TWI236050B - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

The present invention provides a kind of method capable of reducing the consumed amount of cleaning liquid (pure water) when supplying cleaning liquid on the substrate surface to process the substrate. At the beginning, when conveying a substrate W into the processing room 12 of the water washing processing portion 10, cleaning liquid is supplied from the entrance nozzle 20 and the upper nozzle 22 to the substrate. After that, until the substrate is moved out from the processing room 10, cleaning liquid is supplied from the upper nozzle 22 and the lower nozzle 24 to the substrate.

Description

1236050 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for processing a substrate by supplying a cleaning liquid on the surface of a substrate such as a semiconductor substrate, a broken glass substrate for a liquid crystal display device, and a glass substrate or a printed substrate. Substrate processing method and substrate processing apparatus. [Prior art] When a wiring pattern is formed on a substrate surface such as a semiconductor wafer with a metal material such as copper, aluminum, or silver using lithography technology, first, a metal film such as copper, aluminum, or silver is formed on the substrate surface, and After the photoresist film is formed on the metal film, the substrate is subjected to various processes such as exposure, development, and etching to perform desired patterning. Thereafter, the photoresist film film remaining on the substrate is peeled from the substrate surface and removed. In these series of processes, in the step of removing the photoresist film coating from the substrate, for example, an organic stripping solution containing amine can be used. Then, the substrate after the peeling process is cleaned with pure water, and then dried. Here, after the substrate is peeled by using an organic stripping solution containing amine, when pure water is supplied to the surface of the substrate to which the stripping solution is adhered and the cleaning process is performed, the stripping solution containing amine is mixed with pure water to generate strong alkalinity. Solution. As a result, a problem arises that the metal film used to form the wiring pattern is corroded or dissolved. Therefore, in order to solve the above problems, a method is proposed in which pure water in which carbon dioxide is dissolved is used in a cleaning process after the peeling process. In other words, a method is proposed (for example, refer to Patent Document 1): by spraying a large amount of pure carbon dioxide dissolved pure water on the surface of a substrate to which a stripping solution containing amine is attached, the strong alkalinity caused by amine is neutralized to prevent strong Alkali solution production

O: \ 89 \ 89957.DOC 1236050 Fig. 3 is a schematic front view showing an example of a schematic configuration of a conventional substrate processing apparatus having a water-washing processing unit capable of using pure water in which carbon dioxide is dissolved as a cleaning solution. The substrate processing apparatus is provided with a peeling processing unit M, which is adjacent to the water washing processing unit 60 on the front side of the water washing processing unit 60. A part of the peeling processing section 62 is not shown in the figure and does not show a detailed structure, but it has a processing chamber 64, and a roller conveyor 66 'is arranged inside the processing chamber 64 to support the foundation. Transport horizontally. The substrate w is supported by the roller conveyor 66 in a horizontal posture, or it can be transported by being supported in a slightly inclined posture in a direction orthogonal to the substrate conveying direction. The substrate is coated with a photoresist film on the surface of the substrate. Further, a plurality of peeling liquid nozzles (not shown) are provided above the substrate transfer path along the substrate transfer path. Next, in the processing room 6-while using a roller conveyor ^ to transfer the substrate W,-while taking out the liquid from the stripping solution, supply liquid, for example, containing [-methyl-2- ketone, isopropanolamine, ethanolamine, etc. The amine-containing organic 3 peeling liquid is on the substrate W. In this way, the light_coating that covers the surface of the substrate is dissolved and removed from the surface of the substrate. In the peeling processing section 62, the peeling W is first adhered to the surface of the substrate W that can be peeled and can be carried out from the outlet 68 of the processing chamber μ. The substrate ~ can be transported to the washing processing section 6 with the peeling liquid 1 adhered to the surface. 〇. Washing and cleaning department 6. The processing chamber 70 'is provided with an inlet-side opening 72 and an outlet-side: port 74. A roller conveyor% is disposed in the paste portion of the processing chamber, and the substrate w is transported in a horizontal or slightly inclined position to the horizontal direction. In processing a 7. An inlet nozzle 78 is provided near the entrance-side opening 72 of the nozzle 72 for the purpose of spraying the J-screen cleaning liquid onto the substrate W. In addition, there is no board conveyance path

O: \ 89 \ 89957 DOC 1236050 The upper nozzle 80 and the lower nozzle 82 are respectively connected above and below the substrate conveyance path along the substrate conveying path. Each of the cleaning liquid supply pipes 84, 86, and 88 that communicates with the inlet nozzle 78, the upper nozzle 80, and the lower f nozzle 82 communicates with the pipe 90a, respectively, and the pipeline 90a is connected to the discharge port side of the pump 92. The suction inlet side of the pump 92 is connected to the bottom of the water storage tank 94 in which the pure water 2 is stored through a flow path through a pipe 90b. Next, a gas dissolution module 96 is inserted in the middle of the pipe 90a, and a gas supply pipe 98 connected to a carbon dioxide gas supply source such as a gas cylinder is connected to the gas dissolution module 96 so that carbon dioxide can be dissolved through the pipe 90a and sent. To pure water in the cleaning solution supply pipes 84, 86, and 88. A drain pipe 100 is connected to the bottom of the processing chamber 70, and the used cleaning liquid can be discarded by the drain official 100. Although not shown, a plurality of water washing treatment units are provided downstream of the water washing treatment unit 60 in series. Next, in the water washing processing section disposed on the downstream side, the pure water used for substrate cleaning can be sent to the water storage tank of the water washing processing section on the upstream side adjacent to the water washing processing section, so that The water washing treatment unit sequentially sends the used pure water in the water storage tanks of the water washing treatment units located on the upstream side to the water storage tank 94 of the water washing treatment unit 60 through the liquid feed pipe 1 02. In the water-washing processing unit having the structure shown in FIG. 3, the substrate W in the processing chamber 70 is carried through the inlet-side opening 72. First, the curtain-shaped cleaning liquid sprayed from the inlet nozzle 78 onto the substrate W can be washed. Peeling liquid 1 attached to the surface. In addition, while the substrate w is transferred into the processing chamber 70 by the roller conveyor 76, the cleaning liquid is sprayed from the upper nozzle 80 and the lower nozzle 82 to the upper and lower surfaces of the substrate W, thereby washing and adhering to the substrate w. Surface peeling fluid 1. At this time, a peeling liquid and a cleaning liquid (pure water) containing amine are generated on the substrate W

O: \ 89 \ 89957.DOC 1236050 mixed solution, but because carbon dioxide is dissolved in the cleaning solution, it can neutralize the alkalinity caused by amine and prevent the solution from forming strong alkalinity. Next, the substrate w which has undergone the cleaning process in the water-washing processing section 60 is carried out 'from the opening 74 on the outlet side of the processing chamber, and is transferred to the adjacent water-washing processing section. [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-141269 (page 5-16, drawing) The conventional substrate processing apparatus having the structure shown in FIG. The washing process of the substrate W in the water washing processing unit 60 causes the material to be washed from the bottom of the processing chamber 70 through the drain pipe ⑽ and completely discarded. This is because by mixing the peeling liquid with the cleaning solution, the amine contained in the liquid towel will form a tritium component and be contained in the beta cleaning solution using a dagger. In this way, since the used washing liquid can be completely discarded, the amount of pure water that can be supplied to the water storage tank 94 through the liquid feeding pipe 1G2 from the washing processing unit on the downstream side adjacent to the washing processing unit 60 is insufficient. The separable, upper nozzle 80 and lower nozzle 82 are supplied to the substrate w. Pure water must be supplied into the water storage tank 94 from a pure water supply source by other means. In this way, there are the following problems: the amount of pure water used increases, and the consumption of carbon dioxide gas also increases. On the other hand, even if the amount of pure water used is slightly reduced, a part of the used cleaning liquid discharged from the bottom of the processing chamber 70 is returned to the water storage tank 94. Residues of amines in the cleaning solution in 94 (corrosion and wounds) will cause problems on the substrates that are subsequently processed. The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a method for reducing the number of cleaning liquids (pure water) when processing a substrate by supplying a cleaning liquid to the substrate surface.

〇 \ 89 \ 89957 DOC -10- 1236050 used substrate processing method, and a substrate processing device that can implement this method well. [Summary of the Invention] The invention in item 1 of the scope of patent application is a substrate processing method, which is used to convey the substrate from the inside to the inside of the processing chamber while spraying the curtain-shaped cleaning liquid from the vicinity of the entrance of the processing chamber The inlet nozzle to the upper surface of the substrate and the substrate conveying path are sandwiched, respectively, above and below the substrate conveying path along the substrate conveying path, respectively, and the cleaning liquid is sprayed to the upper and lower nozzles of the upper and lower sides of the substrate. The process of processing a substrate with a cleaning liquid is characterized by the following steps: (a) the step of supplying the cleaning liquid to the substrate from the inlet nozzle and the upper nozzle described above when the substrate is first moved into the processing chamber; (b) Then after step (a) is completed, until the substrate is removed from the processing chamber, the upper nozzle and the lower nozzle supply cleaning liquid to the substrate: step, (c) before a certain time elapses after the substrate is moved into the processing chamber, Steps from the process described above to the disposal of the used cleaning solution discharged at the bottom, and after the process described above is completed, until the substrate is ejected from the aforementioned processing chamber, it will be used. The cleaning liquid is recovered to a recovery tank and reused. The substrate that can be transported to the processing chamber is a substrate after peeling treatment, and a stripping solution containing amine is attached to the substrate. The cleaning liquid is dissolved in pure water towel with trioxide. Carbon cleaning solution 0 The invention of item 2 of the scope of patent application is a substrate processing method for transferring substrates in a processing chamber, and from the vicinity of the entrance of the processing chamber, while cleaning the curtain-like cleaning solution. An inlet nozzle ejected onto the upper surface of the substrate, and a substrate conveying path sandwiched therebetween, along the substrate conveying path above and below, respectively

〇 \ 89 \ 89957 DOC 1236050 The cleaning solution is supplied to the upper and lower nozzles and lower nozzles of the substrate. The substrate is supplied with cleaning solution to process the substrate. The characteristics are as follows: (a) the substrate is initially When carrying in the processing chamber, the step of supplying cleaning liquid to the substrate from the inlet nozzle and the upper nozzle (b) separately (a) After the completion of step (a), until the substrate is removed from the processing chamber, from the upper nozzle and the lower portion The step in which the nozzle supplies the cleaning liquid to the substrate, (c) continuous measurement is used to display the amount of amine contained in the used cleaning liquid that can be discharged from the bottom of the processing chamber, and the measured indication value meets the specific requirements. The step of discarding the used cleaning solution, and (d) the above-mentioned measured value is not a step that satisfies the aforementioned specific conditions until the substrate is removed from the processing chamber, and the used cleaning solution is recovered to a recovery tank for reuse; it can be transported to The substrate of the processing chamber A is a substrate after peeling treatment, and an amine-containing peeling liquid is attached to the substrate; the aforementioned cleaning liquid is cleaned by dissolving carbon dioxide in pure water. . For the invention in the third scope of the patent application, in the substrate processing method in the second scope of the patent application, the aforementioned indication value is the pH value, and the pH value measured in the step (c) is below a specific value. The step of discarding the liquid; the step (d) is a step in which the measured pH value is less than a specific value and the substrate is removed from the Lishui processing chamber, and the used cleaning liquid is recovered to a recovery tank and then used. The invention in item 4 of the scope of patent application is a substrate processing apparatus including a processing chamber that can process substrates; a substrate conveying means that can transport substrates in the processing chamber; and an inlet nozzle that can clean curtain-like liquid Sprayed onto the substrate arranged near the entrance of the processing chamber; the upper nozzle and

O: \ 89 \ 89957.DOC -12- 1236050 Lower nozzles can be placed in the processing room of Lishu with the substrate conveying path sandwiched between, above, and below the substrate conveying path, and the cleaning liquid Sprayed onto the top and bottom of the substrate. ^ — 'Younger to younger three cleaning liquid supply piping, which can be divided into the inlet nozzle, the above upper nozzle and the lower nozzle; and cleaning hand &#pass through the aforementioned cleaning liquid Supply piping to supply the cleaning liquid to the inlet nozzle, the upper nozzle, and the lower nozzle, respectively. The second step includes: the first to third switches are controlled, and the first to second cleaning liquids are respectively inserted. Supply piping and draining piping, which are used to discard the used cleaning liquid that can be discharged from the bottom of the processing chamber. The fourth switching control valve is inserted into the draining piping and recovery piping. The used cleaning fluid and the fifth switch control object are collected, which are inserted into the aforementioned recovery pipe, and return to the command line 4+ «η ^ mouth collecting tank, which is used to pass the recovery g through the bottom of the processing chamber. Officially used used cleaning Liquid recovery and control means for controlling the opening and closing operations of the first to fifth switching control valves. The substrate that can be transported to the processing chamber is a substrate after peeling treatment, and an amine-containing peeling liquid is attached to the substrate. The aforementioned cleaning solution is a cleaning solution in which carbon dioxide is dissolved in pure water; the aforementioned control means respectively control: the first action, which initially moves the substrate into the processing chamber, and turns on the first switch control and the second switch control After the valve is turned on, the second switch control valve and the third switch control valve are opened until the substrate is removed from the aforementioned process. The second action is to open the fourth switch before a certain time elapses after the substrate is moved into the processing chamber. The control valve closes the fifth on-off control valve, and thereafter, until the substrate is removed from the processing chamber, the fifth on-off control valve is opened and the fourth on-off control valve is closed.

O: \ 89 \ 89957DOC -13-1236050 The invention of claim 5 of the patent offense is a substrate processing apparatus, which includes a processing chamber, which can process substrates, and a substrate transfer method, which can transfer substrates in the processing chamber. ; A-port nozzle, which can scoop out the curtain-shaped cleaning liquid onto the substrate arranged near the person σ in the processing chamber; the upper nozzle and the lower nozzle, which can be sandwiched by the substrate transport path in the processing chamber, respectively Above and below it are connected along the substrate conveying path, and the cleaning liquid is sprayed onto the top and bottom of the substrate. The first to third cleaning liquid supply pipes can communicate with the inlet nozzle, the upper nozzle, and the lower nozzle, respectively. ; And a cleaning liquid supply hand & which can supply the cleaning liquid to the inlet nozzle, the upper nozzle, and the lower nozzle through the respective cleaning liquid supply pipes, and the bean characteristic further includes: first to third switching control valves , Which are respectively inserted into the aforementioned first to third cleaning liquid supply piping and drainage piping, and are used to discard the used cleaning liquid that can be discharged from the bottom of the processing chamber The fourth switch control valve is inserted into the aforementioned draining pipe and the recovery pipe to recover the used cleaning liquid, and the fifth switch control valve is inserted into the aforementioned recovery pipe and the recovery tank. The used cleaning liquid recovery and measurement means discharged from the bottom of the processing chamber through the recovery piping is used to continuously measure and display the amount of amine contained in the used cleaning liquid discharged from the bottom of the processing chamber, and A control means for controlling the opening and closing operations of the first to fifth on-off control valves; the substrate that can be transported to the processing chamber is a substrate after peeling treatment, and an amine-containing peeling liquid is attached to the substrate; the cleaning liquid is A cleaning solution in which carbon dioxide is dissolved in pure water; the aforementioned control means respectively control: the first action, when the substrate is first moved into the processing chamber, the first on-off control valve and the second on-off valve are opened O: \ 89 \ 89957 .DOC -14-! 235.050 valve 'after' until the substrate is removed from the aforementioned processing chamber, before opening: the second on-off control valve and the third on-off control valve; And the second action: According to the measurement signal from the aforementioned measurement means, when the specified value contained in the cleaning liquid is less than 4 specific levels, before the measured value of the measurement satisfies the special money,… 1, the fourth switching control valve is described and Close the fifth switch control room, and when the phase indicated value satisfies specific conditions until the substrate is removed from the processing chamber, open the fifth switch control valve and close the fourth switch control valve. For the invention in the sixth scope of the patent application, in the substrate processing device in the fifth scope of the patent application, the aforementioned indication value is the PH value; before the aforementioned: the pH value measured by the action system is below the special value, insert it into the aforementioned row The on-off control valve of the liquid piping is opened, and the on-off control valve inserted into the recovery piping is closed, and the measured pH value is below the special value until the substrate is removed from the processing chamber. The on-off control valve is opened, and the on-off control valve inserted into the drainage pipe is closed. When the substrate processing method according to the inventions in claims No. 丨 to No. 3 is applied, and if the substrate processing apparatus in nos. Nos. 4 to 6 is used, when the substrate is first moved into the processing chamber, the inlet nozzle and the upper nozzle are used. The cleaning liquid is supplied to the substrate, and thereafter, until the substrate is removed from the processing chamber. Since the cleaning liquid is only supplied to the substrate from the upper nozzle and the lower nozzle, it is different from the case where the cleaning liquid is often supplied to the substrate from the inlet nozzle, the upper nozzle, and the lower nozzle. In contrast, the amount of cleaning liquid used is reduced. In the substrate processing method for the invention in the scope of patent application No. 1 and in the substrate processing apparatus for the invention in scope of patent application No. 4, since the substrate can be processed into O: \ 89 \ 89957.DOC -15-1236050 After a certain period of time, until the substrate is removed from the aforementioned processing chamber, the used cleaning liquid discharged from the bottom of the processing chamber is recovered to a recovery tank and reused. Therefore, the amount of pure water used as a cleaning liquid can be further reduced, and carbon dioxide can be reduced. Consumption. On the other hand, the used cleaning liquid that can be discharged from the bottom of the processing chamber before a certain time elapses after the substrate is carried into the processing chamber can be discarded. In addition, when a specific time elapses after the substrate is carried into the processing chamber, most of the peeling liquid attached to the substrate is rinsed with a cleaning solution. Therefore, the substrate can be discharged from the bottom of the processing chamber after a specific time has passed since the substrate was carried into the processing chamber. Most used cleaning fluids are amine-free. In this way, even if the used cleaning liquid is recovered in a recovery tank and reused, there is little possibility that amines (corrosive components) remain in the cleaning liquid in the recovery tank. Therefore, there is no problem with the substrates that can be processed after being docked. In the substrate processing method of the invention in the scope of patent application No. 2 and in the substrate processing apparatus in the scope of patent application No. 5, the continuous measurement is used to display the content of the used cleaning liquid that can be discharged from the bottom of the processing chamber. When the amount of amine is indicated, and when the amount of amine contained in the cleaning solution is less than or equal to the specified amount, the measured value is less than or equal to the specified value, that is, the amine-containing peeling liquid can be removed from the substrate Most of the removal is because the used cleaning liquid that can be discharged from the bottom of the processing chamber can be recovered and reused in the recovery tank, so the amount of pure water used as the cleaning liquid can be reduced, and the consumption of dioxin can be reduced. . On the other hand, when the amount of amine contained in the cleaning solution is less than a specific amount and the measured indication value is less than or equal to the specific value, the washed cleaning solution that can be discharged from the bottom of the processing chamber may be discarded. In addition, because the amount of amine contained in the cleaning solution is less than a specific amount, the measured indicator value is a specific value

〇 \ 89 \ 89957 DOC -16-1236050 or above, because the used = lotion that can be discharged from the bottom of the processing chamber does not contain amine, so even if the used washing liquid is recovered and collected, When reused, the residual amine (corrosive component) in the cleaning solution in the recovery tank is less susceptible. Therefore, there is no problem with a substrate that can be processed next. In the substrate processing method claimed for the invention in the third scope of the patent, and in the substrate processing apparatus for the sixth scope of the invention, the pH value of the used cleaning liquid that can be discharged from the process & is continuously measured. When the measured value is less than a specific value, the used cleaning liquid that can be discharged from the bottom of the processing chamber can be recovered to a recovery tank and reprocessed. On the other hand, the used cleaning liquid that can be discharged from the bottom of the processing chamber before the measured p female is below a certain value can be discarded. [Embodiment] Hereinafter, a preferred embodiment of the present invention will be described with reference to Figs. 1 and 2. Fig. 1 is a schematic front sectional view showing an example of an embodiment of the present invention and showing a schematic configuration of a substrate processing apparatus. In the figure, only the water washing processing unit is shown. A peeling processing section is provided on the front side of the water-washing processing section 10, which is adjacent to the water-washing processing section 10. However, since the peeling-processing section has been described above, the description is omitted here. The water-washing processing unit 10 includes a processing chamber 12 having an inlet-side opening 4 and an outlet-side opening 16. A roller conveyor 8 is arranged inside the processing chamber 12 and supports the substrate W in a horizontal posture or a slightly inclined posture. And carry it horizontally. The substrate W with the peeling liquid 1 attached to its surface is transferred from the peeling processing section to the water washing processing section 10. An O: \ 89 \ 89957 DOC -17-1236050 inlet nozzle 20 is provided near the inlet-side opening 14 of the processing chamber 12 and is used to spray a curtain-like cleaning liquid onto the substrate w. In addition, an upper nozzle 22 and a lower nozzle 24 are connected along the substrate conveying path above and below the substrate conveying path, respectively. These structures are the same as those of the conventional devices described above. The inlet nozzle 20, the upper nozzle 22, and the lower nozzle 24 communicate with the cleaning liquid supply pipes 26 '28 and 30, respectively, and the on-off control valves Vi and VP V3 are inserted into the cleaning liquid supply pipes 26, 28, and 30, respectively. Each cleaning liquid supply piping 26, 28, 30 communicates with a piping 32a, and the piping 32a is connected to the discharge port side of the pump. The suction port side of the pump 34 is connected to the reservoir storing pure water 2 through the piping 3213. The bottom of the water tank 36. Next, insert the gas plate / disassembly module 38 into the pipe 32 & and connect the gas supply pipe 40 connected to a carbon dioxide gas supply source such as a gas cylinder to the gas dissolution module% to dissolve carbon dioxide. In pure water that can be sent to the cleaning liquid supply piping 26, 28, and 30 through the piping unit 32a. In addition, the means for dissolving carbon dioxide in pure water is not limited to a configuration in which a gas dissolution module 38 is inserted halfway through the piping Ua. It can also have any structure, for example, foaming pure carbon dioxide in pure water stored in the tank, or manufacturing pure water in which carbon monoxide is dissolved. At the bottom of the processing chamber 12, a liquid outflow pipe 42 and a liquid outflow pipe are communicated. The 42 system is divided into a recovery pipe 44 and a drainage pipe f46. The front-end outlet of the recovery pipe material is introduced into the water storage tank 36. In addition, the used β washing solution can be discarded through the drainage pipe 46. For recycling For piping 44 and drainage The piping M is respectively inserted with the switch control valves v4 and v5. In addition, a pH meter 48 is inserted into the liquid outflow pipe 42 to continuously measure the pH value of the cleaning liquid that can flow through the interior of the material. The measurement signal is input to the controller 50. X, from the control

O: \ 89 \ 89957.DOC -18- 1236050 is a 50-percent control signal that can be transmitted to the on-off control valve (% ~ V) ·, and uses this control signal to control the on-off operations of each on-off control valve Vi ~ v5. — In addition, 'a pure water supply application pipe 52 for introducing the front-end outflow into the water storage tank 48' is provided, which allows pure water to be appropriately supplied into the water storage tank 48 from the pure water supply source through the pure water supply pipe 52. In addition, as shown in FIG. 3, when a plurality of washing treatment units are provided downstream of the washing treatment unit 10 as described above, the washing treatment units located on the most downstream side can be sequentially sent to each washing treatment unit located on the upstream side. The used pure water in the water storage tank is supplied to the water storage tank 48 of the water washing treatment unit 10. Next, an example of the processing operation in the water-washing processing unit 10 having the configuration shown in Fig. 1 will be described with reference to the flowchart shown in Fig. 1. In this processing operation, the liquid outflow pipe 42 may not be provided with a pH meter 48 first. The substrate W with the peeling liquid 丨 attached on its surface is transferred from the peeling processing section to the water washing processing section 10, and the substrate w is carried into the processing chamber 12 of the water washing processing section 10 through the inlet-side opening 4. At this time, the on-off control valves Vi, V2 and% are opened, and the on-off control valves Vs and% are closed. Therefore, only the cleaning liquid is sprayed from the inlet nozzle 20 and the upper nozzle 22, and the cleaning liquid is not sprayed from the lower nozzle 24. Next, the substrates that have been carried into the processing chamber 12 are washed by a curtain-like cleaning solution sprayed from the inlet 20, and the majority of the peeling liquid factory attached to the surface is rinsed. In addition, the cleaning liquid ejected from the upper nozzle 22 to the surface of the substrate w rinses the peeling liquid remaining on the surface of the substrate w. At this time, a solution in which a stripping solution containing amine and a cleaning solution (pure water) are mixed can be generated on the substrate w. However, since carbon dioxide is dissolved in the cleaning solution, neutralizing the alkalinity of the amine can prevent the solution from forming strong sensitivity.

O: \ 89 \ 89957.DOC -19- 1236050 Use the roller conveyor 18 to further transport the base cymbals. When the base cymbals have completely passed the position directly below the inlet nozzle 2G, the on / off control valve is opened, the% and the switch is closed. In the state of the control valve V4, the on-off control valve is closed, and on the other hand, the on-off control valve V3 is opened. Therefore, the cleaning liquid can be ejected only from the upper nozzle 22 and the lower nozzle P24, and the spraying of the cleaning liquid from the inlet nozzle 20 can be stopped. Next, the substrate w in the processing chamber 12 can be transported by the roller conveyor 18, and most of the peeling liquid remaining on the surface of the substrate w can be washed by the cleaning liquid sprayed from the upper nozzle 22 of the k. In addition, the cleaning liquid sprayed from the lower nozzle 24 to the lower surface of the substrate W can wash the peeling liquid coated on the lower side of the substrate boundary. In addition, the switching control valve V3 'may not necessarily be opened at the same time that the switching control valve V% is closed. Open the on / off control valve%, and then close the on / off control valve

Vi 〇 Before the time when the substrate W is carried into the processing chamber '12, the opening and closing control valve V5 is opened, so that the nozzles can be ejected from the inlet nozzle 20, the upper nozzle 22, and the lower nozzle 24 to the substrate w, and upward from the substrate w. The used cleaning liquid flowing down from the bottom of the processing chamber can flow out from the bottom of the processing chamber 12 to the liquid outflow pipe 42, and can be discarded from the liquid outflow pipe 42 through the liquid discharge pipe 46. Then, the cleaning liquid 'can be ejected from the upper nozzle 22 and the lower nozzle 24 to the upper and lower surfaces of the substrate W, and when the peeling liquid 1 is mostly washed away from the substrate ..., the on-off control valve V2 is opened. V3, and the switch control valve V1 is closed, the switch control valve Vs is closed, and on the other hand, the switch control valve v4 is opened. In this way, the used cleaning liquid flows from the bottom of the processing chamber 12 through the liquid outflow pipe 42 and the recovery pipe 44 into the water storage tank 36, and is mixed with the pure water 2 in the water storage tank 36. At this point ', since the peeling liquid 1 attached to the upper surface of the substrate W is cleaned by the cleaning liquid

O: \ 89 \ 89957.DOC -20- 1236050 The large W-knife is rinsed and discarded through the drainage pipe 46. Therefore, the used cleaning solution contains almost no amine. In this way, even if the used cleaning solution is returned to the water storage tank 36, there is little possibility that the cleaning solution (pure water 2) in the water storage tank 36 is mixed with the amine. Therefore, no problem occurs in the substrate that can be processed. When passing through the upper nozzle 22 and the lower nozzle 24, the substrate w of the peeling liquid 1 adhering to the surface is rinsed and washed away with the cleaning liquid from the upper nozzle 22 and the lower nozzle 24, respectively. The inside of the chamber 2 is carried out through the outlet-side opening 16 and is carried to an adjacent washing treatment unit or the like. The substrate material is taken out from the processing room 12, the switch control room% is continuously opened, and the switch control valves v3, v4 are closed, and the switch control rooms v ^, V5 are opened to return to the original state. Next, the substrate W after the peeling treatment to be rinsed is transferred to the water-washing treatment section 10, and the above-mentioned processing operation is repeatedly performed. In the above-mentioned processing operation, the point at which the peeling heart is almost washed out from the substrate W after a certain period of time has elapsed from the substrate in the processing room factory is considered, and the switching operation of the switching control valves v4 and v5 is switched by this time. The used cleaning liquid discarded through the drainage pipe 46 flows into the water storage tank 36 through the recovery pipe 44 to be recovered, but it can also be switched by changing the pH value of the 2 cleaning liquid by flowing out from the bottom of the processing chamber 12 On and off of the control valve I%. That is, as the washing process progresses, the stripping solution i: 'on the substrate W is washed to reduce the amount of amine, and when the stripping solution 1 is still slightly removed from the substrate W ^, the pH of the used cleaning solution is increased.僬 舻 卜 4 / Βί Into the liquid outflow pipe 42_, can hold =: side. Therefore, r ^ is used to measure the pH value of the used 4 fluids inside the flow ’and send the measurement signal to the controller 50.

DOC O: \ 89 \ 8Q957 '21-1236050 The pH value of the cleaning solution is on the acidic side ^ to switch control valves V4 and V5, and close control valve V5. In this way, the used cleaning liquid at this point can be recovered by recycling. The control is transmitted from the controller 50 to open the on-off control valve v4 and close the opening to the receiving pipe 44 discarded through the drain pipe 46 and flow into the water storage tank 36. In addition, in the above-mentioned embodiment, it will be used to measure The pP ^ t48 of the pH value of the used cleaning solution discharged from the bottom 12 is inserted into the liquid outflow tube 42, but in addition to the pH material, a detector that can detect a decrease in the amount of amine contained in the used cleaning solution can be used, such as' A detector for detecting the electrical conductivity or resistivity of the used cleaning solution may also be provided. In addition, with these detectors, the used cleaning solution is discarded before the amount of amine contained in the used cleaning solution is below a certain value. After the amount of amine is below a certain value, the substrate is removed from the processing chamber. The cleaning solution is recycled to the water storage tank (recovery tank) and then reused. In the above-mentioned embodiment, an example of using the present invention in the rinsing process after the peeling process was described. However, the present invention can also be applied to the rinsing process performed after the etching process or after the development process. In addition, when the present invention is used in the rinsing treatment after the etching treatment or the development treatment, since the used cleaning solution is made alkaline by the amine in the stripping solution and is dissolved, the problem of corroding the metal film is eliminated. The following control is not necessarily performed: Often, one of the switching control valves V4, V5 is fully opened or the other is fully closed. Among the substrate processing methods in the scope of claims 1 to j, and the substrate processing methods in the scope of patent applications 4 to 6, the amount of pure water used as a cleaning solution can be further reduced, and the consumption of carbon dioxide can be reduced. Then, O: \ 89 \ 89957 DOC -22-1236050 allows the used cleaning liquid to be recovered and reused, and no problem will occur on substrates that can be processed. [Brief Description of the Drawings] Fig. 1 is a schematic front cross-sectional view showing an example of an embodiment of the present invention, showing a schematic configuration of a substrate processing apparatus. Fig. 2 is a flowchart for explaining an example of processing operations in a water washing processing section of the substrate processing apparatus shown in Fig. 1. Fig. 3 is a schematic front view showing an example of a schematic configuration of a conventional substrate processing apparatus having a water-washing processing section capable of using pure carbon dioxide dissolved pure water as a cleaning solution.

[Schematic representation of symbol W substrate peeling liquid 2 pure water 10 12 14 16 18 20 22 24 26, 28, 30 32a, 32b Washing treatment unit processing chamber processing chamber inlet side opening processing chamber outlet side opening roller conveyor Inlet nozzle Upper nozzle Lower nozzle Cleaning liquid supply piping

O: \ 89 \ 89957 DOC -23-1236050 34 Pump 36 Water storage tank 38 Gas dissolution module 40 Gas supply pipe 42 Liquid outflow pipe 44 Recovery pipe 46 Liquid discharge pipe 48 pH meter 50 Controller 52 Pure water supply pipe Vr V5 On-off Control Valve O: \ 89 \ 89957 DOC ~ 24-

Claims (1)

1236050 Patent application park: 1. A substrate processing method, characterized in that one side of the substrate is transported in the processing chamber, and the other side sprays the cleaning liquid onto the substrate from the vicinity of the population arranged in the processing chamber. The inlet nozzle and the substrate transfer path are arranged above and below the substrate transfer path, respectively, and are connected along the substrate transfer path to scoop out the washing liquid to the upper and lower nozzles above and below the substrate, and supply the cleaning liquid to the substrate. Process the substrate; and have the following steps: (a) the step of supplying the cleaning liquid to the substrate from the inlet nozzle and the uranium upper nozzle at the beginning of moving the substrate into the processing chamber; (b) after the completion of the step (a), until Steps for substrates to be removed from the processing chamber, and cleaning liquid to be supplied to the substrate from the upper and lower nozzles of Lishu; (c) Used substrates discharged from the bottom of the processing chamber after the substrates are moved into the processing chamber until a certain period of time has elapsed The step of discarding the cleaning solution; and (d) after the completion of the above step (c), until the substrate is removed from the processing chamber, the used cleaning solution is removed Close to the recovery tank and the step of re-use; transported to the substrate after said substrate processing chamber based IT release process and peeling solution in 3 above is attached as an amine, the washing liquid based carbon dioxide dissolved in the cleaning liquid pure water. A substrate processing method, characterized in that, while a substrate is being transported in a processing chamber, a cleaning liquid is sprayed onto an upper surface of the substrate from a nozzle disposed near the entrance of the processing chamber and curtain-shaped, and across the substrate transport path. Above and below it are connected along the substrate conveying path and spray the cleaning liquid to the upper and lower nozzles above and below the substrate, and supply clean O: \ 89 \ 89957.DOC 1236050 washing liquid to the substrate to process the substrate. And have the following steps: (a) the initial step of moving the substrate into the processing chamber, the step of supplying the cleaning liquid to the substrate from the inlet nozzle and the upper nozzle; (b) just after the completion of step (a), until the substrate is removed from the substrate; The step of carrying out the processing chamber and supplying the cleaning liquid to the substrate from the upper nozzle and the lower nozzle; (c) continuously measuring and displaying the indicated value of the amount of amine contained in the used cleaning liquid discharged from the bottom of the processing chamber, The step of discarding the used cleaning solution until the measured indication value meets certain conditions; and (d) until the other measured indication value satisfies the foregoing The substrate is transported to the inside in a predetermined condition, and the used cleaning liquid is recovered to a recovery tank for reuse. The substrate transferred to the aforementioned processing chamber is a substrate after peeling treatment, and an amine-containing peeling liquid is attached to the substrate. The cleaning solution is a cleaning solution in which carbon dioxide is dissolved in pure water. 3. If the substrate processing method of item 2 of the patent application range, wherein the aforementioned indication value is a pH value, then step (c) is a step of discarding the used cleaning solution until the measured pH value becomes below a specific value; (D) Step (d) is a step until the measured value of ^] ^ is equal to or less than a specified value and the substrate is removed from the processing chamber described above, and the used cleaning liquid is recovered to a recovery tank and then used. 4. A substrate processing device, comprising: everywhere, it is used for substrate processing; O: \ 89 \ 89957 DOC! 236605, substrate transfer means, it is used to transfer substrates in the processing chamber; It is arranged near the entrance of the processing chamber and sprays the cleaning liquid onto the substrate in a curtain shape; the upper nozzle and the lower nozzle are located in the processing chamber above and below the substrate conveying path, respectively. They are arranged along the substrate conveying path and spray the cleaning liquid onto the upper and lower surfaces of the substrate; the first to third cleaning liquid supply pipes are connected to the inlet nozzle, the upper nozzle, and the lower nozzle, respectively; and the cleaning liquid The supply means is to supply the monthly cleaning liquid to the inlet nozzle, the upper nozzle, and the lower nozzle through the respective cleaning liquid supply pipes, and further includes: (a) the second to the second switching control valves, which are referred to Each tube inserted into the aforementioned first to second cleaning liquid supply piping; (b) A drainage pipe, which is to discard the used cleaning liquid discharged from the bottom of the processing chamber (C) a fourth on-off control valve, which is inserted into the aforementioned drainage pipe; (d) a recovery pipe, which is used to recover the used cleaning liquid; (e) a fifth on-off control valve, which is inserted In the aforementioned recovery piping; (f) a recovery tank that recovers the used cleaning liquid discharged from the bottom of the processing chamber through the recovery piping; and (g) a control hand & which controls the first The fifth to fifth switches control each of the switching operations. For the substrate transferred to the processing chamber is a substrate after peeling treatment and an amine-containing peeling solution is attached to the substrate, the cleaning solution has dioxygen dissolved in pure water. 0: \ 89 \ 89957 DOC 1236050 Carbonized cleaning liquid; The aforementioned control means respectively control: The first action is to open the first on-off control valve and the second on-off control valve at the beginning of moving the substrate into the processing chamber, and then until The substrate is carried out from the processing chamber, the second on-off control valve and the third on-off control valve are opened, and the second operation is performed after the substrate is moved into the processing chamber until a specific time elapses. The fourth switch control valve is opened and the fifth switch control valve is closed, and thereafter, until the substrate is removed from the processing chamber, the fifth switch control valve is closed and the fourth switch control valve is closed. 5. · A substrate processing apparatus, comprising: processing to "the system performs substrate processing; substrate transfer means for transferring substrates in a processing chamber; entrance nozzle" is arranged near the entrance of the processing chamber and The cleaning liquid is sprayed onto the substrate in a curtain shape; the upper nozzle and the lower nozzle are connected to the processing chamber, and are arranged above and below the substrate conveying path through the base conveying path, respectively, and are connected along the substrate conveying path. Sprayed onto the upper and lower sides of the substrate; the first to third cleaning liquid supply pipes are connected to the inlet nozzle, the upper nozzle, and the lower nozzle, respectively; and the cleaning liquid supply means is provided through the foregoing cleaning liquids Piping to supply the smart washing liquid to the inlet nozzle, the upper nozzle, and the lower nozzle, respectively; and further comprising: σ, (a) first to third on-off control valves which are inserted between the first to Oth : \ 89 \ 89957 DOC! 236〇5 02 each pipe of cleaning liquid supply piping; (b) drainage piping, which is the waste of cleaning liquid discharged from the bottom of the processing chamber; (C) The fourth on-off control valve is inserted into the aforementioned drainage pipe. (D) The recovery pipe is used to recover the used cleaning liquid; (e) The fifth on-off control valve is inserted into the aforementioned recovery pipe. With piping; total (f) recovery tank, which is used to recover the used cleaning liquid discharged from the bottom of the processing chamber through the recovery word;-(§) phase means, which are continuously measured and displayed from the processing chamber Indicative value of the amount of amine contained in the used cleaning solution at the bottom; and (h) a control means that controls each of the aforementioned switching operations of the first £ w ^; and is transferred to the aforementioned processing chamber by the control of the fifth switch. If the substrate is a substrate after the peeling process and the peeling liquid on the substrate, the aforementioned cleaning solution is a cleaning solution in which pure dioxide is dissolved in pure water, and the aforementioned control means of the sheep knives are separately controlled. The second processing chamber: the on-off control valve and the second on-off control: When the processing room is moved out, open the second on-off control valve and the second on-off control valve; and ==, which is based on the measurement hand According to the paragraph, "The amine contained in the washing solution becomes special ... 1. If the specific conditions are met, switch on the control valve with the indicated value of the measurement. The current two: Close the control room and close the fifth phase. After specific conditions O: \ 89 \ 89957 DOC 1236050 Until the substrate is removed from the aforementioned processing chamber, open the aforementioned fifth switch control and close the fourth switch control valve described above. 6.::::Substrate processing in item 5 of the patent scope Device, wherein the aforementioned indication value is the pH value; the second action is performed until the measured intermediate value becomes below the special value, = the fourth switch control room and the fifth opening is closed = the special value is below the specific value until the substrate is widened from the aforementioned room. · Close the control valve and close the aforementioned fourth switch control O: \ 89 \ 89957.DOC