TW200811933A - Processing device for processing fluid and substrate processing device having the same - Google Patents

Abstract

The present invention provides a substrate processing device to extend the replacing cycle of the processing fluid, to prevent the decrease of substrate-processing efficiency, and to reduce the processing cost of substrate. The substrate processing device 1 comprises: the first circulation mechanism 20 of processing fluid to circulate the processing fluid between the storage container 11 and the substrate processing mechanism 12; two absorption towers 32, 33 to absorb the metal ions in the processing fluid by the substrate-processing of the substrate processing mechanism 12; the second circulation mechanism 34 of processing fluid to selectively supply the processing fluid in the storage container 11 to any one of the absorption towers 32, 33 and make it circulate; and a control device 28 to control the operation of the second circulation mechanism 34 of processing fluid, so that the absorption towers 32, 33 supplied with the processing fluid can switch alternatively according to the predetermined time interval.

Description

[Technical Field] The present invention relates to a treatment liquid treatment apparatus for performing treatment for removing metal ions contained in a treatment liquid for substrate processing, and a substrate treatment provided with the same Device. [Prior Art] In manufacturing, for example, a semiconductor wafer, a liquid crystal glass substrate, a photomask

In the process of using various substrates such as a glass substrate or a substrate for a disk, a process of supplying various processing liquids such as an etching liquid, a developing solution, and a cleaning liquid to these substrates and processing the substrate is included. Further, as an apparatus for processing a substrate to be used in the process, an etching apparatus disclosed in Japanese Laid-Open Patent Publication No. 2000-96264 is known, and the apparatus for storing a surname is provided with a storage tank for storing a surname. A substrate processing mechanism for performing substrate processing: (4) a liquid circulation mechanism for supplying a liquid stored in the storage tank (4) (4) to the substrate processing mechanism, and recovering the supplied money engraving liquid from the structure, thereby circulating the (IV) liquid between the storage tank mechanisms The concentration sensor is used to detect the concentration of the component stored in the === engraving for the treatment of the _; and from the second: the standard: the concentration of the sound system detected by the concentration sensor The reference concentration is such that the above-mentioned advantageous in the engraving liquid is supplied to the new engraving liquid, so that the substrate processing machine == remains at a constant concentration. The number of conveying rollers is arranged in the processing chamber; there is ===;: direction conveying; and a plurality of nozzle bodies, etc., reverse, 'toward, w body, etc., the plural nozzle system configuration 6 200811933 Above, spray _ liquid on the top of the substrate. J: The entraining circulation mechanism includes: a supply pipe, one end side and a storage=connecting end-side side are disposed in the processing chamber, and an upper body is fixed on the other side of the other side: Each of the nozzle bodies is supplied (four), and the one end side of the recovery pipe is connected to the bottom W of the processing chamber, and the other end side is connected to the storage tank. In the case of the engraving device, the substrate is conveyed in a predetermined direction by the conveyance roller, and the engraved liquid stored in the storage tank is supplied from the supply pipe to each nozzle body by the supply pipe, and the substrate is liquid-etched from the nozzle body to the upper surface of the substrate. The skirting field is proud of: and the name of the engraved liquid sprayed onto the substrate flows through the recovery pipe, and is recovered from the inside to the inside of the storage tank. The waste is detected by the wave sensor at any time. The concentration of the above-mentioned favorable components in the engraving liquid, the concentration of the favorable component of the Gu Shi r #八,曲—一μ” detected by the concentration sensor deviates from the predetermined reference concentration, and the hunting is supplied to the storage tank by the rhyme replenishing mechanism. In the case of a new engraving liquid, the concentration of the above-mentioned advantageous component in the engraving of the engraving is maintained at a certain concentration. Patent Document 1: Japanese Laid-Open Patent Publication No. 2000-96264. Indium tin oxide is carried out: engraved 'by the job, the steel that constitutes the metal film and: the special genus will be dissolved in the 巍 years old | the 士 j liquid. Therefore, in the etchant in the storage tank In the conventional engraving apparatus configured by the method of circulating between processing mechanisms, the concentration of the above-mentioned metal contained in the surname engraving liquid gradually rises, and if a metal concentration reaches m or more, a (four) speed drop is generated = 7 200811933 High precision etching The concentration of the above-mentioned metal contained in the shape is increased, and the etchant is generated in the sputum to generate the oxidized liquid t to form the oxidized component of the genus, and the composition of the liquid is crystallized to precipitate the inner surface of the m-type reservoir or the particle. Form ~ # Attached in the survival of the living must be cut (four) title 'will also produce the problem of the inside of the deposit of the deposit. In the above-mentioned conventional money engraving device, the storage engraving must be periodically replaced, and, due to the process of replacing the etching solution,

Therefore, the substrate processing efficiency is lowered. In addition, due to: the reduction of processing efficiency and the cost of replacement of the cost (replaced etch: 'text waste: processing costs and replacement of the purchase cost of the replacement liquid will increase the cost of processing. In view of the above circumstances, the object of the present invention is to provide a treatment (four) device capable of reprocessing (4) of the treatment liquid, and to provide the treatment liquid treatment device, and to extend the replacement cycle of the treatment liquid, to prevent the substrate treatment efficiency from being lowered, and to reduce the pressure. In order to achieve the above object, the present invention relates to a treatment liquid processing apparatus for performing a process for removing metal ions contained in a treatment liquid for processing a substrate, characterized in that it comprises: a tank for storing the treatment liquid; a metal ion adsorption unit having at least two adsorbed soils arranged in parallel, in each of the adsorption towers, filled with a chelating agent for adsorbing metal ions in the treatment liquid; and for removing the treatment a circulation unit having means for supplying the above adsorption towers 8 200811933 to the storage tank a treatment liquid supply pipe for the treatment liquid, a treatment liquid recovery pipe for the material (4) at the time of the adsorption of the adsorption towers, and a supply liquid supply pipe for controlling the supply to the adsorption towers The first switching valve of the processing liquid is configured to selectively supply and circulate the processing liquid to any one of the adsorption towers by the (iv) the i-th switching valve. The processing liquid processing apparatus removes The treatment circulation unit selectively supplies the treatment liquid stored in the storage tank to any one of the adsorption towers via the treatment liquid supply pipe, and after circulating in the adsorption tower, is recovered into the storage tank through the treatment liquid time tube. Circulating between the storage tank and the adsorption tower. In the adsorption tower, # is filled with a meal mixture filled therein to adsorb the genus M7 of the 厶M7 / Τ3 in the treatment liquid (dissolved in the treatment) Gold in liquid

When the adsorption tower to which the treatment liquid is supplied is, for example, determined that the metal adsorbed by the chelating agent has reached a substantially saturated state, the adsorption tower is switched to the other adsorption tower 1 by the operation of the (four) 1 switching valve, whereby the metal ion adsorption unit can be used. The adsorption capacity of the metal ions is kept at the same time, and the chelating agent is appropriately regenerated by using an eluent for eluting the metal adsorbed on the chelating agent. . According to the treatment liquid processing apparatus of the present invention, by circulating the treatment liquid in the storage tank between the storage tank and the adsorption tower, the metal ions in the treatment liquid can be adsorbed and removed, thereby enabling the Since the treatment liquid is reused, it is possible to save the cost of buying a new treatment liquid and the cost of disposal of the treatment liquid of 9200811933, and the cost of the treatment liquid can be reduced, and the cost of the substrate treatment using the treatment liquid can be reduced. In addition, by switching the first switching valve, the processing liquid in the storage tank is circulated while switching the adsorption tower to which the processing liquid is supplied, so that the metal ion adsorption capacity of the metal ion adsorption unit is not lowered, and processing can be performed. Removal of metal ions in the liquid can effectively remove metal ions. Further, the treatment liquid treatment apparatus further includes an eluent supply unit having an eluent supply tube for supplying the eluent to the adsorption towers to elute the metal adsorbed by the chelating agents of the adsorption towers. And a second switching valve provided on the eluent supply pipe for controlling supply of the eluent to each of the adsorption towers, and switching the second switching valve to selectively perform any of the adsorption towers One of the eluent is supplied; and the eluent recovery unit recovers the eluent after flowing in each of the adsorption towers; and by switching the second switching valve, the supply of the treatment liquid is stopped. The chelating agent may be configured such that the adsorption column in which the metal ion is adsorbed in the metal ion state is supplied to the eluent. When the adsorption tower to which the treatment liquid is supplied is switched by the first switching valve of the removal processing cycle, the second switching valve for switching the eluent supply is appropriately operated, and the supply of the treatment liquid can be stopped. The adsorption tower supplies the eluent. The metal (metal ion) adsorbed by the chelating agent of the adsorption tower is eluted by the eluent, and the eluent containing the eluted metal ions is recovered by the eluent recovery unit. regeneration. In addition, there are also very expensive metals in the metal in the dissolution treatment solution, which is suitable if it can be recovered. However, it is also effective to properly recover the metal ions in the eluate collected in the above-mentioned manner back to 200811933. The metal dissolved in the treatment liquid is recovered. Further, the processing liquid processing apparatus further includes a cleaning liquid supply unit having a cleaning liquid supply pipe for supplying the cleaning liquid to the adsorption towers to clean the inside of each adsorption tower, and the cleaning liquid supply pipe is installed in the cleaning The third switching valve of the liquid supply pipe for controlling the supply of the cleaning liquid to each of the adsorption towers is configured to selectively supply the cleaning liquid to any of the adsorption towers by switching the third switching valve. And a cleaning liquid discharge pipe for discharging the cleaning liquid which has flowed through the adsorption towers to the outside; and supplying the washing liquid to the adsorption tower after the supply of the eluent by switching the third switching valve The method of cleaning the liquid is also possible. When the elution of the metal adsorbed by the chelating agent is completed, the third switching valve of the cleaning liquid supply unit is switched by an appropriate operation, and the cleaning liquid is supplied to the adsorption tower after the supply of the eluent. The inside of the adsorption tower is washed by the cleaning liquid, and the cleaning liquid is discharged from the cleaning liquid discharge pipe to the outside. Once the eluent _ 豸: inside the adsorption tower, when the treatment liquid in the storage tank is supplied to the adsorption tower, the treatment liquid is mixed with the eluent, which may adversely affect the substrate treatment using the treatment liquid. However, it is possible to effectively prevent the occurrence of this by washing away the eluent remaining in the adsorption tower by the washing liquid. Further, the processing liquid processing apparatus includes the above-described first switching at a predetermined time interval! The configuration of the control unit of the switching valve is also possible. In this case, the adsorption tower to which the treatment liquid is supplied is controlled by the control unit at a predetermined time interval, that is, at a time interval at which the metal adsorbed by the chelating agent of the adsorption tower is estimated to be substantially saturated. In addition to 11 200811933 to deal with the use of the cycle unit! Switching valve Therefore, even if it is used, it is the adsorption tower. All of the ions 11 can also keep the "ion adsorption capacity of the metal ion adsorption unit constant, so the effect is good. Ding Yi is the same as the other two, the above treatment liquid treatment device" has the metal ion concentration "early" For example, detecting the concentration of ions stored in the storage tank; and switching the above-mentioned first valve when the "metal enthalpy detection" detected by the metal enthalpy detection unit of the above-mentioned all is "predetermined reference value" In the case of the control unit, the control of the removal process by the control unit is performed as follows: The metal adsorbed by the sound agitating agent reaches a substantially saturated state, and the adsorption capacity of the metal ion decreases. The metal ion concentration in the treatment liquid in the storage tank increases, and the metal ion concentration detected by the metal ion concentration detecting unit is still predetermined. When the reference value is switched, the switching valve is switched, and the adsorption tower to which the treatment liquid is supplied is switched to another adsorption tower. Therefore, even if & Since the metal ion adsorption capacity of the metal ion adsorption unit can be kept constant, the same effects as described above can be obtained. In addition, 'when the ith switching width switching control is performed according to the elapsed time, 'based on rabbit hare 4* pK m The concentration of the metal ions contained in the treatment liquid of the decapitated horse is reduced, and the time at which the metal adsorbed by the nutrient of the adsorption tower is substantially saturated is different, so it is difficult to set the switching. Time, but 'by performing the switching control based on the metal ion concentration in the treatment liquid in the storage tank, the (four) control can be performed more effectively. 12 200811933 Further, in accordance with the elapsed time and metal ion concentration by the above control unit When the switching control of the first switching valve is performed, the eluent supply unit and the eluent recovery unit, the cleaning liquid supply unit, and the cleaning liquid discharge pipe may be provided, and the eluent supply may be performed by the control unit. Switching control of the second switching valve of the unit and the third switching valve of the cleaning liquid supply unit. Further, the present invention relates to The substrate processing apparatus comprising: '

The processing liquid processing apparatus; the processing unit for processing the substrate by the processing liquid; and the processing unit for circulating the substrate processing unit, wherein the unit is recovered and circulated between the units in the storage tank. And supplying the processing liquid stored in the processing unit to the processing unit, and processing the processing liquid in the storage tank and the processing rice field processing recycling unit, and causing the bedding to exist in the processing tank in the storage tank. The unit and the processing unit are further processed by the processing liquid. On the other hand, in the circulating treatment liquid, there is a metal ion (metal dissolution) in the process including the completion of this work and the early printing. In addition, the retort unit of the metal crystallization storage treatment in the treatment liquid stored in the Beiding storage tank is stored in the sputum, so that the storage 升 升 1 1 is removed. In the storage tank, the door of any one of the 漭 塔 towers, 隹 1 m night in the trekking tank and adsorption metal ions. The chelating agent of the phlegm is absorbed - or the treatment liquid in the storage tank is dryly tuned by the substrate treatment in the storage tank, and is removed by a few times. At 13 200811933, use the % unit to pass the g between the storage tank and any one of the adsorption towers. Thereby, the processing unit performs the substrate treatment using the treatment liquid; on the other hand, in the adsorption tower, the metal ions contained in the treatment liquid are treated by the substrate treatment. Further, in some cases, similarly to the above, while the adsorption tower is appropriately switched, the treatment (four) row is circulated, so that the adsorption capacity of the gold gas of the metal adsorption unit is maintained. In addition, the adsorption tower is switched, and the treatment liquid is switched. The chelating agent of the adsorption tower to be supplied can be appropriately regenerated using an eluent or the like. As described above, according to the substrate processing apparatus of the present invention, it is possible to adsorb and remove the metal ions contained in the treatment liquid during the substrate treatment, thereby reusing the treatment liquid and removing the metal ions from the treatment liquid while performing the substrate treatment. Therefore, the service life of the treatment liquid can be prolonged, the replacement period of the treatment liquid can be prolonged, and the substrate treatment cost can be reduced by prolonging the replacement period of the treatment liquid. In addition, when the processing liquid is continuously circulated in the adsorption tower during the substrate processing by the processing unit, the concentration of the metal ions in the treatment liquid can be suppressed to a predetermined degree or less from the W side. Further, it is possible to continuously operate without stopping the processing unit, whereby the yield and the substrate processing efficiency can be improved. Further, since it is possible to prevent the formation of the treatment liquid by the formation of the oxide of the metal ions in the treatment liquid, the precipitate does not adhere to the substrate in the form of particles, and it is not necessary to remove the deposition adhered to the inner surface of the storage tank. The operation of the object. Further, in the above substrate processing apparatus, the above-described 119 刀 2008 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 119 a counting unit, wherein the number of substrates in the processing unit processed by the processing liquid is ten, and when the number of counted sheets reaches a predetermined number of sheets, the processing unit sends a switching signal to the processing unit; . At the same time, the control unit for switching the first switching valve is switched between the processing liquid processing apparatus and the second counting unit when the counting unit receives the switching signal. In the case of 10a, when the number of substrate-treated sheets in the processing unit reaches a predetermined number, that is, when the number of sheets in which the metal adsorbed by the chelating agent of the adsorption tower is estimated to be substantially saturated is reached, the adsorption tower to which the treatment liquid is supplied is supplied. The first switching valve is switched by the control unit. Therefore, even if it is configured in this manner, the adsorption ability of the metal ions of the metal ion adsorption unit can be kept constant, so that the same effects as described above can be obtained. Further, the above-mentioned substrate processing apparatus includes: a component for detecting the concentration of the favorable component, for detecting a concentration of a component which is treated in the processing liquid stored in the storage tank, and a concentration adjusting unit; The advantageous component = concentration in the treatment liquid stored in the storage tank may be adjusted according to the concentration of the advantageous component detected by the advantageous component concentration detecting means, and may be maintained within a predetermined range. In this way, since the concentration of the advantageous component in the treatment liquid stored in the storage tank can be kept within a predetermined range, it is possible to prevent the concentration of the favorable component of the treatment liquid in the storage tank from occurring due to the treatment of the substrate or the like. The problem is that it is impossible to obtain a predetermined processing capability, and the substrate processing ability of the processing liquid can be maintained at an optimum state. In the case of the above-mentioned substrate, for example, a semiconductor wafer, a liquid crystal glass substrate, a glass substrate for a photomask, and a substrate for a disk are exemplified, but the invention is not limited thereto. Further, examples of the treatment liquid include, for example, #刻液, developing solution, and cleaning solution, but the browning is not limited thereto. Further, 'generally, a chelating agent is an organic compound which is collectively referred to as an aminocarboxylic acid salt, which has a property of adsorbing metal ions and being adsorbed by a specific solution. Specifically, exemplified by EDTA (ethylenediaminetetraacetic acid), NTA (triacetic acid amine), DTpA (diethylenetriaminepentaacetic acid) 'gldaCl·glutamic acid diacetic acid), and hedta (hydroxyethylethylene glycol) Amine triacetic acid), GEDTA (ethylene glycol ether diamine tetraacetic acid), TTHA (triethylenetetramine hexaacetic acid), mDA (hydroxyethyliminodiacetic acid), and DHEG (hydroxyethylglycine), but It is not limited to this. As described above, according to the treatment liquid processing apparatus and the substrate processing apparatus of the present invention, it is possible to adsorb and remove metal ions in the treatment liquid and reuse the treatment liquid, thereby suppressing the cost of the treatment liquid and the cost of the substrate treatment. Further, it is possible to effectively remove metal ions from the k treatment liquid without lowering the adsorption ability of the metal ions. In addition, when the processing liquid is circulated in the adsorption tower during the substrate processing, the concentration of the metal ions in the treatment liquid can be suppressed to a predetermined level or less, and the substrate treatment can be continuously performed simultaneously, and the occurrence of defects can be prevented. In the case, the substrate processing can be performed at a lower level. [Embodiment] Hereinafter, specific embodiments of the present invention will be described with reference to the accompanying drawings. 1 is a schematic view showing a configuration of a substrate at a substrate according to an embodiment of the present invention. As shown in FIG. 1, the substrate processing apparatus of this example etches the substrate K on which the copper oxide tin film (metal film) is formed, using, for example, a surname liquid L having an oxalic acid concentration (% by weight) of about 3%. The substrate processing mechanism 12 for storing the storage tank η of the etching liquid 1, the substrate processing mechanism 12 for the Lie liquid L _ substrate κ, and the first etching liquid circulation mechanism for circulating the etching liquid L between the storage tank u and the substrate processing mechanism Η (Circulation mechanism for etching treatment), removal mechanism for removing indium and tin (metal) dissolved in the contact liquid L, and the like. Further, the built-in substrate processing apparatus i includes a concentration sensor 24 that detects the oxalic acid concentration of the surname liquid L stored in the storage chute 11 (concentration of the component which is advantageous for the residual processing), and adjusts the storage in the storage. The concentration adjustment mechanism 25 of the oxalic acid concentration of the last name in the groove u, and the operation of the substrate processing mechanism core 余i re-circulation mechanism 2 〇 and the removal mechanism % are set to = (4) control | The control device 28 includes a first 8a that controls the liquid circulation mechanism 2G based on the = mechanism 12 and the first (four), and a second control unit 28b that controls the decoupling 3G. In the above structure, 2 4^^, the over-discharge tank 11, the removal mechanism 30, and the work-P8b function as a surname engraving treatment device. = Substrate processing mechanism 12 includes a processing chamber 3 having a sealed space, a plurality of transporting members 14 , is (in the case of a non-directional direction), a substrate K, and a supply (four) liquid engraving liquid in which the flow tube is disposed in the processing chamber i 3 The circulation mechanism 20, and the plurality of mouthpieces 16 and the like, the nozzle body of the plurality 17200811933 is fixedly disposed on the flow tube 15, and the engraving liquid l-L roller 14 is ejected onto the upper surface of the substrate κ from the processing chamber. The remaining liquid of the bottom of the 13 is discharged from the outside. The above-mentioned first-order circulatory circulation mechanism 20 includes: the supply end side is connected to the storage tank 1, and a pump 22 is connected to the flow tube 15 by the first flow; the supply part 1 is controlled by the first part 28a. The pipe 2! is supplied to the (IV) liquid L, the recovery pipe 23, and the like, and the recovery pipe =. The processing-external-side and storage-removing mechanism 30 includes a metal ion adsorption mechanism Μ, and the adsorption is dissolved in the surname liquid L by the etching treatment in the substrate processing mechanism 12, and is included in the Indium ions and tin ions in the liquid L (metal ion wide second (four) liquid circulation mechanism (recycling mechanism for removing treatment) Μ, the etching liquid L is circulated between the storage tank U and the metal ion adsorption mechanism 3; the eluent supply mechanism 42. The eluent is supplied to elute the indium and tin adsorbed by the metal ion adsorption mechanism η; the eluent recovery mechanism 48 recovers the eluent from the metal ion adsorption mechanism 31; the cleaning liquid supply mechanism 54 is supplied for washing The cleaning liquid m cleaning liquid mechanism 58 of the net metal ion adsorption mechanism 31 recovers the cleaning liquid from the metal ion adsorption mechanism 31. The metal ion adsorption mechanism 31 is provided with a chelating agent filled with adsorbed steel ions and tin ions. At least two adsorption towers (not shown) (t-th adsorption tower 32 and second adsorption tower 33). In general, a chelating agent (not shown) is an organic amine-based organic carboxylate. Object Qualitative, which has the property of adsorbing metal ions, and the adsorbed metal can be eluted by a specific solution of the solution 18200811933. Specifically, EDTA (ethylenediaminetetraacetic acid), hydrazine (triacetic acid amine) can be cited as an example. , DTPA (diethylenetriamine pentaacetic acid), GLDA (L. glutamic acid diacetic acid), HEDTA (ethyl ethylamine monoamine), GEDTA (ethylene glycol quinone diamine tetraacetic acid), ττΗΑ (triethylene tetra Amine hexaacetic acid), HIDA (hydroxyethylimine diacetic acid), and DHE (} (with ethyl glycine), etc., but are not limited thereto. The second etching liquid circulation mechanism 34 includes an etching liquid The supply pipe 35 has one end side connected to the storage tank U, the other end side branched, and connected to each of the adsorption towers 32 and 33. The supply spring 36 is controlled by the second control unit Na, and is passed through the surname liquid supply pipe 35. The inside of the adsorption towers 32 and 33 is supplied with (4) liquid L; the etching liquid recovery pipe 37 is connected to the storage tank u at one end side, and is connected to each adsorption tower 32, 33 at the other end side; First supply side switching valve 38 盥 second supply side switching valve of the other end side branch portion of 35 39; and a separate valve 41 or the like provided in the residual liquid recovery pipe 37. The outlet switching valve 40 and the second discharge side switch the respective switching valves 38, 39, 4, and 丄# 〇41 by the second control unit 28b Control, the member is switched on the supply side of the brother 1 μ 2 4it / \ ^ σ brother 1 discharge switching valve 40 is opened, the brother 2 supply side switching valve % and 2μ #弟 2 discharge side switching valve 41 is closed, · in the 2 supply side switching valves 3 9 and 9 ^ , when the discharge side switching valve 41 is opened, the first supply side switching valve 38 and the first side switching valve 1 recognize that the side switching valve 40 is closed. Then, it is supplied to the tank... Suction: In the second 324, 'when the driving supply 36, %, 39 is controlled, and °, 33 will be supplied to the side of the switching valve Dingzi trough 11 through the etching liquid 19 200811933 supply tube 35 It is supplied to any one of the adsorption towers 32 3 . That is, when the Jth supply, the a side switching valve 3 8 is opened, what? When the supply side switching valve 39 is closed, the etching liquid L is supplied to the adsorption tower 32, and the supply side switching valve 38 is closed, the younger 2 i, and the supply side switching valve 39 are aligned. The second adsorption column 33 supplies the etchant liquid L. „ ^ and the money entrained liquid L supplied to any one of the adsorption towers 32 and 33 and flowing through the adsorption tower: from the adsorption through the residual liquid recovery pipe 37 The columns 32, 33 are recovered into the storage tank u. The liquid supply mechanism 42 includes a supply unit that operates by: '邛28b control' to supply a washing liquid composed of, for example, hydrochloric acid or sulfuric acid, and an eluent supply #44, the end side of which is connected to the supply unit 43, The other side branches with each of the um masts 7. Q. ^ Q and the attached towers 32, 33 are connected; the eluent supply valve 45 is controlled by the second control unit 28b, and is provided on the eluent supply pipe 44 = one end side; and is respectively provided in the eluent The first supply-side switching valve 46, the second supply-side switching valve 47, and the like of the other end side branch portion of the f 44 are supplied. Each of the above-described switching valves 46 and 47 is controlled by the second control 邛 28b so that when the jth: the supply side switching valve 46 is opened, the second supply side switching valve 47 is closed; at *4, . When the side switching valve 47 is opened, the i-th supply side switching valve 46 is closed. The eluent recovery mechanism 48 includes a recovery portion eluent recovery unit 50 for recovering the eluate, one end side of which is connected to the recovery unit 49, and the other end side branch is connected to each of the adsorption towers 32 and 33; The second discharge side switching valve 51 and the second discharge side switching port 52 of the other end side branch portion of the eluent recovery unit 5; the eluent recovery unit 53#, the operation of the eluent recovery valve is The control unit 28b controls and is provided on the end side of the eluent recovery pipe 20 200811933 50. Each of the switching valves 51 and 52 is controlled by the second control unit so that when the ith discharge side switching port 51 is opened, the second discharge side: the valve 52 is closed; and when the second discharge side switching valve 52 is opened, the The side switching valve 5 1 is closed. m

In the eluent supply mechanism 42 and the eluent recovery unit 48, when the supply unit 43 is driven, the adsorption towers 32 and 33 to which the eluent is supplied are controlled by the supply-side switching valves 46 and 47. The eluent is supplied from the supply unit 曰43 to the adsorption towers 32 and 33 via the eluent supply tube 44. In other words, when the first supply-side switching valve 46 is opened and the second supply-side switching valve 47 is closed, the eluent is supplied to the second adsorption tower 32; the first supply-side switching valve 46 is closed, and the second supply-side switching valve 47 is closed. When it is opened, the eluent is supplied to the second suction tower 33. Further, the eluent which is supplied to any one of the adsorption towers 32 and 33 and which is passed through the adsorption tower =, 33 @, is recovered from the adsorption crucibles 32 and 33 into the recovery unit 49 via the eluent recovery tube 5 . Further, the supply side switching valve 52 is closed. When the second supply side switching valve 47 is opened, the second discharge side switching valve 52 is opened. The discharge side switching valve 5! is closed. Further, once the supply unit 43 is driven, the eluent supply valve 45 (4) liquid recovery recovery 阙Μ is opened. The cleaning liquid supply mechanism 54 includes a supply unit 55 whose operation is controlled by the first control 28b, and supplies a cleaning liquid composed of, for example, pure water; the end of the nail supply liquid supply pipe 56 is connected to the supply unit 55, and - the branch portion and the one end side of the end side disc eluent supply tube 44 are connected, and the eluent supply tube 44 is connected to each of the (four) towers 32, 33 via 21 200811933, and the cleaning liquid supply valve 5 is operated. It is controlled by the second control unit 28b, and is provided in the cleaning liquid supply, '° 5 56', the first supply-side switching valve 46, the second supply-side switching valve 47, and the like.上上久+7? „ μ μ each of the knife-replacement valves 46, 47 is controlled by the second control section in the same manner as described above, so that when the i-th supply-side switching valve 46 is opened, the second: the supply-side switching valve 47 is closed; When the second supply-side switching valve 47 is opened, the first supply-side switching valve 46 is closed. The cleaning liquid recovery mechanism 58 includes a recovery portion 59 for recovering the cleaning liquid, and a washing liquid recovery pipe (washing liquid discharge pipe). 6(), the end side is connected to the recovery portion 59. The other end side is separated from the branch portion of the eluent recovery tube % and the eluent recovery valve 53, and # 丄 丄 _ The liquid recovery pipe 5 is connected to the tower (four); the above-mentioned first] discharge side switching 阙" and the first; the discharge side 7 is replaced by 2; and the washing liquid recovery valve 61, etc., the washing liquid recovery valve The second control unit 28b controls and is provided on the other end side of the cleaning liquid recovery pipe. The respective switching widths 51 and 52 are controlled by the first control in the same manner as described above. P 28b controls the switching valve η on the i-th discharge side. When the p 2 2 discharge valve 52 is closed, the second discharge side switching valve 52 is turned 4, and the first discharge switching valve 5 J is closed. 幵 The cleaning liquid supply mechanism 54 and In the cleaning liquid recovery unit 58, the suction supply unit 55 is supplied with the cleaning liquid, and the supply side switching ports 46 and 47 are controlled to control the liquid, and the cleaning liquid is supplied from the supply unit 55. The liquid supply pipe 56 and the eluent supply pipe 44 are supplied to 4% of the adsorption tower 32. That is, when the jth supply side switching valve "2 is supplied, the supply side switching valve 47 is closed" to the first adsorption tower 32. Supply of the cleaning liquid; 22 200811933 When the supply side switching valve 4 is closed, and the valve 9 is turned off, the supply side switching valve 47 is opened, and the cleaning liquid is supplied to the second adsorption column 33. Further, the cleaning liquid supplied to any one of the adsorption towers 32, 33 φ # ^ ^ 32, 33 & % s and flowing through the adsorption tower, 60 - ^ , , by the sputum recovery pipe 50 and The washing liquid & 60 is recovered from the adsorption tower 32 in the town 7 #% to the recovery section 59. Further, when the supply side switching valve 46 of the younger brother 1 is in the position of 9 sisters, the closing guard 1 discharge switching valve 51 is opened, the second discharge switching valve 52 is closed, and when the supply side switching valve 47 is opened.

The second discharge switch valve 52 is opened, and the output valve 51 is closed. In addition, when the "supply supply unit 5" is driven, the three-person 59 will open. And the liquid leveling valve and the cleaning liquid recovery valve 1 concentration adjusting mechanism 25 include: a supply tank 27 to the storage tank; the supply tube 27, one end side of which is connected to the storage tank U at the other end side of the supply system; And the first control unit. The first control unit controls the operation of the supply unit 26 based on the early acid concentration of the concentration sensor 24. The first control unit 28a controls the supply of the first etching liquid circulation mechanism 20 so that the etching liquid L is between the storage tank 11 and the substrate processing mechanism 12, and the first control unit 28a is based on the concentration. The sensor 24 detects the bite of the grass, and controls the supply unit 26 to maintain the oxalic acid concentration of the etched X night L stored in the storage tank 11 within a predetermined range. For example, the concentration of oxalic acid detected by the concentration ϋ 24 is higher than the above-mentioned predetermined range. . When the door is in a month, pure water is supplied to the storage tank 11; when the concentration of oxalic acid measured by the concentration sensing core is lower than the predetermined range, oxalic acid is supplied to the storage tank 11 to make the etching liquid L The oxalic acid concentration is within the pre-set range of 23 200811933. Furthermore, the first control unit 28a is using the first! When the etching cycle mechanism 20 starts and ends the circulation of the etching liquid L, the correlation signal (start signal and end signal) is transmitted to the second control unit 28b. When the second control unit receives the start money from the i-th control unit w, the second control unit controls the supply of the second engraving liquid circulation mechanism 34 and the valve-switching valves 38, 39, .4, 4, and The adsorption towers 32 and 33 to which the money engraving liquid L is supplied are switched at a predetermined time interval 7, and the (four) liquid L in the storage tank 11 is supplied to any of the adsorption: two, 33, and I is switched. The adsorption tower to which the surname L· is supplied is supplied; 3 2, 3 3, ,] First, the supply unit 43 of the eluent supply mechanism 42 and the eluent supply axe are controlled. The switching valves 46 and 47 and the respective cut and 52 of the eluent recovery mechanism 48 and the washing & liquid recovery valve 53 terminate the adsorption towers 32 and 33 which supply the liquid (4) by switching the adsorption towers 32 and Ϊ. In the middle, the liquid is supplied for a predetermined period of time, and then the supply unit Η, the second liquid supply valve 57, the respective switching valves 46 and 47, the cleaning liquid recovery mechanism, and the switching valves 51 are controlled. 52 and the cleaning liquid recovery valve 61 are processed at the timing and supply of the cleaning liquid. Further, when the second control unit bird receives the end signal ' from the second second portion 28a, the circulation of the etching liquid by the second etching liquid length mechanism 34 is stopped. * According to the substrate processing apparatus 本 of the present example having the above-described structure, the etching liquid L stored in the storage tank 11 is controlled by the first control unit 28a, and the supply pump 22 of the two-dimension circulatory circulation mechanism 2G is used via the supply tube. 2ι and a flow tube are supplied to the respective nozzle bodies 16, and the nozzle bodies 16 are ejected from the nozzles of the substrate K. Then, the remaining liquid B ejected onto the upper surface of the substrate κ flows from the discharge port 13a of the processing chamber η 24 200811933 in the recovery pipe 23 and is recovered in the storage tank, and thus, the liquid in the storage tank 11 The storage tank u and the substrate processing mechanism 12 are circulated. The substrate K is conveyed in a predetermined direction by the conveyance roller 14, and is etched by the etching liquid L (the oxalic acid of the etching liquid) ejected from each nozzle body 16. Further, by the etching treatment, the indium tin oxide film of the substrate κ is dissolved in the J liquid L, and the indium ion and the tin ions are contained in the etching liquid L. Further, the etching liquid L stored in the storage tank U is controlled by the second control unit 2, and the supply liquid of the second etching liquid circulation mechanism 34 and the respective valve-replacement valves 38 and 39 are passed through the surcharge supply pipe. 35 is selectively supplied to the second attachment. Any one of 32 33, and in the adsorption towers 32, 33: pass, and then recovered into the storage tank n via the etching liquid recovery pipe 37, so that it is in the storage tank " and the adsorption towers 32, 33 Circulation. Thereby, the indium ions and tin ions in the residual liquid L are adsorbed by a chelating agent (not shown) filled in the adsorption tower m. The adsorption towers 32 and 33 which are supplied with the surname liquid L are controlled by the second control unit 2 to control the respective switching valves 38, 39, 4, and 41 of the second engraving liquid circulation mechanism at predetermined time intervals. In other words, it is estimated that the indium and tin adsorbed by the chelating agent (not shown) of the adsorption towers 32 and 3 are alternately switched at a time interval of substantially saturated state, and when the adsorption tower to which the etching liquid is supplied is switched, 33, the following processing is performed by the second control unit 28b. That is, first, the second control unit 28b controls the supply unit 43 of the eluent supply mechanism 42, the eluent supply valve 45, the switching valves 46 and 47, and the respective switching valves 51 and 52 of the eluent recovery mechanism 48. And the eluent recovers 25 200811933 valve 53, whereby the eluent is supplied from the supply unit 43 through the eluent supply tube 44 to the adsorption tower 32 which stops the supply of the etching liquid 1 by switching the adsorption tower 32, %, 33 (when switching from the first adsorption tower 32 to the second adsorption tower =, the second adsorption tower 32 is supplied to the second adsorption tower 32; and the second adsorption tower 33 is switched to the first and the auxiliary tower 32% 'to the second adsorption tower 33 Supply), supplied wash

The liquid is supplied to the adsorption towers 32 and 33, and then recovered into the recovery unit 49 via the eluent recovery tube 50. Thereby, indium and tin adsorbed by the chelating agent (not shown) of the adsorption towers 32 and η are eluted by the eluent, and the eluent containing the eluted indium ions and tin ions is recovered and recovered. Within the department 49. Then, the second control unit 28b controls the supply unit 54 of the cleaning liquid supply unit 54, the cleaning liquid supply valve 5, and the switching valves 5 and 52 of the respective switching valves 47, 47 and the cleaning liquid recovery unit 58 and the washing. The cleaning liquid supply valve 61 is supplied from the supply unit 55 via the cleaning liquid supply pipe 56 and the eluent supply pipe 44 to the same adsorption 32w and η as the adsorption 35w and η supplied to the eluent. 33. The supplied cleaning liquid flows through the adsorption tower 32, and then 'recovered through the eluent recovery f 5〇 and the cleaning liquid recovery I 6〇, and is recovered in the recovery unit 59. Thereby, the eluent remaining in the inside of the adsorption towers 32, 33 is washed away by the cleaning liquid. After the suction towers 32 and 33 supplied to the etchant L are sequentially supplied with the eluent and the cleaning liquid, the suction (four) 32, 33 becomes a standby center and is sampled by the switching. The adsorption of the liquid L is sufficient to keep the adsorption capacity of the indium ions and the tin ions of the metal ion adsorption mechanism 31 constant, and it is possible to suppress the concentration of the cerium ion concentrated tin ions in the etching and the liquid L to a certain level or less. Further, 17 26 200811933 Further, the oxalic acid concentration of the etching liquid L stored in the storage tank 11 is maintained within a predetermined range by the /degree adjustment mechanism 25. Further, during the process of receiving the start signal to the reception end signal from the second control unit 28b, that is, during the etching process, the etching liquid L is continuously circulated in the adsorption towers 32, 33 from the etching liquid L. The indium ions and tin ions are removed while etching is performed.

Then, in the substrate processing apparatus 1 of the present embodiment, while the substrate processing unit 12 is etching the substrate K, the second etching liquid circulation mechanism 34 is used to switch the adsorption towers 32 and 33 to which the etching liquid L is supplied. The etching liquid L in the storage tank is often circulated between any one of the adsorption towers 32 and 33, so that the indium ions and tin ions in the money L are adsorbed in the adsorption towers 32 and 33 (not shown). In the case of the adsorption towers 32 and 33' which are supplied with the etchant L, the eluent supply device 42 supplies the eluent to the adsorption towers 32 and 33 which are supplied to the etchant L to be adsorbed. a treatment in which indium and tin in a chelating agent (not shown) are eluted, and the integrator (not shown) is regenerated; and the adsorption towers 32 and 33 are supplied to the eluent by the cleaning liquid supply mechanism W. * The washing liquid is washed, and the eluent remaining in the crotch portions of the adsorption towers 32, 33 is washed away. Therefore, it is possible to effectively remove the steel ions and the tin ions + to suppress the concentration of the indium ions and the tin ions in the etching liquid L to be less than /it. The substrate processing mechanism 12 and the 傕i ^ 叩 are continuously operated to extend the life of the etching liquid L and prolong the replacement period of the etching liquid L. Further, in the case where the etching liquid L contains a high concentration of indium ions, a problem occurs in which 4 / μ h of the decocting liquid L is formed, and indium bismuth oxide and the component oxalic acid crystal 27 in the etching liquid L are deposited. However, in this example, since the indium ion mobility in the etching liquid L can be lowered to a certain level or less, it is possible to prevent the oxalic acid from being emitted. Therefore, the crystals of oxalic acid do not adhere to the substrate κ in the form of particles. Further, it is not necessary to remove the operation of the oxalic acid crystal attached to the inner surface of the storage tank η. Further, by performing the continuous etching treatment in this manner, the etching treatment efficiency is not lowered, and the replacement period of the etching liquid L is prolonged, so that the etching processing cost can also be lowered. In addition, the elution liquid is supplied to the adsorption tower 32^33 in a state in which the supply of the etching liquid L is stopped and the indium ions and tin ions are adsorbed by the chelating agent (not shown), and the eluted indium ions and Since the elution solution of tin ions is recovered in the recovery unit 49, the chelating agent (not shown) can be regenerated, and the cerium ions and tin ions in the recovered eluate can be appropriately recovered, thereby being effective. Indium (very expensive metal) and tin dissolved in the etching liquid L are recovered. Further, after the eluent supply means 42 supplies the eluent, the cleaning liquid supply means 54 supplies the cleaning liquid to the adsorption towers 32, 33 to which the eluent has been supplied, and washes off the adsorption towers 32, 33. Since the internal liquid is supplied to the adsorption towers 3 2 and 3 3 in the storage tank 11, the etching liquid L can be effectively prevented from being washed in the adsorption towers 32 and 33. This liquid pick-up causes a change in the composition of the residual liquid L to adversely affect the etching treatment performed in the substrate processing mechanism 12. Further, the concentration of the oxalic acid of the etching liquid L stored in the storage tank 1 is kept within a predetermined range by the concentration adjusting mechanism 25. Therefore, it is possible to prevent the etching treatment performed in the substrate processing mechanism 12, etc. 28 200811933. The oxalic acid concentration of the etching liquid L in the storage tank 11 is changed, and a problem such as a predetermined rhyme ability cannot be obtained, and the etching processing ability of the etching liquid L can be maintained in an optimum state. In the following, the results of the adsorption experiment of metal ions using "chelestfiber GRY-L (trade name) manufactured by Chelist Corporation, Japan, as a chelating agent will be described. That is, the first diameter is prepared by the KScrn. a column in which the above-mentioned chelating agent having a weight of 4 g, a height of llcm, and a volume of 19 4 mL is filled, and then a metal ion-containing etching solution containing oxalic acid and etching treatment is set at a flow rate of 3 mL/min from the above-mentioned column. The one end side of the column is passed to the other end side. Thus, after a predetermined amount of the etching liquid is passed through, the etching liquid passing through the column is sampled, and the concentration of the metal ion is measured, thereby obtaining the following results. The etching liquid before the liquid has an indium ion concentration of 277 Ppm, a tin ion concentration of 33.7 ppm, and a (iv) sub-concentration of 〇.24 ppm. In contrast, the etchant concentration of the etching solution after the column is passed through is 8 ppm, and the tin ion concentration is When the yield is below PP1PPm and the concentration of the ionic ion is $ Glppm, each ion is reduced to a very low concentration. It can be seen that the mixture can effectively remove the presence in the #刻液Metal ions such as indium ions, tin ions, and aluminum ions. Further, using the same column and integrator as described above, the liquid of the above (4) is supplied to the column at the same flow rate as described above, and is passed through 29 200811933 2 , A certain amount of the liquid was passed through, and the etching liquid after the liquid passage was sampled, and the concentration of the indium ions contained in the etching liquid after the flow was measured. Fig. 2 shows the result / wherein, in Fig. 2, BV (Bed Volume: Bed volume) is the volume '(mL) / (-) of the chelating agent filled in the column is (the amount of etchant passing through the column) / (the volume of chelating agent filled in the column). Thus, the 'horizontal axis' indicates the amount of etchant that has been passed through as much as the amount of chelating agent. a " Figure 2 shows that until the amount of liquid passing through the solution reaches a certain amount (phase = about u times the volume of the chelating agent) Since the amount of indium ions was not detected from the engraved liquid after the circulation, the indium ions were completely adsorbed by the integrator. It is also known that even if a large amount of the engraved liquid is supplied, the adsorption of the chelating agent is lowered. From the chelating agent to which the metal material is adsorbed as described above The experimental results of eluting the metal ions are described. Also, the same column and chelating agent as described above are used, and the same amount of etching liquid as described above is supplied to the column at the flow rate of the above-mentioned two, and the liquid is passed through. After the indium ion is adsorbed in the chelating agent, one equivalent of sulfonium (1N-H2S04) is supplied from the end of the column to the end of the column at a flow rate of 1 / · mountain A_5 mL / min. The sulfuric acid after the liquid passing is sampled, and the concentration of the cerium ions contained in the sulfuric acid after the circulation is determined. Figure 3 shows the result. Wherein, the BV (Bound Volume) is: the volume of the chelating agent in the column, (mL) / (mL-fiber) is (the amount of sulfuric acid in the two main streams) (filling The chelating agent in the column is a sulphuric acid. Therefore, the cross-section 矣 _, the sleeve table has not been permeable to the amount of chelating agent volume of 30 200811933 sulfuric acid. In addition, in the measurement of the indium ion concentration in the previous paragraph, The time until the presence of indium ions is not confirmed in the sulfuric acid after the circulation, the product of the ion concentration at the point, and the amount of the liquid in the time zone are calculated as the amount of the ion eluted at each time point, and the cumulative amount is calculated. The value is obtained as the amount of all the eluted indium. The value obtained by dividing the amount of ruthenium eluted at each time point by the amount of the all eluted granules is defined as the elution rate at each time point (by The ratio of the indium adsorbed by the chelating agent to the sulfuric acid is shown in Fig. 3. As can be seen from Fig. 3, the indium adsorbed by the chelating agent is eluted with sulfuric acid, and the sulfuric acid is passed through. The amount of liquid reaches a certain amount (equivalent to a volume of 42.8 times the volume of the chelating agent), The indium adsorbed by the chelating agent is completely eluted. Further, the use of sulfuric acid can effectively regenerate the chelating agent adsorbed with indium, and the use of sulfuric acid can also efficiently recover the metal adsorbed by the chelating agent. Although an embodiment has been described, the specific mode that can be employed in the present invention is not limited thereto. In the above example, the time intervals of the adsorption extraction 32, 3, ... to which the etching liquid L is supplied are alternately switched. However, it is not limited thereto, and, for example, it can be configured to perform switching control of the adsorption towers 32 and 33 according to the number of sheets of the substrate K remaining in the substrate processing mechanism Η, or according to: In the etching in the slot i, the concentration of indium ions in the night L and the tin ions and/or the degree of switching between the adsorption columns 32 and 33 are controlled. When the switching control is performed based on the number of words of the substrate K, the above-mentioned base: The processing unit 12' is provided with a sensor (for example, disposed at an appropriate position such as the outside or inside of the processing 13), and detects the substrate K in the loading processing 31 200811933 to 13 or moves from the processing chamber 13 Substrate κ, 'not shown'. The ith control unit 28a functions as a counter unit that counts the number of sheets of the substrate κ that is engraved in the earth sheet processing unit 12. According to the configuration, the number of the substrates κ loaded into the processing chamber I] or the sheets of the substrate κ carried out from the processing chamber 13 are processed based on the output signals obtained from the sensing benefits (not shown). The number (the number of the substrate defects that are surnamed in the substrate processing mechanism 12) is processed by ten, and in addition to the start signal and the end signal, the control unit 2 8 b is also turned off. , Shih Tzu #, Tian Shu 5 counts of the number of pieces reached the pre-set of the stupid signal (switching Xunyi, & old change heart tiger) processing. The second control unit 28b is configured to control the supply pump 36 of the second engraving liquid circulation mechanism 34, the switching valves 38 and 39, "/μ upper 39 40, il, and the second control unit 28a. Receiving the center of the cut---switching the adsorption towers 32, 33, -k to which the pure entrained liquid L is supplied, and supplying any one of the adsorbents 32, 33 to the retentate L in the storage tank ii and circulating it. The 帛1 control unit 28a is configured to reset the count value and count the number of pieces to a predetermined number of pieces once the number of pieces counted up to the previous time is reached. In the second part, the etching liquid L is circulated by the second etching liquid circulation mechanism 34 during the reception of the start signal to the reception end signal. The right and the above-described configuration constitute the substrate processing apparatus, and the number of counts reaches a predetermined number of sheets. In other words, when it is estimated that the integrator (not shown) of the adsorption tower m and the indium and tin to which the attached indium and tin are substantially saturated, the switching is performed 3 2 . , , 39 , 40 , 4 1 , switching is supplied to the etching night

Adsorption towers 32, 33. From L 32 200811933, this p is used to form the substrate processing apparatus 1 in the above manner, and it is also possible to maintain the adsorption capacity of the metal ion adsorption mechanism 31 (tetra) ions and tin ions - the indium ion concentration and the tin ion concentration in l Since the suppression is below the predetermined level, the same effects as described above can be obtained.

On the other hand, in the case of switching control according to the cesium ion concentration and the tin ion concentration, the upper etchant processing apparatus 5 includes detecting the concentration of indium ions and/or tin ions in the liquid L stored in the storage tank u(4)(4). The metal ion concentration detection sensing H (not shown) is configured, and the second control port 28b is configured to control the supply pump 36 of the second etching liquid circulation mechanism 34 and the switching valves 38 and 39. , 4〇, 41, when the indium ion Hanta and/or tin ion concentration from the metal ion concentration detecting sensor (not shown) (4) is higher than the reference value set by 贱, the side is switched to be supplied with the etching liquid L The adsorption towers 32 and 33' supply the etching liquid L in the storage tank U to any one of the adsorption towers 32 and 3'3 and circulate it. When the substrate processing apparatus is configured as described above, once the indium and tin adsorbed by the chelating agent (not shown) of the adsorption towers 32 and 33 reach a substantially saturated state, the adsorption ability of the indium ions and the tin ions is lowered and stored in the storage tank u. The cesium ion concentration and the tin ion concentration in the etching liquid L in the inside increase, and the indium ion concentration and/or the tin ion concentration detected by the metal ion/length detecting sensor (not shown) are higher than a predetermined reference value. Then, the switching valves 38, 39, 4A, and 41 are switched, and the adsorption towers 32 and 33 to which the etching liquid L is supplied are switched. Therefore, even if the substrate processing apparatus i is configured as described above, the adsorption ability of the indium ions and the tin ions of the metal ion adsorption mechanism 31 can be kept constant, and the indium ion concentration and the tin ion concentration in the etching liquid L can be suppressed. Since it is a certain level or less, the same effect as the above can be obtained. In addition, when the switching control of the adsorption towers 32 and 33 is performed based on the elapsed time or the number of etched sheets, the etching conditions in the substrate processing mechanism 12 and the type of the substrate K as the object of the last name are dissolved in the residual μ. The amount of indium and tin dissolved is different. 'The time during which the indium and tin adsorbed by the adsorption towers 32 and 33 #chelating agent (not shown) reach a substantially saturated state and the number of etching sheets are different, so it is difficult to set the switching time and etching. In the number of sheets, the switching control of the suctions 32 and 33 is performed based on the indium ion concentration and/or the tin ion concentration in the liquid L in the storage tank U, whereby the adsorption towers 32 and 33 can be more effectively implemented. Switch control. Further, in the above-described example, during the etching of the substrate 基板 in the substrate processing mechanism 12, the surname L is continuously circulated in the adsorption towers η, η, but not limited to brown, for example, 'only etching may be started. After the treatment = the time period of the time phase 'or the number of (4) sheets of the substrate 达到 reaches the predetermined w = the concentration of indium ions in the etching & L in the tank T and the tin: 丨 ^ exceeds the predetermined concentration, in order to remove the indium The etchant L is circulated in the adsorption columns 32, 33 by ions and tin ions. In the above-described example, the etching liquid processing apparatus 5 is provided in the substrate processing apparatus, and ####斯斯, ' > is limited thereto, and for example, the etching liquid processing apparatus of Fig. 4 may be used for processing. The storage tank 70 and the above-mentioned division==set 6' are the removal unit 28b and the second control mechanism Π the storage tank 7", and are stored in the storage tank 11 for the second storage. In the etchant processing apparatus 6 shown in FIG. 4, the same components as those of the substrate processing apparatus 1 shown in FIG. 34 200811933 are denoted by the same reference numerals, and detailed description thereof will be omitted. In this case, the etching liquid L in the storage tank 7 is controlled by the second control unit 28b, and any of the storage tanks 7 and the adsorption towers 32 and 33 by the second etching liquid circulation mechanism 34. Between the two, the indium ions and the tin ions in the etching solution L are adsorbed and removed by the chelating agent (not shown) of the adsorption columns 32 and 33. At this time, for example, the supplied surcharge L is alternately switched at a predetermined time interval. The adsorption towers 3 2, 3 3 are supplied from the adsorption towers 32, 33 The etching liquid L in the storage tank 7 starts to elapse for a certain period of time, and once the indium ion concentration and the tin ion concentration of the surname 1 in the storage tank 7 are lower than a predetermined reference value, the circulation of the etching liquid L is stopped, indium. The removal process of the ions and tin ions is completed. Then, after the removal treatment in the storage tank 70, the (4) infusion liquid 1 is appropriately returned to the storage tank 1 1 for the last name.

In addition, the eluent supply mechanism 42 stops the supply of the (4) & L adsorption towers 32, 33_ by the switching of the adsorption towers 32, 33, and supplies the eluent, and then supplies the cleaning liquid by the cleaning liquid supply mechanism 54. The second eluent is recovered by the eluent recovery mechanism 48 and the supplied cleaning (4) by the cleaning liquid recovery mechanism 58. Even if the engraved liquid L of the storage tank 7 is circulated between the storage tank 70 and the adsorption towers 32, 33 according to the residual liquid treatment device 6, it is sufficient to adsorb and remove the etching liquid L. Indium does not kick the ions, so that the etching liquid L can be reused. Therefore, it is possible to save the cost of the "code" new etching liquid L and the use of the used etching liquid L. / / 97 In order to reduce the cost of the etching process, the cost of the etching process can be reduced. Further, since the etching liquids 1 in the storage tank 70 are circulated while switching the adsorption towers 32 and 33 to which the etching liquid L is supplied, the adsorption capacities of the indium ions and tin ions of the adsorption towers 3 2, 3 3 are not caused. By reducing the indium ions and tin ions from the residual liquid L, indium ions and tin ions can be effectively removed. Further, in the above example, the substrate κ on which the indium tin oxide film was formed was etched using an etching liquid L' having an oxalic acid concentration of about 3 Å/〇, and indium and tin dissolved in the etching liquid L were recovered, but The kind of the etching liquid 1 and the kind of the recovered metal are not limited thereto. Further, in the above-described example, the substrate κ is etched, but a development process or a cleaning process may be performed, and the substrate Κ includes a semiconductor wafer, a liquid crystal glass substrate, and a photomask. Various substrates κ such as a glass substrate and a substrate for a disk. Further, the metal ion adsorption mechanism 31 may include three or more adsorption towers 3 2, 3 3 . Further, in the above-described example, the switching chambers 38, 39, 40, and 41 of the second etching liquid circulation mechanism 34, the supply unit 43 of the eluent supply mechanism 42, the eluent supply valve 45, and the respective switching valves 46, 47. Each of the switching valves 51 and 52 of the eluent recovery mechanism 48, the eluent recovery valve 53, the supply unit 54 of the cleaning liquid supply mechanism 54, the cleaning liquid supply width 57, and the respective switching valves 46, 47, and washing The operation control of each of the switching valves 51 and 52 and the cleaning liquid recovery valve 61 of the cleaning liquid recovery unit 58 is performed by the second control unit 28b, but can be manually operated by an operator. Further, in the above-described example, the i-th control unit 28a and the second control unit 36200811933 port P28b constitute the control skirt 28, but the invention is not limited thereto, and the first control unit 28a may be provided. The function and function of the second control unit 28b. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a configuration diagram showing a schematic configuration of a substrate processing apparatus according to an embodiment of the present invention. ^ 疋 shows the relationship between the amount of money entrained in the column and the concentration of indium ions contained in the liquid entrainment. Θ 疋 indicates the relationship between the amount of sulfuric acid that passes through the column, the concentration of the ion in the sulfuric acid after the liquid is passed, and the ratio of the elution of the daughter ion adsorbed by the meal (by elution with sulfuric acid) (extraction rate). Figure. Fig. 4 is a configuration diagram showing a schematic configuration of an etching liquid processing apparatus according to another embodiment of the present invention. [Description of main component symbols] 1 substrate processing apparatus 5 residual liquid processing apparatus 11 storage tank 12 substrate processing mechanism 20 first etching liquid circulation mechanism 24 concentration sensor 25 concentration adjustment mechanism 28 control device 28a first control unit 28b second Control unit 37 200811933

30 Removal mechanism 31 Metal ion adsorption mechanism 32 First adsorption tower 33 Second adsorption tower 34 Second etching liquid circulation mechanism 3 5 Etching liquid supply pipe 36 Supply pump 37 1 Insect liquid recovery pipe 38 to 41 Switching valve 42 Eluent Supply mechanism 43 supply unit 44 eluent supply pipe 45 eluent supply valve 46 > 47 switching valve 48 eluent recovery mechanism 49 recovery unit 50 eluent recovery pipe 51, 52 switching valve 53 eluent recovery valve 54 Cleaning liquid supply mechanism 55 Supply unit 56 Cleaning liquid supply pipe 5 7 Cleaning liquid supply valve 58 Cleaning liquid recovery mechanism 38 200811933 59 Recovery unit 60 Cleaning liquid recovery pipe 61 Cleaning liquid recovery valve K Substrate L Remnant

39

Claims (1)

200811933 X. Patent application scope: The treatment liquid processing apparatus is a treatment for removing metal ions contained in a treatment liquid for processing a substrate, and is characterized by comprising: a storage tank for storing the treatment liquid; An adsorption unit having at least two adsorption towers disposed side by side in the inner crucible of each adsorption tower, filled with a chelating agent for adsorbing metal ions in the treatment liquid; and ▲ *processing unit for use, which has a treatment liquid supply pipe for supplying the treatment liquid in the storage tank to each of the adsorption towers, and a treatment liquid recovery pipe for collecting the treatment liquid flowing through the respective adsorptions into the storage tank, and providing: The liquid supply pipe is for controlling the switching valve for supplying the processing liquid to the adsorption towers, and by switching the first switching valve, selectively supplying and circulating the processing liquid to any one of the adsorption towers. . 2. The treatment liquid treatment apparatus according to claim 1, further comprising: an eluent supply unit having a chelating agent for supplying elution liquid to each adsorption tower by the adsorption towers The eluent of the adsorbed metal is supplied to the eluent supply pipe for controlling the 帛2 switching valve for supplying the eluent to the I adsorption tower, by switching the second switching valve, the selectivity The eluent and the eluent recovery unit are supplied to any one of the adsorption towers, and the extracting liquid is supplied to the respective adsorption towers; the washing and hunting after the circulation in the adsorption towers is switched by switching the second switching valve to The elution tower in which the treatment liquid is stopped and the chelating agent adsorbs the metal ion state is supplied to the elution liquid 200811933. 3. The treatment liquid treatment apparatus according to the second aspect of the patent application, comprising: 〃, / 液液液单单' having a washing liquid for supplying the cleaning liquid to each adsorption tower to wash the inside of each adsorption tower The cleaning liquid supply pipe and the third switching valve provided in the washing/supply liquid supply to control the supply of the cleaning liquid to the adsorption towers are selectively switched to the respective third switching valves a supply of the cleaning liquid in the adsorption tower; and a cleaning liquid discharge pipe for discharging the cleaning liquid after the adsorption towers are externally discharged; ° /; IL fine by switching the third switching width The cleaning solution is supplied to the adsorption technique after the supply of the eluent. σ 4· The processing liquid processing apparatus according to claim 1, further comprising a control unit that switches the second switching valve at a predetermined time interval. 5. The treatment liquid treatment apparatus according to claim 1, further comprising: a metal ion concentration detection unit that detects a metal ion concentration in the treatment liquid stored in the storage sample; and a control unit When the metal ion concentration detected by the metal ion concentration detecting means is higher than a predetermined reference value, the seventh switching valve is switched. 6. The treatment liquid treatment device according to claim 4 or 5, further comprising: ^ 200811933 an eluent supply unit having a pot for supplying an eluent to each of the adsorption towers The eluent supply pipe for the metal adsorbed by the sound agitation agent of the adsorption tower and the eluent supply pipe provided for controlling the supply to the adsorption towers. The 帛2 switching valve of the eluate extracting device selectively supplies the eluent to any one of the adsorption towers by switching the second switching valve; and the eluent recovery unit is recovered The eluent after circulation in each adsorption tower; uhai control unit' is once switched! The switching valve switches the second switching valve to supply the eluent to the adsorption tower in which the treatment liquid is stopped and the chelating agent adsorbs metal ions. 7. The processing liquid processing apparatus according to claim 6 further comprising: a cleaning liquid supply unit having a cleaning liquid for supplying the adsorption towers to wash the internal adsorption of the adsorption towers The cleaning liquid supply pipe of the crucible and the third switching valve that is provided in the washing liquid for controlling the supply of the cleaning liquid to the adsorption towers by selectively switching the crucible 3 switching valve The cleaning liquid is supplied to any one of the adsorption towers; and the cleaning liquid discharge pipe is configured to discharge the cleaning liquid flowing through the adsorption towers to the outside; the control unit ends the eluent The supply, that is, the switching of the third switching valve 'and the supply to the washing (four), is supplied to the cleaning liquid. 8. A substrate processing apparatus comprising: a processing liquid processing apparatus according to any one of claims 1 to 7; a processing unit for processing a substrate using the processing liquid; and 42 200811933 ^ substrate processing The processing unit supplies the processing liquid stored in the bead storage tank to the processing unit, and collects the supplied processing liquid from the processing unit into the ejection tank, so that the processing liquid is processed in the storage tank cycle. A substrate processing apparatus comprising: a processing liquid processing apparatus according to claim 1 of the patent application scope; a processing unit for processing the substrate by the processing liquid; and a circulating unit for processing the I board The processing unit is supplied with the treatment liquid stored in the bedding reservoir, and the supplied treatment liquid is recovered from the treatment unit into the storage tank, and the treatment liquid is circulated between the storage tank and the treatment unit; 70, counting the number of substrates processed by the processing unit in the processing unit, and when the number of counted reaches a predetermined number of sheets, transmitting a switching signal to the processing liquid processing apparatus; the processing liquid processing apparatus further A control unit that switches the first switching valve when receiving the switching signal from the counting unit. The substrate processing apparatus of claim 9, wherein the processing liquid processing apparatus further comprises: an eight μ eluent i, a single weir, which is provided to supply the eluent to the adsorption towers An eluent supply pipe for eluting the metal adsorbed by the chelating agent of each adsorption column, and a second switching valve provided in the eluent supply pipe for controlling the supply of the eluent to the adsorption towers by Switching the second switching width, selectively supplying the eluent to any one of the adsorption towers; and extracting the liquid recovery unit to recover the washing liquid after the circulation in the adsorption towers; 200811933; The control unit switches the first switching valve, that is, switches the second eight: valve, and supplies the eluent to the adsorption tower in which the treatment liquid is stopped and the nutrient is adsorbed with the monoxide ion state. The substrate processing apparatus according to claim 10, wherein the processing liquid processing apparatus further comprises: , a liquid supply, and a single S' having a cleaning for supplying the adsorption towers: Washing: 洗: the cleaning liquid supply pipe inside each adsorption tower and the third switching valve provided in the washing liquid supply officer for controlling the supply of the cleaning liquid to the adsorption towers by switching the third a switching valve for selectively supplying the cleaning liquid to any one of the adsorption towers; and, the liquid venting discharge I′ is for discharging the cleaning liquid after being blown in the adsorption towers to the outside; When the supply of the eluent is completed, the fourth switching valve is switched, and the cleaning liquid is supplied to the adsorption tower after the eluent is supplied. # # 12. The substrate processing device for the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The concentration of the component treated by the substrate; and the concentration adjusting unit adjusts the concentration of the favorable component in the treatment liquid stored in the storage tank according to the concentration of the favorable component detected by the favorable component concentration detecting unit, thereby maintaining Within the preset range. 44