the conductivity meter  11  never decreased by 10% or more from the set value. 
     Example 3 
     The operation was performed in the same manner as in Example 1 except that the ultrapure water was passed at 3 L/min. This test was continued for 30 days during which the conductivity detected by the conductivity meter  11  never decreased by 10% or more from the set value. 
     Example 4 
     By use of the dilute solution production apparatus shown in  FIG.  2   , a  29 % NH 3  solution was added at the same ultrapure water flow rate (60 L/min) and target conductivity (3 μS/cm) as in Example 1. 
     In Example 4, at the moment when the flow rate was detected to be 0 by the flowmeter  13 , the degassing valve  9  was controlled to open for 5 seconds for degassing, and then the degassing valve  9  was controlled to close to return to the normal state. This test was continued for 30 days during which the conductivity detected by the conductivity meter  11  never decreased by 10% or more from the set value. 
     Example 5 
     By use of the apparatus of  FIG.  1   , the liquid in the tank  4  was set as a 60% H 2 O 2  solution, the ultrapure water flow rate was set to 60 L/min, an oxidation-reduction potential meter was used as the sensor  11 , and H 2 O 2 -containing ultrapure water having an H 2 O 2  concentration of 0.5 ppb was supplied to the use point. At the moment when an oxidation-reduction potential detected by the oxidation-reduction potential meter  11  dropped by 5% from the set value, the degassing valve  9  was controlled to open for 5 seconds for degassing, and then the degassing valve  9  was controlled to close to return to the normal state. 
     This test was continued for 30 days during which the oxidation-reduction potential detected by the oxidation-reduction potential meter  11  never decreased by 10% or more from the set value. 
     Example 6 
     The operation was performed in the same manner as in Example 5 except that H 2 O 2  was added so that the H 2 O 2  concentration in the ultrapure water was 1000 ppb. This test was continued for 30 days during which the oxidation-reduction potential detected by the oxidation-reduction potential meter  11  never decreased by 10% or more from the set value. 
     Example 7 
     The operation was performed in the same manner as in Example 5 except that the ultrapure water flow rate was set to 3 L/min. This test was continued for 30 days during which the oxidation-reduction potential detected by the oxidation-reduction potential meter  11  never decreased by 10% or more from the set value. 
     Example 8 
     By use of the dilute solution production apparatus shown in  FIG.  2   , the operation was performed so as to supply ultrapure water having an H 2 O 2  concentration of 0.5 ppb at the same ultrapure water flow rate and target oxidation-reduction potential as in Example 5. In Example 8, at the moment when the flow rate was detected to be 0 by the flowmeter  13 , the degassing valve  9  was controlled to open for 5 seconds for degassing, and then the degassing valve  9  was controlled to close to return to the normal state. This test was continued for 30 days during which the oxidation-reduction potential detected by the oxidation-reduction potential meter  11  never decreased by 10% or more from the set value. 
     Comparative Examples 1 to 3 
     The operation was performed under the same conditions as in Examples 1 to 3 respectively except that an apparatus without the degassing pipe  8  and the valve  9  was used, as shown in  FIG.  3   . The time until the conductivity decreased by 10% of the set value was measured. The results are shown in Table 1. 
     Comparative Examples 4 to 6 
     The operation was performed under the same conditions as in Examples 5 to 7 respectively except that an apparatus without the degassing pipe  8  and the valve  9  was used, as shown in  FIG.  3   . The time until the H 2 O 2  concentration decreased by 10% of the set value was measured. The results are shown in Table 1. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                 Ultrapure 
                   
                 Set 
                   
                 Time until 
               
               
                   
                   
                 water flow 
                 Second 
                 conductivity or 
                   
                 deviating 
               
               
                   
                 Apparatus 
                 rate 
                 liquid 
                 concentration 
                 Degassing 
                 from ±10% 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Example 1 
                 FIG. 1 
                 60 L/min 
                 29% NH 3   
                 Conductivity of 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                 3 μS/cm 
                   
                 days or more 
               
               
                 Example 2 
                 FIG. 1 
                 60 L/min 
                 29% NH 3   
                 Conductivity of 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                 1500 μS/cm 
                   
                 days or more 
               
               
                 Example 3 
                 FIG. 1 
                  3 L/min 
                 29% NH 3   
                 Conductivity of 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                 3 μS/cm 
                   
                 days or more 
               
               
                 Example 4 
                 FIG. 2 
                 60 L/min 
                 29% NH 3   
                 Conductivity of 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                 3 μS/cm 
                   
                 days or more 
               
               
                 Example 5 
                 FIG. 1 
                 60 L/min 
                 60% H 2 O 2   
                 H 2 O 2  0.5 ppb 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                   
                   
                 days or more 
               
               
                 Example 6 
                 FIG. 1 
                 60 L/min 
                 60% H 2 O 2   
                 H 2 O 2  1000 ppb 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                   
                   
                 days or more 
               
               
                 Example 7 
                 FIG. 1 
                  3 L/min 
                 60% H 2 O 2   
                 H 2 O 2  0.5 ppb 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                   
                   
                 days or more 
               
               
                 Example 8 
                 FIG. 2 
                 60 L/min 
                 60% H 2 O 2   
                 H 2 O 2  0.5 ppb 
                 Yes 
                 None for 30 
               
               
                   
                   
                   
                   
                   
                   
                 days or more 
               
               
                 Comparative 
                 FIG. 3 
                 60 L/min 
                 29% NH 3   
                 Conductivity of 
                 No 
                 13 hr 
               
               
                 Example 1 
                   
                   
                   
                 3 μS/cm 
               
               
                 Comparative 
                 FIG. 3 
                 60 L/min 
                 29% NH 3   
                 Conductivity of 
                 No 
                 30 hr 
               
               
                 Example 2 
                   
                   
                   
                 1500 μS/cm 
               
               
                 Comparative 
                 FIG. 3 
                  3 L/min 
                 29% NH 3   
                 Conductivity of 
                 No 
                 17 hr 
               
               
                 Example 3 
                   
                   
                   
                 3 μS/cm 
               
               
                 Comparative 
                 FIG. 3 
                 60 L/min 
                 60% H 2 O 2   
                 H 2 O 2  0.5 ppb 
                 No 
                 38 hr 
               
               
                 Example 4 
               
               
                 Comparative 
                 FIG. 3 
                 60 L/min 
                 60% H 2 O 2   
                 H 2 O 2  1000 ppb 
                 No 
                 85 hr 
               
               
                 Example 5 
               
               
                 Comparative 
                 FIG. 3 
                  3 L/min 
                 60% H 2 O 2   
                 H 2 O 2  0.5 ppb 
                 No 
                 45 hr 
               
               
                 Example 6 
               
               
                   
               
            
           
         
       
     
     As is clear from Table 1, according to the present invention, ultrapure water containing NH 3  or H 2 O 2  at a specified dilute concentration can be stably supplied to the use point. 
     Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention. 
     The present application is based on Japanese Patent Application No. 2020-404474 filed on Mar. 13, 2020, which is incorporated by reference in its entirety. 
     DESCRIPTION OF REFERENCE NUMERALS 
     
         
           1 : first pipe 
           2 : flowmeter 
           4 : tank 
           5 : second pipe 
           6 : pump 
           7 : flow regulating valve 
           8 : degassing pipe 
           9 : degassing valve 
           11 : water quality sensor 
           12 : control device 
           13 : flowmeter