JP2008291312A - Substrate processing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate processing apparatus capable of preventing reduction in the concentration of a surfactant included in processing liquid caused by regeneration of the processing liquid. <P>SOLUTION: The substrate processing apparatus 1 is provided with: a storage tank 11 storing a processing liquid containing the surfactant; a processing mechanism 12 processing a substrate by the processing liquid; a first circulation mechanism 20 circulating the processing liquid in the storage tank 11 between the storage tank 11 and the processing mechanism 12; adsorption vessels 32, 33 with the inside parts packed with an adsorbent material adsorbing metal ions comprised in the processing liquid by substrate processing in the processing mechanism 12; a second circulation mechanism 34 feeding the processing liquid in the storage tank 11 into the adsorption vessels 32, 33 to be circulated, further recovering the circulated processing liquid from the adsorption vessels 32, 33 to the storage tank 11, and circulating the processing liquid between the storage tank 11, and the adsorption vessels 32, 33; and a feeding mechanism 70 feeding the surfactant to the processing liquid recovered from the processing liquid stored in the storage tank 11 or the processing liquid recovered from the adsorption vessels 32, 33 to the storage tank 11. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a storage tank for storing a processing liquid containing a surfactant, a processing means for processing a substrate with the processing liquid, and a processing liquid circulation for circulating the processing liquid between the storage tank and the processing means. And a substrate processing apparatus.

  In the process of manufacturing various substrates such as semiconductor (silicon) wafers, liquid crystal glass substrates, glass substrates for photomasks, and substrates for optical disks, various processing solutions such as an etching solution, a developing solution, and a cleaning solution are supplied to these substrates. There is a process to process.

  For example, the processing using the etchant (etching process) includes a storage tank that stores the etchant, a substrate processing mechanism that etches the substrate, and an etchant in the storage tank that is supplied to the substrate processing mechanism. This is carried out by an etching apparatus provided with an etching processing circulation mechanism that collects the substrate from the substrate processing mechanism and circulates an etching solution between the storage tank and the substrate processing mechanism (see Japanese Patent Laid-Open No. 2000-96264). .

  The substrate processing mechanism includes a processing chamber having a closed space, a plurality of transport rollers disposed in the processing chamber and transporting the substrate horizontally, and disposed in the processing chamber and etching toward the upper surface of the substrate. The etching circulation mechanism includes a supply pipe that connects the storage tank and each nozzle body, and a supply pump that supplies the etching liquid to each nozzle body via the supply pipe And a recovery pipe connecting the bottom of the processing chamber and the storage tank.

  And in this etching apparatus, the etching liquid in the storage tank supplied to each nozzle body via the supply pipe by the supply pump is directed from the nozzle body toward the upper surface of the substrate conveyed in a predetermined direction by the conveyance roller. The substrate is etched by such an etchant. Note that the etching solution discharged onto the upper surface of the substrate is recovered from the processing chamber into the storage tank through the recovery tube.

  By the way, for example, when etching is performed on a metal film such as an indium tin oxide film formed on the upper surface of the substrate, the metal such as indium and tin constituting the metal film is dissolved in the etching liquid, so that the etching liquid is stored. In the etching apparatus configured to circulate between the tank and the substrate processing mechanism, the metal component contained in the etching solution in the storage tank gradually increases, and the etching process cannot be performed efficiently. There arises a problem and a problem that an accurate etching shape cannot be obtained.

  Therefore, in the above etching apparatus, the etching solution in the storage tank must be periodically replaced, and the processing is performed at the cost of replacing the etching solution (the disposal cost of the replaced etching solution and the purchase cost of the etching solution to be replaced). Cost increases.

  Accordingly, the applicant of the present application has proposed an etching apparatus that can remove a metal component in the etching solution and regenerate the etching solution (Japanese Patent Application No. 2007-101392). In addition to the structure of the etching apparatus, the etching apparatus supplies an adsorbing tower filled with a chelating material that adsorbs metal ions in the etching solution, and supplies the etching solution in the storage tank to the adsorption tower for circulation. At the same time, it further includes a removal processing circulation mechanism that collects the circulated etching solution from the adsorption tower and circulates the etching solution between the storage tank and the adsorption tower.

  In the etching apparatus according to the applicant's proposal, the etching solution is circulated between the storage tank and the adsorption tower by the removal processing circulation mechanism, so that the metal ions ( Since the metal dissolved in the etching solution is adsorbed and removed, the above-mentioned problems are prevented.

JP 2000-96264 A

  However, the etching apparatus according to the above-mentioned proposal by the applicant of the present application also has the following problems. That is, a surfactant may be added to the etching solution to prevent residues after etching. In such a case, when the etching solution in the storage tank is supplied to the adsorption tower, This surfactant is adsorbed to the chelate material together with the metal component, and the concentration of the surfactant contained in the etching solution is lowered. When the surfactant concentration is lower than a certain reference concentration, it is impossible to prevent the generation of residues.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a substrate processing apparatus capable of preventing the concentration of the surfactant contained in the processing liquid from being lowered due to the regeneration of the processing liquid. To do.

To achieve the above object, the present invention provides:
A storage tank for storing a processing liquid containing a surfactant, a processing means for processing a substrate with the processing liquid, a processing liquid stored in the storage tank is supplied to the processing means, and the supplied processing liquid is supplied A substrate processing apparatus comprising a first processing liquid circulating means for recovering from the processing means to the storage tank and circulating a processing liquid between the storage tank and the processing means,
An adsorption container filled with an adsorbent that adsorbs metal ions that are included in the treatment liquid by the substrate treatment in the treatment means;
The processing liquid stored in the storage tank is supplied and distributed in the adsorption container, and the distributed processing liquid is recovered from the adsorption container to the storage tank and processed between the storage tank and the adsorption container. A second processing liquid circulating means for circulating the liquid;
A substrate processing apparatus comprising: a supply unit configured to supply the surfactant to the processing liquid stored in the storage tank or the processing liquid recovered from the adsorption container to the storage tank.

  According to this invention, the processing liquid in the storage tank containing the surfactant is circulated between the storage tank and the processing means by the first processing liquid circulating means, and the processing means uses the processing liquid to circulate the substrate. Are appropriately processed. Further, the processing liquid in the storage tank is circulated between the storage tank and the adsorption container by the second processing liquid circulation means, and in the adsorption container, the processing in the processing means is performed by the adsorbent filled therein. In the process, metal ions (metal dissolved in the treatment liquid) that are contained in the treatment liquid are adsorbed and removed.

  When the processing liquid is supplied into the adsorption container, the surfactant in the processing liquid is adsorbed and removed together with the metal component on the adsorbent, but the surfactant is removed from the processing liquid or the adsorption container in the storage tank by the supply means. It is supplied to the processing liquid collected in the storage tank, and this prevents a decrease in the concentration of the surfactant contained in the processing liquid in the storage tank.

  Even if the processing liquid is always supplied to the inside of the adsorption container while processing the substrate by the processing means, for example, when the elapsed time from the start of the substrate processing reaches a predetermined time. Alternatively, the processing liquid may be supplied for a predetermined time when the number of processed substrates reaches a predetermined number, or when the concentration of metal ions contained in the processing liquid in the storage tank exceeds a predetermined concentration. However, it is not limited to such an aspect.

  In addition, when the processing liquid is constantly supplied into the adsorption container, the surfactant may be supplied at a constant amount, for example, when the elapsed time from the start of the substrate processing reaches a predetermined time. Alternatively, a certain amount may be supplied when the number of processed substrates reaches a predetermined number, or when the concentration of the surfactant contained in the processing liquid in the storage tank falls below a predetermined concentration. On the other hand, when the elapsed time from the start of substrate processing reaches a predetermined time or when the number of processed substrates reaches a predetermined number, the concentration of metal ions contained in the processing liquid in the storage tank exceeds the predetermined concentration. In the case where the processing liquid is supplied into the adsorption container, for example, when the processing liquid is supplied into the adsorption container, a certain amount of the surfactant is preferably supplied. However, it is not limited to such an aspect.

  Thus, according to the substrate processing apparatus of the present invention, the concentration of the surfactant contained in the processing liquid in the storage tank is higher than the constant reference concentration even if the processing liquid is supplied into the adsorption container and regenerated. It can prevent becoming low. Thereby, it is possible to prevent a problem in substrate processing (for example, a defective product is produced) due to a decrease in the surfactant concentration.

  In addition, by regenerating the treatment liquid, it is possible to extend the life of the treatment liquid and extend its replacement cycle. Therefore, the treatment liquid can be saved without purchasing new treatment liquids or discarding spent treatment liquids. Therefore, the substrate processing can be performed continuously without stopping for the replacement of the processing liquid and the cost for the substrate processing can be kept low. In addition, it is possible to reduce the amount of processing liquid to be disposed of and to require a new processing liquid only for the amount reduced by the substrate processing, which can contribute to environmental protection.

  The substrate processing apparatus includes at least two adsorption containers and control means for controlling the operation of the second processing liquid circulating means, and the second processing liquid circulating means is configured to perform processing in the storage tank. A treatment liquid supply pipe for supplying a liquid to each adsorption container, a treatment liquid recovery pipe for collecting the treatment liquid flowing through each adsorption container in the storage tank, and a treatment liquid supply pipe are provided. And a first switching valve for controlling the supply of the processing liquid to each adsorption container, and the first switching valve selectively supplies the processing liquid to any one of the adsorption containers. The control means may be configured to perform switching control of the first switching valve.

  If it does in this way, while the processing liquid in a storage tank will be selectively supplied with respect to any one of adsorption containers via a processing liquid supply pipe by the 2nd processing liquid circulation means, After the circulation, it is collected in the storage tank via the treatment liquid recovery pipe and circulated between the storage tank and the adsorption container. At this time, the adsorption container to which the processing liquid is supplied is changed to another adsorption container by switching the first switching valve, for example, when the controller determines that the adsorbent has reached a substantially saturated state. . Thereby, the adsorption | suction capability of the adsorbent in an adsorption | suction container can be maintained constant, and a metal component can be removed efficiently. When the adsorption container to which the processing liquid is supplied is switched, the adsorption container in which the supply of the processing liquid is stopped is appropriately regenerated using an eluent that elutes the metal adsorbed by the adsorbent. .

  Further, the substrate processing apparatus is provided in an eluent supply pipe for supplying an eluent for eluting the metal adsorbed by the adsorbent of each adsorption container to each adsorption container, and the eluent supply pipe, A second switching valve for controlling the supply of the eluent to each adsorption vessel, and the second switching valve selectively supplies the eluent to any one of the adsorption vessels. Liquid supply means, and eluent recovery means for recovering the eluent flowing through each of the adsorption containers, and the control means controls the second switching valve when the first switching valve is switched. The supply of the processing liquid may be stopped, and the eluent may be supplied to an adsorption container in a state where the adsorbent has adsorbed metal ions.

  In this way, when the adsorption container to which the processing liquid is supplied is switched, the second switching valve is controlled by the control means, and the elution liquid is supplied to the adsorption container where the supply of the processing liquid is stopped. The metal (metal ions) adsorbed on the adsorbent in the adsorption container is eluted by this eluent, and the eluent containing the eluted metal ions is recovered by the eluent recovery means. Thereby, the adsorbent can be regenerated. In addition, some metals dissolved in the treatment liquid are very expensive, and it is convenient if they can be recovered. However, by appropriately collecting metal ions in the eluent, the metal dissolved in the treatment liquid can be recovered. Can be effectively recovered.

  The substrate processing apparatus is provided in the cleaning liquid supply pipe for supplying a cleaning liquid for cleaning the inside of each adsorption container to each of the adsorption containers, and the cleaning liquid supply pipe, and the cleaning liquid is supplied to each of the adsorption containers. A third switching valve for controlling supply, and a cleaning liquid supply means for selectively supplying the cleaning liquid to any one of the adsorption containers by the third switching valve; A cleaning liquid discharge pipe for discharging the cleaning liquid to the outside, and when the control means finishes supplying the eluent, the control means controls the third switching valve so that the adsorbing container after the eluent is supplied The cleaning liquid may be supplied.

  In this way, when the elution of the metal adsorbed on the adsorbent is completed, the third switching valve is controlled by the control means, and the cleaning liquid is supplied to the adsorption container after the eluent is supplied. The inside of the adsorption container is cleaned by this cleaning liquid, and this cleaning liquid is discharged to the outside from the cleaning liquid discharge pipe. If the eluent remains in the adsorption container, the treatment liquid and the eluent may be mixed when the treatment liquid is supplied into the adsorption container, which may adversely affect the substrate processing in the processing means. By supplying the cleaning liquid after the supply of the eluent, it is possible to prevent the inconvenience caused by washing away the eluent remaining in the adsorption container.

  The control means may be configured to switch the first switching valve at a preset time interval. If it does in this way, the 1st change-over valve will be switched by the control means at the predetermined time interval (at the time interval presumed that the adsorbent of the adsorption container reaches a substantially saturated state), and the adsorption to which the processing liquid is supplied The container is switched. Therefore, even if comprised in this way, the effect similar to the above can be acquired.

  The control means may be configured to count the number of substrates processed by the processing means, and to switch the first switching valve when the counted number reaches a preset number. . In this case, the first switching is performed by the control means when the number of processed substrates in the processing means reaches a predetermined number (when the number of adsorbents in the adsorption container is estimated to reach a substantially saturated state). The valve is switched, and the adsorption container to which the processing liquid is supplied is switched. Therefore, even if comprised in this way, the effect similar to the above can be acquired.

  The substrate processing apparatus further includes a first detection unit that detects a concentration of metal ions contained in the processing liquid stored in the storage tank, and the control unit detects the concentration detected by the first detection unit. May be configured to switch the first switching valve when becomes higher than a preset reference value. In this way, the adsorbent in the adsorption container reaches a substantially saturated state, the adsorption capacity thereof decreases, the concentration of metal ions contained in the treatment liquid in the storage tank increases, and is detected by the first detection means. When the concentration becomes higher than a predetermined reference value, the first switching valve is switched, and the adsorption container to which the processing liquid is supplied is switched.

  Therefore, even if comprised in this way, the effect similar to the above can be acquired. In addition, since the amount of metal dissolved in the processing liquid varies depending on the processing content and processing conditions in the processing means, it is difficult to set the time until the adsorbent in the adsorption container reaches a substantially saturated state and the number of processed sheets. If the switching control of the 1 switching valve is performed based on the concentration of metal ions contained in the treatment liquid in the storage tank, this switching control can be performed with higher accuracy.

  The substrate processing apparatus includes: a second detection unit that detects a concentration of the surfactant contained in the processing liquid stored in the storage tank; and the supply unit based on the concentration detected by the second detection unit. A control means for controlling the operation of the control liquid to bring the concentration of the surfactant contained in the treatment liquid into a preset concentration, or the substrate processing apparatus further comprises the second detection means, The control means is configured to control the operation of the supply means based on the concentration detected by the second detection means so that the concentration of the surfactant contained in the processing liquid is set to a preset concentration. May be.

  In this case, the supply means is controlled by the control means based on the concentration detected by the second detection means, and the concentration of the surfactant contained in the processing liquid is maintained at a predetermined concentration. The concentration of the active agent can be controlled with high accuracy. In addition, depending on the type of surfactant added to the treatment liquid, the type of adsorbent filled in the adsorption container, the amount of metal adsorbed on the adsorbent, the surface activity adsorbed on the adsorbent Since the amount of the agent changes, it is difficult to set the amount of the surfactant to be supplied by the supply means. However, if the supply means is controlled based on the detected concentration by the second detection means, the surface activity in the treatment liquid The agent concentration can always be the optimum concentration.

  As the substrate, for example, a semiconductor (silicon) wafer, a liquid crystal glass substrate, a photomask glass substrate, an optical disk substrate, etc. are adsorbed, and as the processing liquid, for example, an etching solution, a developing solution, a cleaning solution, etc. are adsorbed. Examples of the metal to be adsorbed by the adsorbent in the container include indium, and examples of the adsorbent include, but are not limited to, a chelate material and an ion exchange resin. When a chelating material is used as the adsorbent, hydrochloric acid, sulfuric acid or caustic soda can be used as the eluent, and pure water or the like can be used as the cleaning liquid. When an ion exchange resin is used as the adsorbent, Hydrochloric acid or sodium hydroxide can be used as the eluent, and pure water or the like can be used as the cleaning liquid. Examples of the surfactant include naphthalene sulfonic acid formaldehyde condensates and salts thereof, polysulfonic acid compounds such as polystyrene sulfonic acid and salts thereof, lignin sulfonic acid and salts thereof, polyoxyethylene-polyoxypropylene block copolymers, dodecyl. Sulfonates such as alkylbenzene sulfonic acids such as benzene sulfonic acid and salts thereof, alkyl sulfate esters and salts thereof, dialkyl esters of sulfosuccinic acid and salts thereof, polyoxyethylene alkyl ether sulfonic acids and polyoxyethylene allyl ether sulfonic acids and salts thereof Type anionic surfactants, fluorinated nonionic surfactants such as perfluoroalkylethylene oxide and perfluoroalkenyl ethylene oxide, perfluoro And the like can be mentioned Luque sulfonic acids and salts thereof and perfluoro alkenyl carboxylic acids and fluorine-containing anionic surfactant such as a salt, but is not limited thereto.

  As described above, according to the substrate processing apparatus of the present invention, it is possible to prevent the concentration of the surfactant contained in the processing liquid from being lowered even when the processing liquid is regenerated. In addition, for example, problems such as production of defective products can be prevented.

  Hereinafter, specific embodiments of the present invention will be described with reference to the accompanying drawings. FIG. 1 is an explanatory diagram showing a schematic configuration of a substrate processing apparatus according to an embodiment of the present invention.

  As shown in FIG. 1, the substrate processing apparatus 1 of this example includes a storage tank 11 that stores an etching solution L, a substrate processing mechanism 12 that etches a substrate K with the etching solution L, a storage tank 11, and a substrate processing mechanism 12. The first circulation mechanism 20 that circulates the etchant L between the first and second components, the removal mechanism 30 that removes the metal dissolved in the etchant L, and the concentration of a specific component contained in the etchant L in the storage tank 11 are detected. The operation of the concentration sensor 65, the supply mechanism 70 for supplying a specific component to the etching solution L in the storage tank 11, the substrate processing mechanism 12, the first circulation mechanism 20, the removal mechanism 30, and the supply mechanism 70 is controlled. It is comprised from the control apparatus 25 grade | etc.,.

  In the storage tank 11, for example, an etching solution L adjusted so that oxalic acid and a surfactant each have a predetermined concentration is stored. Examples of the surfactant include naphthalenesulfonic acid formaldehyde condensate and salts thereof, polysulfonic acid compounds such as polystyrene sulfonic acid and salts thereof, lignin sulfonic acid and salts thereof, polyoxyethylene-polyoxypropylene block copolymers, and dodecylbenzene. Sulfonate types such as alkylbenzene sulfonic acid and its salts such as sulfonic acid, alkyl sulfate and its salt, dialkyl ester and its salt of sulfosuccinic acid, polyoxyethylene alkyl ether sulfonic acid and polyoxyethylene allyl ether sulfonic acid and their salts Anionic surfactants, fluorine-based nonionic surfactants such as perfluoroalkyl ethylene oxide and perfluoroalkenyl ethylene oxide, and perfluoroalkenes And the like can be mentioned Rusuruhon acid and fluorine-containing anionic surfactant such as a salt thereof and perfluoro alkenyl carboxylic acids and salts thereof, but is not limited thereto.

  In addition, one end side of a new liquid supply pipe 26 provided with a supply control valve 28 and one end side of a replenishment pipe 27 provided with a supply control valve 29 are connected to the storage tank 11. Connected to the other end of the supply pipe 26 is a supply device (not shown) for supplying the etching solution L to each storage tank 11 of the plurality of substrate processing apparatuses 1. Are connected to a supply device (not shown) provided in each of the supply device (not shown) or the substrate processing apparatus 1 for supplying the etching solution L into the storage tank 11. . Furthermore, in the storage tank 11, two liquid level detection sensors 66 and 67 for detecting the liquid level position of the etching liquid L are provided with an interval in the vertical direction.

  The substrate processing mechanism 12 is disposed in a processing chamber 13 having a closed space and a lower portion in the processing chamber 13, and horizontally supports, for example, a substrate K having an upper surface formed with an indium tin oxide film (metal film). A plurality of transport rollers 14 for transporting in a predetermined direction (arrow direction), a flow pipe 15 disposed in the upper part of the processing chamber 13 and through which the etchant L supplied by the first circulation mechanism 20 flows, A plurality of nozzle bodies 16 that are fixed to the flow pipe 15 and discharge the etching liquid L toward the upper surface of the substrate K conveyed by the conveying roller 14 are formed. The etching liquid L in the processing chamber 13 13 is discharged outside through a discharge port 13a formed on the bottom surface.

  The first circulation mechanism 20 has a supply pipe 21 having one end connected to the storage tank 11 and the other end connected to the flow pipe 15, and a supply pump that supplies the etching solution L into the flow pipe 15 through the supply pipe 21. 22, one end side is connected to the discharge port 13 a of the processing chamber 13, and the other end side is composed of a recovery pipe 23 connected to the storage tank 11.

  The removal mechanism 30 includes an adsorption mechanism 31 that adsorbs metal ions (indium ions and tin ions) that are dissolved in the etchant L by the etching process in the substrate processing mechanism 12 and are contained in the etchant L, and a storage mechanism. A second circulation mechanism 34 that circulates the etching liquid L between the tank 11 and the adsorption mechanism 31, and an eluent supply mechanism that supplies an eluent for eluting the metal (indium or tin) adsorbed by the adsorption mechanism 31. 42, an eluent recovery mechanism 48 that recovers the eluent from the adsorption mechanism 31, a cleaning liquid supply mechanism 54 that supplies a cleaning liquid for cleaning the adsorption mechanism 31, and a cleaning liquid recovery mechanism 58 that recovers the cleaning liquid from the adsorption mechanism 31. Is provided.

  The adsorption mechanism 31 includes two adsorption containers (a first adsorption container 32 and a second adsorption container 33) filled with a chelating material (not shown) as an adsorbent that adsorbs metal ions (indium ions and tin ions). Is provided. The chelating material (not shown) is a general term for organic aminocarboxylates, and adsorbs metal ions and elutes the adsorbed metal by a specific solution. It is equipped with. Specifically, EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), DTPA (diethylenetriaminepentaacetic acid), GLDA (L-glutamic acid diacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), GEDTA (glycol ether diamine tetraacetic acid) Acetic acid), TTHA (triethylenetetramine hexaacetic acid), HIDA (hydroxyethyliminodiacetic acid), DHEG (hydroxyethylglycine) and the like can be mentioned as examples, but are not limited thereto.

  The second circulation mechanism 34 has an etchant supply pipe 35 connected at one end side to the storage tank 11 and branched at the other end side and connected to the adsorption containers 32 and 33, and each adsorption container via the etchant supply pipe 35. A supply pump 36 for supplying the etchant L into the interiors of 32 and 33; an etchant recovery pipe 37 having one end connected to the storage tank 11 and the other end branched and connected to the adsorption vessels 32 and 33; and an etchant A first supply side switching valve 38 and a second supply side switching valve 39 provided on the other end side of the supply pipe 35 and a first discharge side switching valve 40 provided on the other end side of the etching solution recovery pipe 37, respectively. And a second discharge side switching valve 41.

  Each of the switching valves 38, 39, 40, 41 closes the second supply side switching valve 39 and the second discharge side switching valve 41 when the first supply side switching valve 38 and the first discharge side switching valve 40 are open. Thus, when the 2nd supply side switching valve 39 and the 2nd discharge side switching valve 41 are open, it is controlled by the control apparatus 25 so that the 1st supply side switching valve 38 and the 1st discharge side switching valve 40 may close. .

  In the second circulation mechanism 34, the etching liquid L in the storage tank 11 is selectively supplied to one of the adsorption containers 32 and 33 via the etching liquid supply pipe 35 by the supply pump 36. That is, when the first supply side switching valve 38 is opened and the second supply side switching valve 39 is closed, the first supply side switching valve 38 is closed and the second supply side switching valve 39 is opened in the first adsorption container 32. The etching solution L is supplied to the second adsorption container 33 when the operation is in progress. Then, the etching solution L supplied to one of the adsorption vessels 32 and 33 and circulated through the adsorption vessels 32 and 33 is collected in the storage tank 11 by the etching solution collection pipe 37.

  The eluent supply mechanism 42 includes, for example, an eluent supply unit 43 that supplies an eluent made of hydrochloric acid, sulfuric acid, or caustic soda, and one end connected to the eluent supply unit 43 and the other end branched to each adsorption vessel 32. , 33, an eluent supply valve 45 provided on one end side of the eluent supply pipe 44, and a first supply side switch provided on the other end side of the eluent supply pipe 44. It consists of a valve 46 and a second supply side switching valve 47.

  Each of the switching valves 46, 47 is configured such that the second supply side switching valve 47 is closed when the first supply side switching valve 46 is open, and the first supply side switching is performed when the second supply side switching valve 47 is open. It is controlled by the control device 25 so that the valve 46 is closed.

  The eluent recovery mechanism 48 includes an eluent recovery section 49 that recovers the eluent, and an eluent recovery pipe having one end connected to the eluent recovery section 49 and the other end branched and connected to the adsorption vessels 32 and 33. 50, a first discharge side switching valve 51 and a second discharge side switching valve 52 provided on the other end side of the eluent recovery pipe 50, and an eluent recovery valve provided on one end side of the eluent recovery pipe 50, respectively. 53.

  Each of the switching valves 51 and 52 is configured such that when the first discharge side switching valve 51 is open, the second discharge side switching valve 52 is closed, and when the second discharge side switching valve 52 is open, the first discharge side switching is performed. It is controlled by the control device 25 so that the valve 51 is closed.

  In the eluent supply mechanism 42 and the eluent recovery mechanism 48, the eluent is selectively supplied from the eluent supply unit 43 to one of the adsorption containers 32 and 33 via the eluent supply pipe 44. That is, when the first supply side switching valve 46 is opened and the second supply side switching valve 47 is closed, the first supply side switching valve 46 is closed and the second supply side switching valve 47 is opened in the first adsorption container 32. During the operation, the eluent is supplied to the second adsorption container 33. Then, the eluent supplied to one of the adsorption containers 32 and 33 and flowing through the adsorption containers 32 and 33 is recovered in the eluent recovery section 49 via the eluent recovery pipe 50.

  When the first supply side switching valve 46 is open, the first discharge side switching valve 51 is open, the second discharge side switching valve 52 is closed, and when the second supply side switching valve 47 is open. The second discharge side switching valve 52 is opened, and the first discharge side switching valve 51 is closed. Further, when the eluent supply unit 43 is driven, the eluent supply valve 45 and the eluent recovery valve 53 are opened.

  The cleaning liquid supply mechanism 54 includes, for example, a cleaning liquid supply unit 55 that supplies a cleaning liquid made of pure water, one end side connected to the cleaning liquid supply unit 55, and the other end side a branch portion of the eluent supply pipe 44 and an eluent supply valve 45. Are connected to each of the adsorption containers 32 and 33 via the eluent supply pipe 44, a cleaning liquid supply valve 57 provided in the cleaning liquid supply pipe 56, and the first supply side. It consists of a switching valve 46 and a second supply side switching valve 47.

  Each of the switching valves 46 and 47 is similar to the above in that the second supply-side switching valve 47 is closed when the first supply-side switching valve 46 is open, and the second supply-side switching valve 47 is opened. It is controlled by the control device 25 so that the 1 supply side switching valve 46 is closed.

  The cleaning liquid recovery mechanism 58 has a cleaning liquid recovery part 59 for recovering the cleaning liquid, one end side connected to the cleaning liquid recovery part 59, and the other end side connected between the branch part of the eluent recovery pipe 50 and the eluent recovery valve 53. The cleaning liquid recovery pipe (cleaning liquid discharge pipe) 60 connected to each of the adsorption containers 32 and 33 via the eluent recovery pipe 50, the first discharge side switching valve 51 and the second discharge side switching valve 52, and the cleaning liquid recovery The cleaning liquid recovery valve 61 is provided in the pipe 60.

  Each of the switching valves 51 and 52 is similar to the above in that the second discharge side switching valve 52 is closed when the first discharge side switching valve 51 is open, and the second discharge side switching valve 52 is open when the second discharge side switching valve 52 is open. It is controlled by the control device 25 so that the 1 discharge side switching valve 51 is closed.

  In the cleaning liquid supply mechanism 54 and the cleaning liquid recovery mechanism 58, the cleaning liquid is selectively supplied from the cleaning liquid supply unit 55 to one of the adsorption containers 32 and 33 via the cleaning liquid supply pipe 56 and the eluent supply pipe 44. That is, when the first supply side switching valve 46 is opened and the second supply side switching valve 47 is closed, the first supply side switching valve 46 is closed and the second supply side switching valve 47 is opened in the first adsorption container 32. The cleaning liquid is supplied to the second adsorption container 33 when it is in operation. The cleaning liquid supplied to one of the adsorption containers 32 and 33 and circulated through the adsorption containers 32 and 33 is recovered in the cleaning liquid recovery unit 59 via the eluent recovery pipe 50 and the cleaning liquid recovery pipe 60. .

  When the first supply side switching valve 46 is open, the first discharge side switching valve 51 is open, the second discharge side switching valve 52 is closed, and when the second supply side switching valve 47 is open. The second discharge side switching valve 52 is opened, and the first discharge side switching valve 51 is closed. Further, when the cleaning liquid supply unit 55 is driven, the cleaning liquid supply valve 57 and the cleaning liquid recovery valve 61 are opened.

  The concentration sensor 65 detects the concentrations of oxalic acid and surfactant contained in the etching solution L in the storage tank 11.

  The supply mechanism 70 includes a supply unit 71 for supplying oxalic acid and pure water into the storage tank 11, a supply pipe 72 having one end connected to the supply unit 71, and the other end connected to the storage tank 11, and a surfactant. The stored storage tank 73, one end side connected to the storage tank 73, the other end side connected to the storage tank 11, and the surfactant in the storage tank 73 in the storage tank 11 via the supply pipe 74. And a supply pump 75 for supplying.

  When the control device 25 controls the supply pump 22 to circulate the etching solution L between the storage tank 11 and the substrate processing mechanism 12 and operates the supply pump 22, the supply pump 36 and each switching valve are operated. 38, 39, 40 and 41 are controlled, and the adsorption containers 32 and 33 to which the etching solution L is supplied are set to a predetermined time interval, that is, the chelating material (not shown) in the adsorption containers 32 and 33 is substantially omitted. A process of supplying and circulating the etching liquid L in the storage tank 11 to either one of the adsorption vessels 32 and 33 while alternately switching at time intervals estimated to reach a saturated state, and an adsorption supplied with the etching liquid L When the containers 32 and 33 are switched, the eluent supply unit 43, the eluent supply valve 45, the eluent recovery valve 53 and the switching valves 46, 47, 51, 52 are controlled to switch the adsorption containers 32, 33. When the eluent is supplied to the adsorbing vessels 32 and 33 for which the supply of the rinsing liquid L has been stopped for a predetermined time and when the eluent is supplied for a predetermined time, the cleaning liquid supply unit 54, the cleaning liquid supply valve 57, the cleaning liquid recovery valve 61, and each switching The valve 46, 47, 51, 52 is controlled to execute a process of supplying the cleaning liquid to the same adsorption container 32, 33 as the adsorption container 32, 33 supplied with the eluent for a predetermined time.

  Further, the control device 25 further controls the supply unit 71 based on the concentration of oxalic acid detected by the concentration sensor 65, that is, supplies pure water or oxalic acid from the supply unit 71 into the storage tank 11, The supply pump 75 is controlled based on the treatment for maintaining the oxalic acid concentration of the etching solution L stored in the storage tank 11 within a certain range and the concentration of the surfactant detected by the concentration sensor 65, so that the storage tank 11 And a process of maintaining the surfactant concentration of the stored etching solution L within a certain range.

  Furthermore, the control device 25 is configured to supply the supply device (not shown), the replenishing device (not shown), the supply control valve 28, based on the liquid level position detected by the liquid level detection sensors 66 and 67. 29 is controlled to control the amount of the etching solution L stored in the storage tank 11.

  According to the substrate processing apparatus 1 of the present example configured as described above, first, the etching solution L is supplied to the storage tank 11 in a state where the etching solution L is not stored. Specifically, the supply device (not shown) and the supply control valve 28 are controlled by the control device 25, and the etching solution L is supplied until the liquid level of the etching solution L is detected by the upper liquid level detection sensor 66. The As a result, the inside of the storage tank 11 is filled with a predetermined amount of the etchant L.

  Next, the etching solution L stored in the storage tank 11 is supplied to each nozzle body 16 by the supply pump 22 via the supply pipe 21 and the flow pipe 15 and discharged from each nozzle body 16 toward the upper surface of the substrate K. Is done. Then, the etching liquid L discharged onto the upper surface of the substrate K flows through the collection pipe 23 from the discharge port 13a of the processing chamber 13 and is collected in the storage tank 11, and thus the etching liquid in the storage tank 11 is collected. L circulates between the storage tank 11 and the substrate processing mechanism 12.

  The substrate K is transported in a predetermined direction by the transport roller 14 and is etched by the etching solution L (oxalic acid in the etching solution L) discharged from each nozzle body 16. By this etching process, the indium tin oxide film of the substrate K is dissolved in the etching solution L, and the etching solution L contains indium ions and tin ions.

  The etching liquid L stored in the storage tank 11 is adsorbed by the supply pump 36 via the etching liquid supply pipe 35 while the adsorption containers 32 and 33 to be supplied are alternately switched at a preset time interval. In addition to being supplied to one of the containers 32 and 33, after flowing through the adsorption containers 32 and 33, it is collected in the storage tank 11 through the etching solution recovery pipe 37, and the storage tank 11 and the adsorption containers 32 and 33 are collected. Circulate between. As a result, indium ions and tin ions, which are metal components in the etching solution L, are adsorbed and removed by the chelating material (not shown) in the adsorption vessels 32 and 33, and the etching solution L is regenerated (to be reusable). )

  When the adsorption containers 32 and 33 to which the etching liquid L is supplied are switched, first, the adsorption containers 32 and 33 whose supply of the etching liquid L is stopped by this switching (from the first adsorption container 32 to the second adsorption container 33). When switched, the eluent passes from the eluent supply section 43 to the eluent supply pipe 44 through the first adsorption container 32 and from the second adsorption container 33 to the first adsorption container 32 when switched. The supplied eluent flows through the adsorption vessels 32 and 33 and is then recovered in the eluent recovery section 49 via the eluent recovery pipe 50. As a result, indium and tin adsorbed on the chelating material (not shown) of the adsorption vessels 32 and 33 are eluted by this eluent, and the eluent containing the eluted indium ions and tin ions is recovered in the eluent recovery unit 49. Is done.

  Thereafter, the cleaning liquid is supplied from the cleaning liquid supply unit 55 via the cleaning liquid supply pipe 56 and the elution liquid supply pipe 44 to the same adsorption containers 32 and 33 as the adsorption containers 32 and 33 to which the eluent is supplied. After being circulated through the adsorption containers 32 and 33, it is recovered in the cleaning liquid recovery unit 59 via the eluent recovery pipe 50 and the cleaning liquid recovery pipe 60. As a result, the eluent remaining in the adsorption containers 32 and 33 is washed away by the cleaning liquid.

  In this manner, the elution liquid and the cleaning liquid are sequentially supplied to the adsorption containers 32 and 33 from which the supply of the etching liquid L is stopped, and the adsorption containers 32 and 33 thereafter enter a standby state.

  During the etching process, the controller 25 controls the supply unit 71 based on the concentration of oxalic acid detected by the concentration sensor 65, and the oxalic acid concentration of the etchant L is controlled within a certain range. . Specifically, when the oxalic acid concentration detected by the concentration sensor 65 is higher than the predetermined range, pure water is supplied from the supply unit 71 via the supply pipe 72 into the storage tank 11, and is higher than the predetermined range. When it is low, oxalic acid is supplied into the storage tank 11 from the supply section 71 via the supply pipe 72, and the concentration of oxalic acid contained in the etching solution L is set within the predetermined range.

  Further, the etching solution L in the storage tank 11 is reduced by the etching process, but the controller 25 supplies the supply device (not shown) and the supply control valve 28 or the replenishment device (not shown) and the supply control valve 29. Is controlled, and the etching solution L is supplied into the storage tank 11. Specifically, when the liquid level of the etching liquid L is detected by the lower liquid level detection sensor 67, the etching liquid L is supplied until the liquid level of the etching liquid L is detected by the upper liquid level detection sensor 66. Is done. Thereby, the etching liquid L in the storage tank 11 is maintained at a constant amount.

  By the way, the chelating material (not shown) in the adsorption vessels 32 and 33 adsorbs not only the indium ions and tin ions in the etching solution L but also the surfactant contained in the etching solution L. When supplied into the adsorption containers 32 and 33, the surfactant in the etching solution L is removed together with indium ions and tin ions, and the concentration of the surfactant contained in the etching solution L is reduced.

  Therefore, in the substrate processing apparatus 1 of this example, the control device 25 controls the supply pump 75 based on the concentration of the surfactant detected by the concentration sensor 65, so that the etching liquid L stored in the storage tank 11 is adjusted. The concentration of the surfactant contained is maintained within a certain range. That is, the surfactant in the storage tank 73 is supplied into the storage tank 11 by an amount adsorbed and removed by the chelating material (not shown) by the supply pump 75 and is contained in the etching liquid L in the storage tank 11. A reduction in the concentration of the surfactant is prevented.

  Therefore, according to the substrate processing apparatus 1 of this example, the concentration of the surfactant contained in the etching liquid L in the storage tank 11 is constant even when the etching liquid L is circulated in the adsorption containers 32 and 33 and regenerated. Since lower than the range can be prevented, it is possible to prevent problems in the etching process due to a decrease in the concentration of the surfactant (for example, etching failure).

  In addition, by regenerating the etching solution L, the life of the etching solution L can be extended and the replacement cycle can be lengthened. Therefore, the purchase cost of the new etching solution L and the disposal cost of the used etching solution L can be reduced. It is possible to save the cost for the etching solution L and to perform the etching process continuously without stopping the replacement of the etching solution L, and to reduce the cost for the substrate processing. Moreover, since the etching solution L to be disposed of can be reduced, or the new etching solution L can be required only by the amount reduced by the etching process, it is possible to contribute to environmental protection. Furthermore, since the etching solution L is circulated in the adsorption vessels 32 and 33 at all times during the etching process, the concentration of indium ions and the concentration of tin ions contained in the etching solution L in the storage tank 11 are adjusted. The etching solution L can always be kept in the same state as a new one by always maintaining a low state below a certain level, and this can also prevent problems such as defective etching.

  Further, since the etching liquid L is circulated between the storage tank 11 and one of the adsorption containers 32 and 33 while switching the adsorption containers 32 and 33, a chelate material (not shown) in the adsorption containers 32 and 33 is shown. ) Can be maintained constant, indium ions and tin ions can be efficiently removed, and the concentration of indium ions and tin ions contained in the etching solution L can be suppressed to a certain level or less.

  Further, the supply of the etching solution L is stopped, and the elution solution is supplied into the adsorption vessels 32 and 33 in a state where the chelating material (not shown) has adsorbed the indium ions and tin ions, and contains the eluted indium ions and tin ions. The eluent is recovered in the eluent recovery unit 49. This chelating material (not shown) can be regenerated, and indium ions and tin ions are appropriately recovered from the eluent in the eluent recovery unit 49. Thus, indium (which is a very expensive metal) and tin dissolved in the etching solution L can be effectively recovered.

  In addition, since the cleaning liquid is supplied after the eluent is supplied and the eluent remaining in the adsorption containers 32 and 33 is washed away, the etching liquid L in the storage tank 11 is supplied into the adsorption containers 32 and 33. Sometimes, the etching solution L and the eluent remaining in the adsorption vessels 32 and 33 are mixed to change the components of the etching solution L, thereby effectively preventing adverse effects on the etching process in the substrate processing mechanism 12. Can do.

  In addition, since the oxalic acid concentration of the etching solution L stored in the storage tank 11 is controlled to be within a certain range, there is a disadvantage that the oxalic acid concentration of the etching solution L varies and a predetermined etching ability cannot be obtained. And the etching processing capacity can be maintained in an optimum state.

  As mentioned above, although one Embodiment of this invention was described, the specific aspect which this invention can take is not limited to this at all.

  In the above example, the removal mechanism 30 is provided with the eluent supply mechanism 42, the eluent recovery mechanism 48, the cleaning liquid supply mechanism 54, and the cleaning liquid recovery mechanism 58. However, the present invention is not limited to this, and is shown in FIG. As described above, these can be omitted. In this case, the removal mechanism 80 includes an adsorption mechanism 81 that adsorbs metal ions and a second circulation mechanism 85 that circulates the etchant L between the storage tank 11 and the adsorption mechanism 81 as shown in FIG. Become.

  The adsorption mechanism 81 is filled with the chelating material (not shown) and has a plurality of adsorption containers 82 configured to be portable, and a first attachment part to which the adsorption containers 82 are detachably attached. 83 and a second attachment portion 84. At the upper end of each adsorption vessel 82, a supply part (not shown) for supplying the etching solution L, the eluent, and the cleaning solution to the inside, and the etching supplied from the supply part (not shown) to the inside. A discharge part (not shown) for discharging the liquid L, the eluent, and the cleaning liquid to the outside is formed.

  The second circulation mechanism 85 has an etchant supply pipe 86 having one end connected to the storage tank 11 and the other end branched to be connected to a supply unit (not shown) of each adsorption vessel 82, and an etchant. A supply pump 87 for supplying the etching solution L to the inside of the adsorption vessel 82 via the supply pipe 86, and one end side is connected to the storage tank 11, and the other end side is branched to discharge portions (not shown) of each adsorption vessel 82. Of the etching solution recovery pipe 88, the first supply side switching valve 89 and the second supply side switching valve 90 provided on the other end side of the etching solution supply pipe 86, and the etching solution recovery pipe 88, respectively. The first discharge side switching valve 91 and the second discharge side switching valve 92 provided on the other end side, respectively. When the adsorption container 82 is attached to each of the attachment portions 83 and 84, the etching solution supply pipe 86 The other end side is each adsorption container 8 The supply unit (not shown), so that the other end of the etchant recovery pipe 88 is connected to the discharge portion of the adsorber vessel 82 (not shown).

  The switching valves 89, 90, 91 and 92 are closed when the first supply side switching valve 89 and the first discharge side switching valve 91 are open. Thus, when the second supply side switching valve 90 and the second discharge side switching valve 92 are open, the first supply side switching valve 89 and the first discharge side switching valve 91 are controlled by the control device 25 so as to close. .

  In the second circulation mechanism 85, the etching liquid L in the storage tank 11 is selectively supplied to one of the adsorption containers 82 via the etching liquid supply pipe 86 by the supply pump 87. That is, when the first supply side switching valve 89 is open and the second supply side switching valve 90 is closed, the first supply side switching valve 89 is closed to the adsorption container 82 on the first mounting portion 83 side, and the second supply side switching valve 89 is closed. When the switching valve 90 is open, the etching solution L is supplied to the adsorption container 82 on the second attachment portion 84 side. Then, the etching liquid L supplied to one of the adsorption containers 82 and circulated in the adsorption container 82 is recovered in the storage tank 11 by the etching liquid recovery pipe 88.

  When the control device 25 operates the supply pump 22, the control device 25 controls the supply pump 87 and the switching valves 89, 90, 91, 92 to set the adsorption container 82 to which the etching solution L is supplied at a preset time interval. The etching solution L in the storage tank 11 is supplied to one of the adsorption containers 82 while alternately switching at a time interval (a time interval estimated that the chelate material (not shown) in the adsorption container 82 reaches a substantially saturated state). Circulate.

  In the removing mechanism 80 configured in this manner, the supply liquid 87 and each switching valve 89 are changed while the suction liquid 82 in the storage tank 11 is alternately switched at a preset time interval. , 90 is supplied to one of the adsorption containers 82 via the etching liquid supply pipe 86 and is circulated in the adsorption container 82 and then collected in the storage tank 11 via the etching liquid collection pipe 88. It circulates between the storage tank 11 and the adsorption container 82. Then, indium ions and tin ions contained in the etching solution L are adsorbed and removed by a chelating material (not shown) in the adsorption vessel 82.

  When the adsorption container 82 to be supplied is switched, the adsorption container 82 after use (adsorption container 82 in which indium or tin is adsorbed to a chelate material (not shown)) is replaced with an unused adsorption container 82 (chelate material). It is appropriately replaced with an adsorption vessel 82 (not shown) in which indium and tin are not adsorbed. That is, when the adsorption container 82 of the first attachment part 83 is switched to the adsorption container 82 of the second attachment part 84, the used adsorption container 82 is removed from the first attachment part 83, and the unused adsorption container 82 is replaced. When the adsorption container 82 of the second attachment part 84 is switched to the adsorption container 82 of the first attachment part 83, the used adsorption container 82 is removed from the second attachment part 84, and the unused adsorption container 82 is used. Is attached.

  Then, after the eluent is passed through the used adsorbing vessel 82 from the supply unit (not shown) and discharged from the discharge unit (not shown), The cleaning liquid flows through the supply unit (not shown) into the interior and is discharged from the discharge unit (not shown), and regenerates the chelating material (not shown) or chelate material (not shown). The indium and tin adsorbed on the metal are collected.

  If the removal mechanism 80 is configured in this manner, the apparatus configuration can be simplified as compared with the removal mechanism 30, so that the etching solution L can be regenerated with simple and inexpensive equipment.

  In the above example, the control device 25 controls the supply pump 75 based on the surfactant concentration detected by the concentration sensor 65 to adjust the surfactant concentration of the etching solution L in the storage tank 11. However, the present invention is not limited to this, and the supply pump 75 always supplies a constant amount of surfactant from the storage tank 73 into the storage tank 11 or the elapsed time since the etching process was started. A predetermined amount of surfactant may be supplied from the storage tank 73 into the storage tank 11 by the supply pump 75 when a predetermined time has elapsed or when the number of etched sheets reaches a predetermined number.

  However, in this case, depending on the type of surfactant added to the etching solution L, the type of chelating material (not shown), the amount of indium and tin adsorbed on the chelating material (not shown), etc. Since the amount of the surfactant adsorbed on the material (not shown) varies, it is difficult to set the amount of the surfactant supplied by the supply pump 75, and the surfactant is based on the concentration detected by the concentration sensor 65. There is a possibility that the surfactant concentration in the etching solution L cannot always be set to the optimum concentration as in the case of controlling the supply amount of the liquid.

  Further, in the above example, the control device 25 controls the etching in the storage tank 11 to any one of the adsorption containers 32, 33, 82 while alternately switching the adsorption containers 32, 33, 82 at a preset time interval. Although the liquid L is supplied, the present invention is not limited to this. For example, the number of the substrates K etched by the substrate processing mechanism 12 and the indium ions and tin ions contained in the etching liquid L in the storage tank 11 are described. Alternatively, the adsorption containers 32, 33, and 82 that supply the etching solution L may be switched based on the concentration of the above.

  When switching control is performed based on the number of etched substrates K, the substrate processing mechanism 12 is disposed at an appropriate position, for example, outside or inside the processing chamber 13, and the substrate K or the substrate K carried into the processing chamber 13 A sensor (not shown) for detecting the substrate K unloaded from the processing chamber 13 is further provided, and the control device 25 loads the processing chamber 13 into the processing chamber 13 based on an output signal obtained from the sensor (not shown). The number of substrates K that have been transferred or the number of substrates K that have been unloaded from the processing chamber 13, that is, the number of substrates K that have been etched by the substrate processing mechanism 12, is counted. Sometimes, the etching solution L in the storage tank 11 is supplied to one of the adsorption containers 32, 33, and 82 while alternately switching the adsorption containers 32, 33, and 82 to be supplied. . Note that when the counted number reaches the preset number, the control device 25 resets the count value and again counts to the preset number.

  In this way, when the number of counted sheets reaches a preset number, that is, the number of etched sheets becomes a predetermined number, and the number of chelate materials (not shown) estimated to reach a substantially saturated state. At this time, the switching valves 38, 39, 40, 41, 89, 90, 91, 92 are switched to switch the adsorption containers 32, 33, 82 to which the etching solution L is supplied.

  Therefore, even in this case, the adsorption capacity of the adsorption containers 32, 33, and 82 is maintained constant, and the concentration of indium ions and tin ions contained in the etching solution L is suppressed to a certain level or less.

  On the other hand, when switching control is performed based on the indium ion concentration or the tin ion concentration, the substrate processing apparatus 1 detects the concentration of indium ions and / or the concentration of tin ions contained in the etching liquid L in the storage tank 11. The controller 25 further includes a concentration detection sensor (not shown), and the control device 25 has an indium ion concentration and / or a tin ion concentration detected by a metal ion concentration detection sensor (not shown) higher than a preset reference value. Then, the etching solution L in the storage tank 11 is supplied to any one of the adsorption containers 32, 33, and 82 while alternately switching the adsorption containers 32, 33, and 82 to be supplied.

  In this way, the chelating material (not shown) reaches a substantially saturated state, the adsorption capacity thereof decreases, the concentration of indium ions and tin ions contained in the etching solution L in the storage tank 11 increases, and the metal When the indium ion concentration and / or tin ion concentration detected by an ion concentration detection sensor (not shown) becomes higher than a predetermined reference value, each switching valve 38, 39, 40, 41, 89, 90, 91, 92 is switched to switch the adsorption containers 32, 33, 82 to which the etching solution L is supplied.

  Therefore, even in this case, the adsorption capacity of the adsorption containers 32, 33, and 82 is maintained constant, and the concentration of indium ions and tin ions contained in the etching solution L is suppressed to a certain level or less. Further, since the amounts of indium and tin dissolved in the etching solution L differ depending on the etching conditions in the substrate processing mechanism 12 and the type of the substrate K to be etched, chelating materials (not shown) of the adsorption vessels 32, 33, and 82 are not shown. However, it is difficult to set the time until the number of etchings reaches the substantially saturated state and the number of etchings. This switching control can be performed with higher accuracy if it is performed based on the concentration of tin ions.

  Further, the etching solution L may not be supplied to only one of the adsorption containers 32, 33, and 82, but may be supplied to both simultaneously. Further, the removal mechanism 30 may be configured to include three or more or only one adsorption container 32, 33, or the removal mechanism 80 may be configured to be capable of attaching three or more adsorption containers 82 or only one. good.

  In the above example, while the substrate processing mechanism 12 is etching the substrate K, the etching solution L is constantly supplied to the adsorption containers 32, 33, 82. However, the present invention is not limited to this. When the elapsed time from the start of the etching process reaches a predetermined time, or when the number of etched substrates K reaches a predetermined number, the concentrations of indium ions and tin ions contained in the etching solution L in the storage tank 11 are increased. The etching solution L may be supplied to the adsorption containers 32, 33, and 82 to adsorb indium ions and tin ions when a predetermined concentration is exceeded. In this case, when the etching solution L is supplied to the adsorption containers 32, 33, and 82, a certain amount of surfactant is preferably supplied from the storage tank 73 into the storage tank 11 by the supply pump 75.

  Further, the mode of replenishing the etching liquid L into the storage tank 11 is not limited to the above-described one. For example, a constant amount of the etching liquid L is supplied into the storage tank 11 or the substrate K is supplied. A fixed amount may be supplied every time a predetermined number of sheets are processed, or a fixed amount may be supplied when an elapsed time from the start of the etching process reaches a predetermined time.

  Further, when supplying the surfactant, it may be supplied into the storage tank 11 as in the above example, or may be supplied to the etching solution L flowing through the etching solution recovery pipes 37 and 88. .

It is explanatory drawing which showed schematic structure of the substrate processing apparatus which concerns on one Embodiment of this invention. It is explanatory drawing which showed schematic structure of the substrate processing apparatus which concerns on other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate processing apparatus 11 Reservoir 12 Substrate processing mechanism 20 1st circulation mechanism 25 Control apparatus 30 Removal mechanism 31 Adsorption mechanism 32 1st adsorption container 33 2nd adsorption container 34 2nd circulation mechanism 35 Etching liquid supply pipe 36 Supply pump 37 Etching Liquid recovery pipe 38, 39, 40, 41 Switching valve 42 Eluent supply mechanism 43 Eluent supply section 44 Eluent supply pipe 45 Eluent supply valve 46, 47 Switching valve 48 Eluent recovery mechanism 49 Eluent recovery section 50 Eluent Recovery pipe 51, 52 selector valve 53 Eluent recovery valve 54 Cleaning liquid supply mechanism 55 Cleaning liquid supply section 56 Cleaning liquid supply pipe 57 Cleaning liquid supply valve 58 Cleaning liquid recovery mechanism 59 Cleaning liquid recovery section 60 Cleaning liquid recovery pipe 61 Cleaning liquid recovery valve K Substrate L Etching liquid

Claims (9)

A storage tank for storing a processing liquid containing a surfactant, a processing means for processing a substrate with the processing liquid, a processing liquid stored in the storage tank is supplied to the processing means, and the supplied processing liquid is supplied A substrate processing apparatus comprising a first processing liquid circulating means for recovering from the processing means to the storage tank and circulating a processing liquid between the storage tank and the processing means,
An adsorption container filled with an adsorbent that adsorbs metal ions that are included in the treatment liquid by the substrate treatment in the treatment means;
The processing liquid stored in the storage tank is supplied and distributed in the adsorption container, and the distributed processing liquid is recovered from the adsorption container to the storage tank and processed between the storage tank and the adsorption container. A second processing liquid circulating means for circulating the liquid;
A substrate processing apparatus comprising: a supply unit configured to supply the surfactant to the processing liquid stored in the storage tank or the processing liquid recovered from the adsorption container to the storage tank. A control means for controlling the operation of the second treatment liquid circulation means, and at least two of the adsorption containers;
The second processing liquid circulation means collects the processing liquid in the storage tank and the processing liquid supply pipe for supplying the processing liquid in the storage tank to each of the adsorption containers, and the processing liquid circulated in each of the adsorption containers. And a first switching valve that is provided in the processing liquid supply pipe and controls the supply of the processing liquid to each adsorption container. The first switching valve causes each adsorption container to have a first switching valve. Is configured to selectively supply and circulate the treatment liquid to any one of
The substrate processing apparatus according to claim 1, wherein the control unit is configured to perform switching control of the first switching valve. An eluent supply pipe for supplying an eluent for eluting the metal adsorbed by the adsorbent of each adsorption container to each adsorption container, and the elution liquid supply pipe provided in the eluent supply pipe, An eluent supply means for selectively supplying the eluent to any one of the adsorption containers by the second switch valve,
An eluent recovery means for recovering the eluent flowing through each of the adsorption containers;
When the control unit switches the first switching valve, the control unit controls the second switching valve to stop the supply of the processing liquid and the elution into the adsorption container where the adsorbent has adsorbed metal ions. The substrate processing apparatus according to claim 2, wherein the substrate processing apparatus is configured to supply a liquid. A cleaning liquid supply pipe for supplying a cleaning liquid for cleaning the inside of each adsorption container to each of the adsorption containers, and a third switching valve provided in the cleaning liquid supply pipe for controlling the supply of the cleaning liquid to each of the adsorption containers Cleaning liquid supply means for selectively supplying the cleaning liquid to any one of the adsorption containers by the third switching valve;
A cleaning liquid discharge pipe for discharging the cleaning liquid flowing through each of the adsorption containers to the outside;
The control means is configured to control the third switching valve to supply the cleaning liquid to the adsorption container after the supply of the eluent when the supply of the eluent is completed. 3. The substrate processing apparatus according to 3.   5. The substrate processing apparatus according to claim 2, wherein the control unit is configured to switch the first switching valve at a preset time interval.   The control means is configured to count the number of substrates processed by the processing means, and to switch the first switching valve when the counted number reaches a preset number. The substrate processing apparatus according to claim 2. A first detection means for detecting the concentration of metal ions contained in the processing liquid stored in the storage tank;
The control means is configured to switch the first switching valve when the concentration detected by the first detection means becomes higher than a preset reference value. 5. The substrate processing apparatus according to any one of claims 4 to 4. Second detection means for detecting the concentration of the surfactant contained in the treatment liquid stored in the storage tank;
Control means for controlling the operation of the supply means based on the concentration detected by the second detection means to bring the concentration of the surfactant contained in the treatment liquid into a preset concentration. The substrate processing apparatus according to claim 1. A second detection means for detecting the concentration of the surfactant contained in the treatment liquid stored in the storage tank;
The control means is configured to control the operation of the supply means based on the concentration detected by the second detection means so that the concentration of the surfactant contained in the processing liquid is set to a preset concentration. The substrate processing apparatus according to claim 2, wherein the substrate processing apparatus is formed.

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