Patent Publication Number: US-8980114-B2

Title: Film removing method, nozzle for removing film, and film removing device

Description:
TECHNICAL FIELD 
     The present invention relates to a method for removing a film formed on a substrate, and also relates to a nozzle for removing a film and a film removing device that are used for the application. 
     BACKGROUND ART 
     Japanese Patent Laid-Open Publication No. 2008-018301 discloses a method in which a coating film is removed in a desired pattern by relatively moving a stage on which a substrate is placed while making a suction port of a suction nozzle contact a wet coating film formed on the substrate and suck the coating film. 
     CITATION LIST 
     Patent Literature 
     Patent Literature 1: Japanese Patent Laid-Open Publication No. 2008-018301 (see  FIG. 1  and  FIG. 3 ) 
     SUMMARY OF INVENTION 
     Technical Problem 
     The method disclosed in Japanese Patent Laid-Open Publication No. 2008-018301 may damage a film formed on the substrate and the substrate itself because this method is a contact type method. In addition, this method is not applicable to a film in a dry state. It is to be noted that although disclosing, as a modified preferred embodiment, the wet state is promoted by spraying wet state promoting liquid onto a coating film in a wet state, Japanese Patent Laid-Open Publication No. 2008-018301 does not describe or suggest whether this method is applicable to a film in a dry state. It is also clear that a film in a wet state cannot be formed easily enough to follow a required process speed even if the method is applied to a film in a dry state. 
     On the one hand, the method disclosed in Japanese Patent Laid-Open Publication No. 2008-018301 causes a problem that when the moving speed of a stage is excessively increased, a coating film cannot be sucked well and may remain without being sucked. On the other hand, when the sucking speed of the coating film is excessively increased, a problem that the coating film may be sucked more than necessary may also be caused. Thus, the efficiency of a process is low. 
     In order to resolve the above technical problems, it is an object of the present invention to provide a film removing method in which a film in a dry state can efficiently dissolved and removed, a nozzle for removing a film, and a film removing device. 
     Solution to Problem 
     A film removing method according to a preferred embodiment of the present invention includes steps of: moving a nozzle head close to a soluble film formed on a substrate; forming a liquid pool of chemical liquid between the nozzle head and the film by continuously and simultaneously discharging and sucking the chemical liquid from the nozzle head; and horizontally moving the substrate in a state in which the nozzle head and a surface of the film are not contacted so as to relatively move the liquid pool of the chemical liquid on the substrate. 
     Alternatively, a film removing method according to another preferred embodiment of the present invention includes steps of: moving a nozzle head close to a soluble film formed on a substrate; forming a liquid pool of chemical liquid between the nozzle head and the film by continuously and simultaneously discharging and sucking the chemical liquid from the nozzle head; and horizontally moving the nozzle head on the substrate in a state in which the nozzle head and a surface of the film are not contacted so as to move the liquid pool of the chemical liquid on the substrate. 
     This configuration makes it possible to form a liquid pool of the chemical liquid, by surface tension, between the nozzle head close to the surface of the film and the soluble film and to dissolve a part of the film in contact with the liquid pool. This liquid pool is continuously formed by the continuously discharged chemical liquid and the continuously sucked chemical liquid while being always replaced with new chemical liquid. Then, the chemical liquid that has dissolved the part of the film is sucked, and accordingly, the part of the film is removed. Furthermore, the liquid pool is also moved on the substrate along with the horizontal movement of the substrate or the nozzle head, so that the film can be removed in accordance with a movement track of the substrate or the nozzle head. 
     Moreover, air may be preferably injected into a chemical liquid discharge passage of the nozzle head, so that a flow velocity of the chemical liquid that flows through the chemical liquid discharge passage of the nozzle head will be accelerated by air, and the chemical liquid will come to be squirted (sprayed) from a discharge port of the chemical liquid discharge passage. This applies a mechanical impact to the film and promotes the dissolution and removal of the film by the liquid pool. 
     In the case of a film in which the above described film is made of a solution or a dispersion, as chemical liquid that dissolves the film, chemical liquid constituting the solution and the dispersion may be preferably used. It should be noted if the film is water soluble, water can be used as the chemical liquid, which will contribute to reduce process costs. 
     A nozzle for removing a film according to a preferred embodiment of the present invention may preferably include a nozzle head having a chemical liquid discharge passage and a chemical liquid suction passage that are formed hollow. The nozzle for removing a film may preferably have a configuration in which the nozzle head has a tip end surface, the tip end surface includes a linear groove, and a discharge port of the chemical liquid discharge passage and a suction port of the chemical liquid suction passage are open to the both ends of the linear groove. 
     A droplet scattering suppression wall may be preferably provided around the nozzle head, which can suppress a splash of the chemical liquid from being scattered in a wide range of the surface of the film due to impact caused when the chemical liquid is discharged from the nozzle head. In this case, it is more effective when air in space surrounded by the droplet scattering suppression wall is sucked. 
     It is to be noted the nozzle for removing a film according to a preferred embodiment of the present invention, in the above described configuration, may preferably have a configuration in which an air injection passage in which air is injected into the chemical liquid discharge passage is connected to the chemical liquid discharge passage. 
     In addition, a film removing device according to a preferred embodiment of the present invention may preferably include the above described nozzle for removing a film. The film removing device may preferably include: a stage on which a substrate is placed; a chemical liquid supply portion that supplies chemical liquid to the chemical liquid discharge passage; and a chemical liquid suction portion that sucks the chemical liquid from the chemical liquid suction passage. 
     It should be noted in a case of the nozzle for removing a film having a configuration in which the air injection passage in which air is injected into the chemical liquid discharge passage is connected to the chemical liquid discharge passage, the film removing device according to a preferred embodiment of the present invention may preferably further include an air supply portion that supplies air into the air injection passage. 
     Additionally, the film removing device according to a preferred embodiment of the present invention may preferably configure the stage as a stage capable of moving in a horizontal direction or may preferably include a nozzle moving portion that horizontally moves the nozzle for removing a film. 
     Advantageous Effects of Invention 
     According to the preferred embodiments of the present invention, a film in a dry state can be efficiently dissolved and removed. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic configuration view illustrating a film removing device according to a first preferred embodiment of the present invention. 
         FIG. 2A  is a partially cutaway side view illustrating a nozzle for removing a film,  FIG. 2B  is a bottom view illustrating the nozzle for removing a film,  FIG. 2C  is a cross sectional view taken as viewed from an arrow line II-II in  FIG. 2A , and  FIG. 2D  is an enlarged view illustrating a tip portion of a nozzle head in  FIG. 2C . 
         FIG. 3A  to  FIG. 3C  are explanatory views schematically illustrating each step of a film removing method according to preferred embodiments of the present invention. 
         FIG. 4  is a cross sectional view taken as viewed from an arrow line IV-IV in  FIG. 3B . 
         FIG. 5  is a schematic configuration view illustrating a film removing device according to a second preferred embodiment of the present invention. 
         FIG. 6  is a schematic configuration view illustrating a film removing device according to a third preferred embodiment of the present invention. 
         FIG. 7  is a table showing respective film removal characteristics when a flow rate of supplying chemical liquid to the nozzle for removing a film is excessively low, appropriate, or excessively high. 
         FIG. 8A  is a schematic view illustrating a way of a flow of chemical liquid that flows between a nozzle head and a substrate when the flow rate of supplying chemical liquid to a nozzle for removing a film is excessively low,  FIG. 8B  is a schematic view illustrating a way of the flow of the chemical liquid that flows between the nozzle head and the substrate when the flow rate of supplying the chemical liquid to the nozzle for removing a film is appropriate, and  FIG. 8C  is a schematic view illustrating a way of the flow of the chemical liquid that flows between the nozzle head and the substrate when the flow rate of supplying the chemical liquid to the nozzle for removing a film is excessively high. 
         FIG. 9A  is a sectional view taken along a line IX-IX in  FIG. 8A ,  FIG. 9B  is a sectional view taken along a line IX-IX in  FIG. 8B , and  FIG. 9C  is a sectional view taken along a line IX-IX in  FIG. 8C . 
         FIG. 10A  is a view illustrating a state of a cross section of a film removed region formed when the flow rate of supplying chemical liquid to the nozzle for removing a film is excessively low,  FIG. 10B  is a view illustrating a state of a cross section of a film removed region formed when the flow rate of supplying the chemical liquid to the nozzle for removing a film is appropriate, and  FIG. 10C  is a view illustrating a state of a cross section of a film removed region formed when the flow rate of supplying the chemical liquid to the nozzle for removing a film is excessively high. 
         FIG. 11A  is a schematic view illustrating a chemical liquid scattering preventive mechanism provided in the nozzle for removing a film, and  FIG. 11B  is a bottom view of the nozzle for removing a film equipped with a droplet scattering suppression wall. 
         FIG. 12  is a schematic view illustrating a chemical liquid heating mechanism. 
         FIG. 13  is a view illustrating states of a cross section of a film removed region formed when chemical liquid at a room temperature is supplied to the nozzle for removing a film and when heated chemical liquid is supplied to the nozzle for removing a film. 
         FIG. 14A  and  FIG. 14B  are schematic views illustrating an operation method for each object of the film removing device. 
         FIG. 15  is a view illustrating a cross section of a film removed region formed according to an operation method of the film removing device. 
     
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     First Preferred Embodiment 
     The schematic configuration of a film removing device according to a first preferred embodiment of the present invention will be described with reference to  FIG. 1  and  FIG. 2 . As illustrated in  FIG. 1 , the film removing device  1  includes a nozzle  10 , an air cylinder  20 , pipes  30  to  37 , regulators  41  to  43 , switch valves  51  to  54 , a pressure bottle  60 , a waste liquid bottle  70 , a vacuum ejector  80 , a flow rate controller  90 , and a movable stage  100 . 
     The nozzle  10 , as illustrated in  FIG. 2 , includes a nozzle base  10 A and a nozzle head  10 B. As the material of the nozzle  10 , metals having corrosion resistance to chemical liquid, such as stainless steel, are preferably used. The nozzle base  10 A has a square pole shape and the nozzle head  10 B has a truncated quadrangular pyramidal shape, and both are integrally formed with each other. 
     As illustrated in  FIG. 2A , further provided is a pair of round cross sectional hollow portions (see a vertical hollow portion composed of a downstream side of the chemical liquid discharge passage  112  and the air injection passage  14 , and a vertical hole composed of the chemical liquid suction passage  12 ) that vertically penetrate the nozzle base  10 A and the nozzle head  10 B in such a manner as to be spaced apart from each other in the longitudinal direction of the nozzle head  10 B. The upper ends of the hollow portions are open to the upper surface of the nozzle base  10 A (see connection ports  14 A and  12 B.) The lower ends of the hollow portions are open to the lower surface of the nozzle head  10 B (see a discharge port  11 A and a suction port  12 A.) 
     At a midway point of the hollow portion on the left side as viewed in  FIG. 2A , another hollow portion (see a horizontal hole composed of an upstream side of the chemical liquid discharge passage  111 ) is connected in a perpendicular direction. The hollow portion (see a connection port  11 B) is open to an end face of the nozzle base  10 A. The connection ports  11 B,  12 B, and  14 A are connected to pipes, respectively. 
     The chemical liquid discharge passage  11  includes the upstream side of the chemical liquid discharge passage  111  and the downstream side of the chemical liquid discharge passage  112 . As illustrated, a link portion of both discharge passages  111 ,  112  is connected to the air injection passage  14  so that air can be injected into the chemical liquid flowing through the chemical liquid discharge passage  11 . 
     While a distance (see “P” in  FIG. 2A ) between the downstream side of the chemical liquid discharge passage  112  and the chemical liquid suction passage  12  is not limited, the distance may be set to about 1 to 15 mm, for example. A diameter of the chemical liquid suction passage  12  is set equal to or larger than the diameter of the chemical liquid discharge passage  11 . For example, the diameter of the chemical liquid discharge passage  11  is set to 1 mm and the diameter of the chemical liquid suction passage  12  is set to 2 mm. 
     As illustrated in  FIG. 2B , the tip end surface (the bottom surface) of the nozzle head  10 B includes a groove  13  on a straight line along with the longitudinal direction of the nozzle head  10 B. According to the preferred embodiment of the present invention, as illustrated in  FIG. 2D , a sectional shape of the groove  13  is formed into a semicircular shape. While a width and a depth of the groove  13  are not limited, the width and the depth are set to about 0.1 mm to 1.0 mm, for example. The discharge port  11 A of the chemical liquid discharge passage  11  and the suction port  12 A of the chemical liquid suction passage  12  are open to both ends of the groove  13 , respectively. 
     As illustrated in  FIG. 1 , the nozzle  10  is attached to the film removing device  1  by being fixed to a support element  2  placed in the horizontal direction above the movable stage  100  by screwing through a machine screw. 
     The pipes  30  to  33 ,  36 , and  37  illustrated by outline arrows in  FIG. 1  are pipes through which air flows, and the pipes  34  and  35  illustrated by solid arrows are pipes through which chemical liquid flows. It is desirable for these pipes to use a pipe of which material has resistance to pressure. 
     The air cylinder  20  stores compressed air. The pipe  30  is connected to this air cylinder  20 , and, furthermore, three pipes  31  to  33  are connected to this pipe  30  in parallel. Each of the pipes  31  to  33  includes the regulators  41  to  43  and the switch valves  51  to  53 . The regulators  41  to  43  regulate the flow rate of the air that flows through the pipes  31  to  33 . The switch valves  51  to  53  switch on and off of the circulation of air that flows through the pipes  31  to  33 . 
     The downstream end of the pipe  31  is connected to the air injection passage  14  of the nozzle  10  so as to supply air to the nozzle  10 . The downstream end of the pipe  32  is introduced into the pressure bottle  60 . The pressure bottle  60  is an airtight container that stores the chemical liquid  300 . 
     The upstream end of the pipe  34  is inserted under the surface of the chemical liquid  300  in the pressure bottle  60 . The pipe  34  includes the switch valve  54  and the flow rate controller  90 . The switch valve  54  switches on and off of the circulation of chemical liquid that flows through the pipe  34 . The flow rate controller  90  controls the flow rate of the chemical liquid which flows through the pipe  34 . The downstream end of the pipe  34  is connected to the connection port  11 B of the chemical liquid discharge passage  11  of the nozzle  10 . 
     As the chemical liquid  300 , liquid that dissolves the film  201  on the substrate  200  is preferably used. In particular, when the film  201  is water soluble, water that is easy to be obtained and handled can be used as liquid that dissolves a film, so that process costs can be reduced. 
     The upstream end of the pipe  35  is connected to the connection port  12 B of the chemical liquid suction passage  12  of the nozzle  10 . The downstream end of the pipe  35  is introduced into the waste liquid bottle  70 . The waste liquid bottle  70  is an airtight container that stores the chemical liquid  301  which has dissolved the film  201 . 
     The downstream end of the pipe  33  is connected to an air feed port of the vacuum ejector  80 . The upstream end of the pipe  36  is inserted into the waste liquid bottle  70 . The downstream end of the pipe  36  is connected to an air inlet port of the vacuum ejector  80 . The upstream end of the pipe  37  is connected to an air exhaust port of the vacuum ejector  80 . The downstream end of the pipe  37  is open to an external exhaust line. The pipes  33 ,  36 , and  37  define a vacuum line. 
     The movable stage  100  is configured to be capable of horizontally moving in the XY direction. The substrate  200  is placed on the movable stage  100 . While a moving speed of the movable stage  100  is not limited, the moving speed is set to 50 mm/s, for example. 
     The film  201  in a dry state is formed on the substrate  200 . The film  201  is a film consisting of substance  201 A having a property of dissolving the chemical liquid  300 . While a thickness of the film  201  is not limited, the thickness is preferably set to be 1 μm or less. It is to be noted that film removal to be described below can be efficiently performed by previously applying plasma, UV rays, and the like to the film  201  to decrease the film strength. 
     Subsequently, a film removing method using the film removing device  1  configured as described above will be described with reference to  FIG. 1 ,  FIG. 3 , and  FIG. 4 . 
     To begin with, the nozzle head  10 B of the nozzle  10  is moved closer to the soluble film  201 . At this time, while a distance (see “L” in  FIG. 1 ) between the tip of the nozzle head  10 B and the surface of the substrate  200  is not limited, the distance may be set to about 50 μm, for example. Since a thickness of the film  201  is set to 1 μm or less, such a distance L is suitable to maintain a state in which the nozzle head  10 B is non-contact with the film  201  while the distance between the tip of the nozzle head  10 B and the surface of the film  201  is made as small as possible. In addition, since the tip of the nozzle head  10 B, the film  201 , and the substrate  200  are not contacted, the film removing method of the preferred embodiments according to the present invention can be a process in which the smoothness of the surfaces of the film  201  and the substrate  200  is not required severely and a process in which a film remaining after patterning and the substrate itself are not damaged. 
     Then, while the air cylinder  20  is opened, the regulators  41  to  43 , the switch valves  51  to  54 , and the flow rate controller  90  are properly controlled. Accordingly, air is supplied to the air injection passage  14  of the nozzle  10  through the pipe  31 . Air is also supplied to an enclosed space of the pressure bottle  60  through the pipe  32 , the chemical liquid  300  is pressed out to the pipe  34 , and the chemical liquid  300  is supplied to the chemical liquid discharge passage  11  of the nozzle  10  through the pipe  34 . The pressure of the supplied chemical liquid  300  is regulated by the regulator  54  so as to be set to 0.05 MPa, for example. The final fluid volume of the chemical liquid is controlled by the flow rate controller  90 . Thus, as illustrated in  FIG. 3A , the chemical liquid  300  is discharged from the discharge port  11 A of the chemical liquid discharge passage  11  of the nozzle  10  toward a space between the tip end surface of the nozzle head  10 B and the substrate  200 . 
     Further, air is press injected into the vacuum ejector  80  through the pipe  33 . The air is exhausted and diffused from the air exhaust port of the pipe  37  and discharged to the external exhaust line through the pipe  37 . As a result, the air inlet port of the vacuum ejector  80  becomes in a negative pressure state, and the air in the enclosed space in the waste liquid bottle  70  is sucked through the pipe  36 . Then, the inside of the waste liquid bottle  70  becomes in the negative pressure state, and the air in the chemical liquid suction passage  12  of the nozzle  10  is sucked through the pipe  35 . By the suction of air, as illustrated in  FIG. 3A , the chemical liquid  300  discharged to the space between the tip end surface of the nozzle head  10 B and the substrate  200  is sucked from the suction port  12 A of the chemical liquid suction passage  12 . 
     Thus, between the tip end surface of the nozzle head  10 B and the film  201  (the substrate  200 ), the chemical liquid  300  flows from the discharge port  11 A of the chemical liquid discharge passage  11  toward the suction port  12 A of the chemical liquid suction passage  12  by use of the groove  13  on the straight line of the tip end surface of the nozzle head  10 B as a guide, and a liquid pool  302  is formed by surface tension. The groove  13 , as illustrated in  FIG. 4 , suppresses the liquid pool  302  from spreading, so that the chemical liquid is hard to drip to the outside of the nozzle head  10 B, thereby contributing to improvement in accuracy of film removal. 
     As described above, since the diameter of the chemical liquid suction passage  12  is set to become larger than the diameter of the chemical liquid discharge passage  11 , the flow rate of the chemical liquid which flows through the chemical liquid suction passage  12  increases relatively. Consequently, the chemical liquid smoothly flows along a U-shaped passage across the chemical liquid discharge passage  11 , the groove  13 , and the chemical liquid suction passage  12 . 
     The chemical liquid dissolves the film  201  of which a part is in contact with the liquid pool  302  as illustrated in  FIG. 3B . This liquid pool  302  is continuously formed by the continuously discharged chemical liquid  300  and the continuously sucked chemical liquid  301  while being always replaced with new chemical liquid. Then, the chemical liquid  301  that has dissolved the part of the film  201  is sucked, and accordingly, the part of the film  201  is removed. The chemical liquid  301  flows through the chemical liquid suction passage  12 , and is discharged to and finally stored in the waste liquid bottle  70  through the pipe  35 . 
     As a result of diligent studies, the inventors of the present invention have found that a state of the liquid pool  302  varies by varying the flow rate of supplying chemical liquid to the nozzle  10  by the flow rate controller  90 , and effective film removal requires a range of a proper flow rate, and the quality of the film removal is downgraded when the flow rate is smaller or larger than the range. 
       FIG. 7  is a table showing a relationship between the flow rate of supplying chemical liquid and the film removal characteristics. As illustrated in  FIG. 7 , when the flow rate of supplying chemical liquid was excessively low (less than the flow rate R 1 ), the suction was prioritized, and the film removal could not be performed. When the flow rate of supplying chemical liquid was appropriate (not less than the flow rate R 1  and less than the flow rate R 2 ), the film removal was effectively performed by pulse impact. When the flow rate of supplying chemical liquid was excessively high (not less than R 2 ), the liquid pool  302  was bloated, and the quality of the film removal was downgraded. It should be noted that the values of R 1  and R 2  (R 1 &lt;R 2 ) as threshold values of the flow rate vary according to the specification of the nozzle  10 , the viscosity of the chemical liquid, and the like. 
     Hereinafter, the reason why the film removal characteristics vary in this way will be described with reference to  FIGS. 8A to 8C ,  FIGS. 9A to 9C , and  FIGS. 10A to 10C . FIGS.  8 A to  8 C and  FIGS. 9A to 9C  are schematic views illustrating how the flow of the chemical liquid which flows between the nozzle head and the substrate changes by the flow rate of supplying chemical liquid.  FIGS. 10A to 10C  are views illustrating with a shape of a cross section of a film removed region how the film removal characteristics change by the flow rate of supplying chemical liquid. 
       FIG. 8A  and  FIG. 9A  illustrate a state in which the flow rate of supplying chemical liquid to the nozzle  10  is excessively low, and at this time, as illustrated by the size of the arrows in the views, the sucked amount of the chemical liquid is excessively larger than the discharged amount of the chemical liquid, so that the chemical liquid  300  does not constantly contact the substrate  200  (the film  201 ). Thus, even if the substrate  200  is horizontally moved, as illustrated in  FIG. 10A , the film  201  will not be removed. 
       FIG. 8B  and  FIG. 9B  illustrate a state in which the flow rate of supplying chemical liquid to the nozzle  10  is appropriate, and at this time, as illustrated by the size of the arrows in the views, the sucked amount of the chemical liquid is well-balanced with the discharged amount of the chemical liquid, and the pulse impact by the liquid pool  302  is applied to the film  201  by repeatedly switching between a state in which the chemical liquid  300  contacts the substrate  200  (the film  201 ) and a state in which the chemical liquid  300  does not contact the substrate  200  (the film  201 ) at high speed. As illustrated in  FIG. 10B , the cross section of a film removed region formed in the film  201  by horizontal movement of the substrate  200  with the movable stage  100  has a film removing width of 1.2 mm and a width of an inclined part of both ends of approximately 0.2 mm. 
       FIG. 8C  and  FIG. 9C  illustrate a state in which the flow rate of supplying chemical liquid to the nozzle  10  is excessively high, and at this time, as illustrated by the size of the arrows in the views, the discharged amount of the chemical liquid is excessively larger than the sucked amount of the chemical liquid, so that the liquid pool  302  is constantly generated on the substrate  200  (the film  201 ) and the chemical liquid tends to overflow. As illustrated in  FIG. 10C , the cross section of a film removed region formed in the film  201  by horizontal movement of the substrate  200  with the movable stage  100  has a film removing width of 2 mm and a width of an inclined part of approximately 0.7 mm. Since the flow rate of supplying chemical liquid is high, the film removing width becomes wider and the edge also becomes broader, which shows that the quality of the film removed region is downgraded. 
     As described above, when the flow rate of supplying chemical liquid to the nozzle  10  is appropriate, the chemical liquid repeats contacting and non-contacting the substrate  200  (the film  201 ), so that the impact causes the chemical liquid to splash and scatter widely, resulting in a possibility that the film  201  is dissolved at a place away from a desired film removed region and a defect can be generated. 
     In view of the foregoing, it is necessary to take suppressive measures against scattering of droplets. Specifically, as illustrated in  FIGS. 11A and 11B , a droplet scattering suppression wall  15  is provided in the surroundings of the nozzle head  10 B and an air exhaust hole  15 A provided at one point in the droplet scattering suppression wall  15  is connected to the pipe  33  for exhausting air. The space surrounded by the droplet scattering suppression wall  15  becomes in a negative pressure state by exhausted air. Thus, the droplets of the chemical liquid that are scattered by pulse impact are sucked into the space and can be suppressed from scattering to a place away from the film removed region. 
     In order to improve the film removing efficiency, the chemical liquid supplied to the nozzle  10  may preferably be heated. Specifically, as illustrated in  FIG. 12 , it is possible to employ a configuration in which a hot water line  91  and a waste water line  92  are connected to a heat exchanger  93  equipped with a spiral tube  95  made of Teflon (registered trademark) and the spiral tube  95  is connected to a midway point of the pipe  34  for supplying chemical liquid. The temperature of hot water that flows through the hot water line  91  is set to 80° C. as an example. According to this configuration, the chemical liquid that flows through the pipe  34  and is supplied to the nozzle  10  is heated to, for example, 40° C. 
     When the film  201  is removed by horizontally moving the substrate  200  with the movable stage  100 , as illustrated in  FIG. 13 , and the heated chemical liquid and the room-temperature chemical liquid were compared with the same horizontal movement speed (80 mm/s in this example) and the same horizontal movement frequency (once in this example), the film removing efficiency was improved remarkably in the case of using the heated chemical liquid compared to using the room-temperature chemical liquid. It is considered because dissolution of binder resin that forms the film  201  was accelerated when heat was applied to the chemical liquid, so that the film removal can be performed more effectively. 
     In addition, air is injected into the chemical liquid  300  that flows through the chemical liquid discharge passage  11  via the air injection passage  14 , so that the flow velocity of the chemical liquid  300  that flows through the chemical liquid discharge passage  11  will be accelerated and the chemical liquid  300  will come to be squirted (sprayed) from the discharge port  11 A of the chemical liquid discharge passage  11 . This applies a mechanical impact to the film  201  by liquid pressure of the chemical liquid and promotes the dissolution and removal of the film  201  by the liquid pool  302 . 
     Further, as illustrated in  FIGS. 3B and 3C , while the movable stage  100  horizontally moves in the XY direction, the liquid pool  302  also moves relatively to the substrate  200  and the film  201  can be removed in accordance with a movement track of the movable stage  100 . The film  201  could be linearly removed with a width of 2 mm by applying the method of the present invention to an approximate 100 nm thick film  201  formed on the substrate  200 . 
     According to the preferred embodiments of the present invention, the film  201  in a dry state can be efficiently dissolved and removed. Moreover, the control of a flow rate and liquid pressure of the chemical liquid, and a moving speed of the stage makes it possible to remove a film that is hard to dissolve. An additional tool such as a heater to heat chemical liquid is also effective. 
     Second Preferred Embodiment 
       FIG. 5  is a schematic configuration view illustrating a film removing device according to a second preferred embodiment of the present invention. While, according to the first preferred embodiment of the present invention, the nozzle  10  is fixed, and the liquid pool  302  of the chemical liquid is relatively moved on the substrate  200  by horizontally moving the movable stage  100 , according to the second preferred embodiment of the present invention, as illustrated in  FIG. 5 , the nozzle  10  may be supported against a movable support element  2 ′, and the liquid pool  302  of the chemical liquid may be moved on the substrate  200  by horizontally moving the nozzle head  10 B on the substrate  200  mounted on a fixed stage  100 ′. It is to be noted that the movable support element  2 ′ is configured to be movable not only in a horizontal direction but in a vertical direction so as to make the nozzle  10  spaced away from the substrate  200 . 
     As for a single horizontal movement of the nozzle  10 , although the film removing width of a film removed region is almost the same even if the horizontal movement speed is fast or slow, the inclined parts on both ends of the film removed region will become gentle and the edge will become loose when the horizontal movement speed is fast while the inclined parts on both ends of the film removed region will become steep and the edge will become sharp when the horizontal movement speed is slow. 
     In this preferred embodiment of the present invention, by having employed a nozzle horizontal movement mechanism with a higher mobility compared to a substrate horizontal movement mechanism, it becomes possible to change an operation method of the film removing device  1  in accordance with purposes of removing a film in the use of differences in film removal characteristics by the above described horizontal movement speed. 
     For example, in a certain operation method, as illustrated in  FIG. 14A , chemical liquid is supplied to/sucked from the nozzle  10  while the nozzle  10  is horizontally moved in a left direction at a slow horizontal movement speed (10 mm/s in this example), then, the chemical liquid stops being supplied/sucked and the nozzle  10  is separated once from the substrate  200  at a goal point, the nozzle  10  is moved in a right direction and returns to a start point, and the chemical liquid is again supplied to/sucked from the nozzle  10  while the nozzle  10  is horizontally moved in the left direction. 
     According to this operation method, the cross section of the film removed region formed in the film  201 , as illustrated as a solid line in  FIG. 15 , had a film removing width of 1.2 mm and a width of the inclined part was approximately 0.2 mm. Therefore, this operation method is suitable for a purpose (giving priority to edge accuracy) requiring edge accuracy on both ends of the film removed region although cycle time becomes slow. 
     In another operation method, as illustrated in  FIG. 14B , while chemical liquid is supplied to/sucked from the nozzle  10 , the nozzle  10  is reciprocated to the right and left to horizontally move on the film  201 . The horizontal movement speed may differ between left movement (forward movement) and right movement (backward movement). In this example, the horizontal movement speed of the left movement is 20 mm/s and the horizontal movement speed of the right movement is 80 mm/s. The reason why the left movement and the right movement have such differences in horizontal movement speed is because process steps for removing a film, such as a process step in which the film removed region of the film  201  is previously moisturized with chemical liquid during the left horizontal movement and in which the moisturized film is removed at once during the right horizontal movement, are clearly separated during between the left horizontal movement and the right horizontal movement, which enhances repeatability of removing a film. 
     According to this operation method, the cross section of the film removed region formed in the film  201 , as illustrated as a broken line in  FIG. 15 , had a film removing width of 1.7 mm and a width of the inclined part was 0.3 mm to 0.4 mm. Thus, this operation method is suitable for a purpose (giving priority to film removing speed) requiring only electric insulation ensured between two regions of the film  201  divided in the film removed region although the edge accuracy of the both ends of the film removed region is decreased. According to this operation method, the cycle time can be shortened. Compared with the previous operation method, the film removing width became wider because the film  201  was previously moisturized and then removed. 
     In any operation method, the number of reciprocating movements of the nozzle  10  is not limited to one and may preferably be increased properly in accordance with characteristics of the film  201 . 
     Third Preferred Embodiment 
       FIG. 6  is a schematic configuration view illustrating a film removing device according to a third preferred embodiment of the present invention. According to the third preferred embodiment of the present invention, the structure of the nozzle  10  is simplified and the configuration in which air is injected into chemical liquid which flows through the chemical liquid discharge passage  11  is omitted. That is, as illustrated in  FIG. 6 , the nozzle  10  has no air injection passage and includes only the chemical liquid discharge passage  11  and the chemical liquid suction passage  12  that are arranged in such a manner as to be spaced apart from each other in the longitudinal direction of the nozzle head  10 B and as to vertically penetrate the nozzle base  10 A and the nozzle head  10 B. 
     According to this preferred embodiment, although chemical liquid cannot be squirted from the discharge port  11 A since air is not injected to the nozzle  10 , it is possible to efficiently dissolve and remove a film when the flow rate of supplying chemical liquid is appropriately controlled by the flow rate controller  90  as described above and the liquid pool  302  formed between the tip end surface of the nozzle head  10 B and the substrate  200  applies pulse impact to the film  201 . 
     The above described embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined not by above described embodiments but by the claims. Further, the scope of the present invention is intended to include all modifications that come within the meaning and scope of the claims and any equivalents thereof. 
     INDUSTRIAL APPLICABILITY 
     The present invention is applicable to the field of organic EL elements and organic semiconductors, that is, applications such as patterning of a film formed on a substrate and removal of a part of a film on a border when multiple substrates are obtained from a film uniformly formed on a single substrate. 
     REFERENCE SIGNS LIST 
     
         
         
           
               1 —film removing device 
               2 —support element 
               2 ′—movable support element (nozzle moving portion) 
               10 —nozzle for removing a film 
               11 —chemical liquid discharge passage 
               12 —chemical liquid suction passage 
               13 —groove 
               14 —air injection passage 
               20 —air cylinder 
               30  to  37 —pipe 
               41  to  43 —regulator 
               51  to  54 —switch valve 
               60 —pressure bottle 
               70 —waste liquid bottle 
               80 —vacuum ejector 
               90 —flow rate controller 
               100 —movable stage 
               100 ′—stage 
               20 ,  30 ,  32 ,  42 ,  52 ,  54 ,  60 ,  34 ,  54 ,  90 —chemical liquid supply portion 
               20 ,  33 ,  35 ,  37 ,  43 ,  53 ,  70 ,  80 —chemical liquid suction portion 
               20 ,  30 ,  31 ,  41 ,  51 —air supply portion 
               300 ,  301 —chemical liquid 
               302 —liquid pool