Patent Publication Number: US-10310383-B2

Title: Exposure apparatus, exposure method, and device manufacturing method

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is a Divisional of U.S. application Ser. No. 14/719,937 filed May 22, 2015 (now U.S. Pat. No. 9,753,378), which is a Divisional Application of U.S. application Ser. No. 13/228,032, filed Sep. 8, 2011 (now U.S. Pat. No. 9,041,902), which is a Continuation Application of International Application No. PCT/JP2010/001695, filed on Mar. 10, 2010, which claims priority to U.S. provisional application No. 61/202,533, filed Mar. 10, 2009, the contents of which are incorporated herein by reference. 
    
    
     BACKGROUND 
     Field of the Invention 
     The present invention relates to an exposure apparatus, an exposure method, and a device manufacturing method. 
     Description of Related Art 
     In exposure apparatuses used in photolithography processes, a liquid immersion exposure apparatus that exposes a substrate with exposure light via a liquid, as disclosed in Patent Document (Specification of US Patent Application Publication No. 2007/0139632), for example, is known. 
     In the liquid immersion exposure apparatus, there is a possibility that liquid filling the optical path of exposure light is charged. Moreover, there is also a possibility that a member contacting the liquid is also charged. Due to the charging, there is a possibility that foreign materials may be adsorbed to at least one of the liquid and the member. As a result, there is a possibility that exposure defects may occur, so that defective devices are produced. 
     SUMMARY 
     An object of aspects of the present invention is to provide an exposure apparatus and an exposure method capable of suppressing the occurrence of exposure defects resulting from charging of liquid or the like. Another object of aspects of the present invention is to provide a device manufacturing method capable of suppressing the occurrence of defective devices. 
     According to a first aspect of the present invention, there is provided an exposure apparatus that exposes a substrate with exposure light via a liquid, including: an optical system including an emission surface from which the exposure light is emitted; a liquid supply port that supplies the liquid in order to fill an optical path of the exposure light emitted from the emission surface with the liquid; and a fluid supply port that supplies a fluid including a material capable of changing the specific resistance of the liquid to at least a part of a space around a liquid immersion space that is formed by the liquid. 
     According to a second aspect of the present invention, there is provided an exposure apparatus that exposes a substrate with exposure light, including: an optical system including an emission surface from which the exposure light is emitted; a first supply port that supplies a first liquid in order to fill an optical path of the exposure light emitted from the emission surface with the first liquid having a first specific resistance; and a second supply port that supplies a second liquid having a lower specific resistance than the first liquid to at least a part of a space around a liquid immersion space that is formed by the first liquid. 
     According to a third aspect of the present invention, there is provided an exposure apparatus that exposes a substrate with exposure light via a liquid, including: an optical system including an emission surface from which the exposure light is emitted; a liquid supply port that supplies the liquid in order to fill an optical path of the exposure light emitted from the emission surface with the liquid; a fluid supply port that supplies a fluid including a material capable of changing the specific resistance of the liquid; and a fluid recovery port that recovers at least some of the fluid from at least a part of a space around a liquid immersion space that is formed by the liquid. 
     According to a fourth aspect of the present invention, there is provided a device manufacturing method including: exposing a substrate using the exposure apparatus according to any one of the first, second, and third aspects; and developing the exposed substrate. 
     According to a fifth aspect of the present invention, there is provided an exposure method including: filling an optical path of exposure light between an emission surface of an optical system and a substrate with a liquid; supplying a liquid including a material capable of changing the specific resistance of the liquid to at least a part of a space around a liquid immersion space of the liquid, formed on the substrate; and exposing the substrate with the exposure light via the liquid between the emission surface and the substrate. 
     According to a sixth aspect of the present invention, there is provided an exposure method including: filling an optical path of exposure light between an emission surface of an optical system and a substrate with a first liquid; supplying a second liquid having a lower specific resistance than the first liquid to at least a part of a space around a liquid immersion space of the first liquid, formed on the substrate; and exposing the substrate with the exposure light via the first liquid between the emission surface and the substrate. 
     According to a seventh aspect of the present invention, there is provided an exposure method including: filling an optical path of exposure light between an emission surface of an optical system and a substrate with a liquid; supplying a fluid including a material capable of changing the specific resistance of the liquid; recovering at least some of the fluid from at least a part of a space around a liquid immersion space of the liquid, formed on the substrate; and exposing the substrate with the exposure light via the liquid between the emission surface and the substrate. 
     According to an eighth aspect of the present invention, there is provided a device manufacturing method including: exposing a substrate using the exposure apparatus according to any one of the fifth, sixth, and seventh aspects; and developing the exposed substrate. 
     According to the aspects of the present invention, it is possible to suppress the occurrence of exposure defects. Moreover, according to the present invention, it is possible to suppress the occurrence of defective devices. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic configuration diagram showing an example of an exposure apparatus according to a first embodiment. 
         FIG. 2  is a cross-sectional view showing the vicinity of a terminating optical element and a liquid immersion member according to the first embodiment. 
         FIG. 3  is a cross-sectional view showing the vicinity of the liquid immersion member according to the first embodiment. 
         FIG. 4  is a cross-sectional view showing the vicinity of the liquid immersion member according to a second embodiment. 
         FIG. 5  is a cross-sectional view showing the vicinity of the liquid immersion member according to a third embodiment. 
         FIG. 6  is a cross-sectional view showing the vicinity of the liquid immersion member according to a fourth embodiment. 
         FIG. 7  is a cross-sectional view showing the vicinity of the liquid immersion member according to a fifth embodiment. 
         FIG. 8  is a cross-sectional view showing the vicinity of the liquid immersion member according to a sixth embodiment. 
         FIG. 9  is a cross-sectional view showing the vicinity of the liquid immersion member according to a seventh embodiment. 
         FIG. 10  is a flowchart illustrating an example of the processes of manufacturing microdevices. 
     
    
    
     DESCRIPTION OF EMBODIMENTS 
     Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments. In the following description, an XYZ orthogonal coordinate system is set, and the positional relationship between respective constituent elements will be described with reference to the XYZ orthogonal coordinate system. A predetermined direction within a horizontal plane is defined as the X-axis direction, a direction orthogonal to the X-axis direction is defined as the Y-axis direction, and a direction (that is, a vertical direction) orthogonal to the X and Y-axis directions is defined as the Z-axis direction. Moreover, the directions of rotation (inclination) about the X, Y, and Z axes are defined as the θX, θY and θZ directions. 
     First Embodiment 
     The first embodiment will be described.  FIG. 1  is a schematic configuration view showing an example of an exposure apparatus EX according to the first embodiment. The exposure apparatus EX of the present embodiment is a liquid immersion exposure apparatus that exposes a substrate P with exposure light EL via a liquid LQ. In the present embodiment, a liquid immersion space LS is formed so that at least a part of the optical path of the exposure light EL is filled with the liquid LQ. The liquid immersion space LS is a portion (space or region) filled with the liquid LQ. The substrate P is exposed with the exposure light EL via the liquid LQ in the liquid immersion space LS. In the present embodiment, water (pure water) is used as the liquid LQ. 
     In  FIG. 1 , the exposure apparatus EX includes a mask stage  1  configured to be movable while holding a mask M, a substrate stage  2  configured to be movable while holding the substrate P, an interferometer system  3  that optically measures the positions of the mask stage  1  and the substrate stage  2 , an illumination system IL that illuminates the mask M with the exposure light EL, a projection optical system PL that projects the image of the pattern on the mask M illuminated with the exposure light EL onto the substrate P, a liquid immersion member  4  capable of forming the liquid immersion space LS so that at least a part of the optical path of the exposure light EL is filled with the liquid LQ, a chamber device  5  that accommodates at least the projection optical system PL and the substrate stage  2 , a body  6  that supports at least the projection optical system PL, and a control device  7  that controls the overall operation of the exposure apparatus EX. 
     The mask M includes a reticle on which a device pattern projected onto the substrate P is formed. The mask M includes a transmissive mask which includes a transparent plate such as, for example, a glass plate, and a pattern formed on the transparent plate using a light shielding material such as chromium. A reflective mask may be used as the mask M. 
     The substrate P is a substrate used for manufacturing devices. The substrate P includes a base such as, for example, a semiconductor wafer, and a multi-layer film formed on the base. The multi-layer film is a film in which a plurality of films including at least a photosensitive film is laminated. The photosensitive film is a film formed of a photosensitive material. Moreover, the multi-layer film may include an anti-reflection film and a protective film (top-coat film) for protecting the photosensitive film, for example. 
     The chamber device  5  includes a chamber member  5 A that forms a substantially closed inner space  8  and an environment control device  5 B that controls the environment (temperature, humidity, cleanness, pressure, and the like) of the inner space  8 . The substrate stage  2  grooves inside the inner space  8 . The control device  7  controls the environment of a space (the inner space  8 ), in which exposure of at least the substrate P held on the substrate stage  2  is performed, using the environment control device  5 A. 
     In the present embodiment, the body  6  is disposed in the inner space  8 . The body  6  includes a first column  9  formed on a supporting surface FL and a second column  10  formed on the first column  9 . The first column  9  includes a first supporting member  11  and a first surface plate  13  that is supported on the first supporting member  11  with an anti-vibration device  12  disposed therebetween. The second column  10  includes a second supporting member  14  that is provided on the first surface plate  13  and a second surface plate  16  that is supported on the second supporting member  14  with an anti-vibration device  15  disposed therebetween. Moreover, in the present embodiment, a third surface plate  18  is disposed on the supporting surface FL with an anti-vibration device  17 . 
     The illumination system IL irradiates a predetermined illumination region IR with the exposure light EL. The illumination region IR includes positions which can be irradiated with the exposure light EL emitted from the illumination system IL. The illumination system IL illuminates at least a part of the mask M disposed in the illumination region IR with the exposure light EL having a uniform illuminance distribution. As the exposure light EL emitted from the illumination system IL, deep ultraviolet light (DUV light) such as emission lines (g, h, and i-rays) emitted from a mercury lamp or a KrF excimer laser beam wavelength: 248 nm), vacuum ultraviolet light (VUV light) such as an ArF excimer laser beam (wavelength: 193 nm) or an F 2  laser beam (wavelength: 157 nm), and the like are used, for example. In the present embodiment, the ArF excimer laser beam, which is ultraviolet light (vacuum ultraviolet light), is used as the exposure light EL. 
     The mask stage  1  includes a mask holder  19  that releasably holds the mask M, and is movable on a guide surface  16 G of the second surface plate  16  in a state of holding the mask M. The mask stage  1  is movable relative to the illumination region IR while holding the mask M by the operation of a driving system  20 . The driving system  20  includes a planar motor which includes a movable member  20 A disposed on the mask stage  1  and a stationary member  20 B disposed on the second surface plate  16 . A planar motor capable of moving the mask stage  1  is disclosed in the specification of U.S. Pat. No. 6,452,292, for example. The mask stage  1  is movable in the six directions of the X, Y, and Z-axis directions and the θX, θY, and θZ directions by the operation of the driving system  20 . 
     The projection optical system PL irradiates a predetermined projection region PR with the exposure light EL. The projection optical system PL projects the image of the pattern on the mask M onto at least a part of the substrate P disposed in the projection region PR at a predetermined projection magnification. The projection optical system PL of the present embodiment is a reduction system with a projection magnification, for example, of ¼, ⅕, ⅛, or the like. The projection optical system PL may be either a unity-magnification system or a magnification system. In the present embodiment, the optical axis AX of the projection optical system PL is parallel to the Z axis. Moreover, the projection optical system PL may be any one of a refracting system which does not include a reflective optical element, a reflecting system which does not include a refractive optical element, and a catadioptric system which includes a reflective optical element and a refractive optical element. In addition, the projection system PL may form either an inverted image or an upright image. 
     A plurality of optical elements of the projection optical system PL is held on a holding member (lens barrel)  21 . The holding member  21  includes a flange  21 F. The projection optical system PL is supported on the first surface plate  13  with the flange  21 F disposed therebetween. An anti-vibration device may be provided between the first surface plate  13  and the holding member  21 . 
     The projection optical system PL includes an emission surface  23  from which the exposure light EL is emitted toward the image plane of the projection optical system PL. The emission surface  23  is disposed on a terminating optical element  22  which is closest to the image plane of the projection optical system PL among the plurality of optical elements of the projection optical system PL. The projection region PR includes a position which can be irradiated with the exposure light EL emitted from the emission surface  23 . In the present embodiment, the emission surface  23  faces the −Z direction and is parallel to the XY plane. The emission surface  23  facing the −Z direction may be a convex surface and may be a concave surface. 
     In the present embodiment, the optical axis (an optical axis near the image plane of the projection optical system PL) AX of the terminating optical element  22  is approximately parallel to the Z axis. In addition, an optical axis defined by an optical element adjacent to the terminating optical element  22  may be regarded as the optical axis of the terminating optical element  22 . Moreover, in the present embodiment, the image plane of the projection optical system PL is approximately parallel to the XY plane that includes the X and Y axes. Furthermore, in the present embodiment, the image plane is approximately horizontal. However, the image plane may not be parallel to the XY plane and may be a curved surface. 
     The substrate stage  2  includes a substrate holder  24  that releasably holds the substrate P, and is movable on a guide surface  18 G of the third surface plate  18 . The substrate stage  2  is movable relative to the projection region PR while holding the substrate P by the operation of a driving system  25 . The driving system  25  includes a planar motor which includes a movable member  25 A disposed on the substrate stage  2  and a stationary member  25 B disposed on the third surface plate  18 . A planar motor capable of moving the substrate stage  2  is disclosed in the specification of U.S. Pat. No. 6,452,292, for example. The substrate stage  2  is movable in the six directions of the X, Y, and Z-axis directions and the θX, θY, and θZ directions by the operation of the driving system  25 . 
     The substrate stage  2  includes an upper surface  26  which is disposed around the substrate holder  24  so as to face the emission surface  23 . In the present embodiment, the substrate stage  2  includes a plate member holder  27  that is disposed in at least a part of the circumference of the substrate holder  24  so as to releasably hold the lower surface of a plate member T, as disclosed in the specification and the like of US Patent Application Publication No. 200710177125. In the present embodiment, the upper surface  26  of the substrate stage  2  includes the upper surface of the plate member T. The upper surface  26  is flat. The plate member T may not be releasable from the substrate stage  2 . 
     In the present embodiment, the substrate holder  24  is capable of holding the substrate P so that the surface of the substrate P is approximately parallel to the XY plane. The plate member holder  27  is capable of holding the plate member T so that the upper surface  26  of the plate member T is approximately parallel to the XY plane. 
     The interferometer system  3  includes a first interferometer device  3 A capable of optically measuring the position of the mask stage  1  (the mask M) within the XY plane and a second interferometer device  3 B capable of optically measuring the position of the substrate stage  2  (the substrate P) within the XY plane. When executing an exposure process on the substrate P or executing a predetermined measurement process, the control device  7  operates the driving systems  20  and  25  based on the results of the measurement by the interferometer system  3  to thereby control the positions of the mask stage  1  (the mask M) and the substrate stage  2  (the substrate P). 
     The liquid immersion member  4  is disposed in at least a part of the circumference of the optical path of the exposure light EL. In the present embodiment, at least a part of the liquid immersion member  4  is disposed in at least a part of the circumference of the terminating optical element  22 . In the present embodiment, the liquid immersion member  4  is supported on a supporting mechanism  28 . In the present embodiment, the supporting mechanism  28  is supported on the first surface plate  13 . In the present embodiment, the liquid immersion member  4  is suspended on the first surface plate  13  with the supporting mechanism  28  disposed therebetween. 
     The exposure apparatus EX of the present embodiment is a scanning exposure apparatus (commonly called a scanning stepper) which projects the image of the pattern on the mask M onto the substrate P while moving the mask M and the substrate P in a predetermined scanning direction in a synchronized manner. When exposing the substrate P, the control device  7  controls the mask stage  1  and the substrate stage  2  so as to move the mask M and the substrate P in a predetermined scanning direction within the XY plane crossing the optical axis AX (the optical path of the exposure light EL). In the present embodiment, the scanning direction (synchronized moving direction) of the substrate P is the Y-axis direction, and the scanning direction (synchronized moving direction) of the mask M is also the Y-axis direction. The control device  7  irradiates the substrate P with the exposure light EL via the projection optical system PL and the liquid LQ in the liquid immersion space LS on the substrate P while moving the substrate P in the Y-axis direction relative to the projection region PR of the projection optical system PL and moving the mask M in the Y-axis direction relative to the illumination region IR of the illumination system IL in synchronization with the movement of the substrate P in the Y-axis direction. In this way, the image of the pattern on the mask M is projected onto the substrate P, and the substrate P is exposed with the exposure light EL. 
     Next, the liquid immersion member  4  will be described with reference to  FIGS. 2 and 3 .  FIG. 2  is a side cross-sectional view showing the vicinity of the liquid immersion member  4 , and  FIG. 3  is an enlarged view of a part of  FIG. 2 . 
     In the present embodiment, the liquid immersion member  4  is an annular member. At least a part of the liquid immersion member  4  is disposed around a part of the optical path of the exposure light EL and the terminating optical element  22 . In the present embodiment, the outer shape of the liquid immersion member  4  within the XY plane is circular. The outer shape of the liquid immersion member  4  may be other shapes (for example, a rectangular shape). 
     The liquid immersion member  4  includes a lower surface  30  which is configured to face the surface (upper surface) of an object disposed at a position facing the emission surface  23 . The liquid immersion member  4  forms the liquid immersion space LS so that an optical path K of the exposure light EL between the emission surface  23  and an object disposed at the position facing the emission surface  23  is filled with the liquid LQ. The liquid LQ is held between the surface (upper surface) of the object facing the lower surface  30  of the liquid immersion member  4  and at least a part of the lower surface  30  of the liquid immersion member  4 , and a part of the liquid immersion space LS is formed between the surface of the object and the lower surface  30  of the liquid immersion member  4 . Moreover, in the present embodiment, a part of the liquid immersion space LS is formed between the surface of the object and the terminating optical element  22 , and between the terminating optical element  22  and the liquid immersion member  4 . That is, in the present embodiment, the liquid LQ in the liquid immersion space LS includes the liquid LQ held between the liquid immersion member  4  and the object, the liquid LQ held between the terminating optical element  22  and the object, and the liquid LQ held between the liquid immersions member  4  and the terminating optical element  22 . 
     In the present embodiment, an object that is movable to the position facing the emission surface  23  includes at least one of the substrate stage  2  (the plate member T) and the substrate P held on the substrate stage  2 . During exposure of the substrate P, the liquid immersion member  4  forms the liquid immersion space LS so that the optical path K of the exposure light EL is filled with the liquid LQ. 
     Hereinafter, for the sake of simplicity, a case where the substrate P is disposed at the position facing the emission surface  23  and the lower surface  30 , and the liquid LQ is held between the liquid immersion member  4  and the substrate P, whereby the liquid immersion space LS is formed will be described as an example. In addition, the liquid immersion space LS may be formed between the terminating optical element  22  and the liquid immersion member  4  and other members (the plate member T of the substrate stage  2 , or the like). 
     In the present embodiment, the liquid immersion space LS is formed so that a partial region of the surface of the substrate P including the projection region PR is covered with the liquid LQ when the substrate P is irradiated with the exposure light EL. The exposure apparatus EX of the present embodiment employs a local liquid immersion method. 
     In the present embodiment, a gas-liquid interlace (meniscus) of the liquid LQ in the liquid immersion space LS includes a first interface LG 1  disposed between the lower surface  30  of the liquid immersion member  4  and the surface of the substrate P and a second interface LG 2  disposed between a side surface  31  of the projection optical system PL different from the emission surface  23  and an inner surface  32  of the liquid immersion member  4  different from the lower surface  30 . 
     The lower surface  30  of the liquid immersion member  4  is disposed in at least a part of the circumference of the optical path K of the exposure light EL emitted from the emission surface  23  of the projection optical system PL. The lower surface  30  is configured to face the surface of the substrate P disposed at the position which can be irradiated with the exposure light EL emitted from the emission surface  23 . The emission surface  23  and the lower surface  30  are configured to face the surface of the substrate P disposed below the liquid immersion member  4 . The emission surface  23  and the lower surface  30  face the surface of the substrate P during at least a part of the exposure period for the substrate P. 
     The side surface  31  of the projection optical system PL includes an outer side surface  31 A of the terminating optical element  22  disposed around the emission surface  23  and a lower surface  31 B that is disposed around the outer side surface  31 A and faces downward. The outer side surface  31 A and the lower surface  31 B are surfaces through which the exposure light EL does not pass. 
     The inner surface  32  of the liquid immersion member  4  faces at least a part of the side surface  31  of the projection optical system PL at an upper side than the emission surface  23 . The inner surface  32  of the liquid immersion member  4  includes an inner side surface  32 A of the liquid immersion member  4  facing the outer side surface  31 A and an upper surface  32 B of the liquid immersion member  4  facing the lower surface  31 B. In the present embodiment, the interface LG 2  is disposed between the outer side surface  31 A and the inner side surface  32 A. 
     In the present embodiment, the liquid immersion member  4  includes a plate portion  41  which is disposed so that at least a part thereof faces the emission surface  23  and a body portion  42  in which at least a part thereof is disposed around the terminating optical element  22 . The lower surface  30  is disposed on the plate portion  41  and the body portion  42 . The inner side surface  32 A and the upper surface  32 B are disposed on the body portion  42 . The inner side surface  32 A faces the outer side surface  31 A via a gap. The upper surface  32 B faces the lower surface  31 B via a gap. 
     In the present embodiment, the upper surface  32 B faces at least a part of the surface of the terminating optical element  22 . In the present embodiment, the terminating optical element  22  includes a flange portion  22 F disposed around the outer side surface  31 A, and the lower surface  31 B includes the lower surface of the flange portion  22 F. In addition, the upper surface  32 B may face the surface (lower surface) of the holding member  21  of the projection optical system PL, and may face both the surface of the terminating optical element  22  and the surface of the holding member  21 . Moreover, at least a part of the inner side surface  32 A may face a part of the holding member  21 , and may face the terminating optical element  22  and the holding member  21 . 
     Moreover, the plate portion  41  of the liquid immersion member  4  is disposed in at least a part of the circumference of the optical path K of the exposure light EL, and includes an upper surface  33  in which at least a part thereof faces the emission surface  23 . The upper surface  33  faces in the reverse direction of the lower surface  30 . 
     The liquid immersion member  4  (the plate portion  41 ) includes an opening  34  that the exposure light EL emitted from the emission surface  23  can pass. The lower surface  30  and the upper surface  33  are disposed around the opening  34 . During exposure of the substrate P the exposure light EL emitted from the emission surface  23  is irradiated on the surface of the substrate P through the opening  34 . In the present embodiment, the opening  34  is long in the X-axis direction crossing the sea direction (Y-axis direction) of the substrate P. 
     In the present embodiment, the liquid immersion member  4  includes a liquid supply port  35  for supplying the liquid LQ in order to fill the optical path K of the exposure light EL with the liquid LQ, a gas supply port  36  for supplying a gas GD including a material capable of changing the specific resistance of the liquid LQ to at least a part of a space S 1  around the liquid immersion space LS formed by the liquid LQ, and a gas supply port  37  disposed at a position different from the gas supply port  36  so as to supply a gas GD including a material capable of changing the specific resistance of the liquid LQ to at least a part of a space S 2  around the liquid immersion space LS. 
     The gas supply port  36  supplies the gas GD to at least a part of a space between the liquid immersion member  4  and the substrate P. The gas supply port  36  supplies the gas GD to at least a part of the space S 1  around the interface LG 1 , located between the lower surface  30  of the liquid immersion member  4  and the surface of the substrate P. 
     The gas supply port  37  supplies the gas GD to at least a part of a space between the projection optical system PL and the liquid immersion member  4 . The gas supply port  37  supplies the gas GD to at least a part of the space S 2  around the interface LG 2 , located between the side surface  31  of the projection optical system PL and the inner surface  32  of the liquid immersion member  4 . In the present embodiment, the gas GD supplied from the gas supply ports  36  and  37  includes a larger amount of the material that changes (decreases) the specific resistance of the liquid LQ than the gas in the inner space  8  controlled by the chamber device  5  (the environment control device  5 B). That is, in the present embodiment, by supplying the gas GD from the gas supply ports  36  and  37 , the gas spaces S 1  and S 2  in which the concentration (proportion) of the material that changes the specific resistance of the liquid LQ is higher than that of the inner space  8  are formed in at least a part of the circumference of the liquid immersion space LS. 
     In the present embodiment, the material capable of changing the specific resistance of the liquid LQ is carbon dioxide. The gas supply ports  36  and  37  supply the gas (carbonic acid gas) GD including carbon dioxide. 
     Carbon dioxide is soluble the liquid LQ supplied from the liquid supply port  35 . Moreover, carbon dioxide can decrease the specific resistance of the liquid LQ. 
     At least some of the gas GD supplied from the gas supply port  36  to the space S 1  between the lower surface  30  of the liquid immersion member  4  and the surface of the substrate P comes into contact with the interface LG 1 . The gas GD including carbon dioxide supplied so as to come into contact with the interface LG 1  is dissolved in the liquid LQ, whereby the specific resistance of the liquid LQ is decreased. 
     That is, in the present embodiment, the gas GD including carbon dioxide supplied to the space S 1  around the interface LG 1  of the liquid immersion space LS is mixed into and dissolved in some of the liquid LQ in the vicinity of the interface LG 1 . In this way, some of the liquid LQ (pure water) which is supplied from the liquid supply port  35  and present in the vicinity of the interface LG 1  is changed into carbonated water. Thus, the specific resistance of the liquid LQ in the vicinity of the interface LG 1  decreases. 
     As above, in the present embodiment, the gas GD supplied to the space S 1  is dissolved in some of the liquid LQ in the liquid immersion space LS, located between the liquid immersion member  4  and the substrate P, whereby the specific resistance of some of the liquid LQ is decreased. Thus, charging of the liquid LQ in the vicinity of the interface LG 1  is suppressed. 
     Similarly, at least some of the gas GD supplied from the gas supply port  37  to the space between the side surface  31  of the projection optical system PL and the inner surface  32  of the liquid immersion member  4  comes into contact with the interface LG 2 . The gas GD including carbon dioxide supplied so as to come into contact with the interface LG 2  is dissolved in the liquid LQ in the vicinity of the interface LG 2 , whereby the specific resistance of the liquid LQ in the vicinity of the interface LG 2  is decreased. Thus, the specific resistance of the liquid LQ in the vicinity of the interface LG 2  decreases. 
     In addition, the gas GD may be composed only of carbon dioxide (conductive adhesive agent), and may be a mixed gas of carbon dioxide and other gases (clean air or the like), for example. 
     The material capable of changing the specific resistance of the liquid LQ may not be carbon dioxide but may be ozone or hydrogen, for example. Such materials can decrease the specific resistance of the liquid LQ by being mixed into the liquid LQ. Moreover, the gas GD may include two or more kinds of materials capable of changing the specific resistance of the liquid LQ, and may include two or more kinds of optional materials selected from carbon dioxide, ozone, and hydrogen described above, for example. 
     Moreover, in the present embodiment, the liquid immersion member  4  includes a gas recovery port  38  for recovering at least some of the gas GD and a gas recovery port  39  disposed at a position different from the gas recovery port  38  so as to recover at least some of the gas GD. The gas recovery port  38  recovers at least some of the gas GD in the space S 1  around the interface LG 1 , located between the lower surface  30  of the liquid immersion member  4  and the surface of the substrate P. The gas recovery port  39  recovers at least some of the gas GD in the space S 2  around the interface LG 2 , located between the side surface  31  of the projection optical system PL and the inner surface  32  of the liquid immersion member  4 . 
     Moreover, in the present embodiment, the liquid immersion member  4  includes a liquid recovery port  40  for recovering at least some of the liquid LQ. 
     In the present embodiment, the liquid supply port  35  supplies the liquid LQ to the space between the liquid immersion member  4  and the terminating optical element  22 . In the present embodiment, the liquid supply port  35  is disposed on the inner side surface  32 A. In the present embodiment, the liquid supply port  35  is disposed on a predetermined portion of the liquid immersion member  4  so as to face the optical path K. In the present embodiment, the liquid supply port  35  supplies the liquid LQ to the space between the emission surface  23  and the upper surface  33 . 
     In addition, the liquid supply port  35  may be disposed on the inner side surface  32 A so as to face the outer side surface  31 A and may supply the liquid LQ to the space between the outer side surface  31 A and the inner side surface  32 A. 
     In the present embodiment, the liquid supply port  35  is disposed on each of the +Y and −Y sides in relation to the opening  34  (the optical path K of the exposure light EL). In addition, the liquid supply port  35  may be disposed on each of the +X and −X sides in relation to the opening  34  (the optical path K of the exposure light EL). Moreover, the number of liquid supply ports  35  is not limited to two. The liquid supply port  35  may be disposed at three or more positions around the optical path K of the exposure light EL. 
     The liquid LQ from the liquid supply port  35  is supplied to the optical path K of the exposure light EL. In this way, the optical path K of the exposure light EL is filled with the liquid LQ. 
     In the present embodiment, the liquid recovery port  40  is disposed on at least a part of the lower surface  30 . In the present embodiment, the surface of the substrate P disposed below the liquid immersion member  4  is configured to face the liquid recovery port  40 . 
     In the present embodiment, the liquid recovery port  40  is disposed on the lower surface  30  in at least a part of the circumference of the optical path K (the optical axis AX). The liquid recovery port  40  is capable of recovering the liquid LQ on the substrate P (object) disposed at the position facing the lower surface  30 . In the present embodiment, the shape of the liquid recovery port  40  within the XY plane is ring-shaped (circular and annular). 
     In addition, the shape of the liquid recovery port  40  within the XY plane may be rectangular and annular. Moreover, the liquid recovery port  40  may be disposed in at least a part of the circumference of the optical path K. For example, the liquid recovery port  40  may be disposed on only one side (+Y side) and the other side (−Y side) in the scanning direction of the substrate P in relation to the optical path K (opening  34 ), and a plurality of liquid recovery ports  40  may be disposed on the lower surface  30  around the optical path K at predetermined intervals. 
     In the present embodiment, a porous member  41  is disposed in the liquid recovery port  40 . The porous member  41  is a plate-shaped member including a plurality of openings or pores. In addition, the porous member  41  may be a mesh filter which is a porous member  41  in which a number of small openings or pores are formed in a network shape. The liquid recovery port  40  recovers the liquid LQ on the substrate P through the openings or pores of the porous member  41 . 
     In the present embodiment, the operation of recovering the liquid LQ by the liquid recovery port  40  is executed concurrently with the operation of supplying the liquid LQ by the liquid supply port  35  during at least a part of the exposure period for the substrate P. During at least a part of the exposure period for the substrate P, at least some of the liquid LQ supplied from the liquid supply port  35  to the space between the emission surface  23  and the upper surface  33  is supplied to the space between the lower surface  30  and the surface of the substrate P through the opening  34 , whereby the optical path K of the exposure light EL is filled with the liquid LQ. Moreover, some of the liquid LQ is held between the lower surface  30  and the surface of the substrate P. Since the operation of recovering the liquid LQ by the liquid recovery port  40  is executed concurrently with the operation of supplying the liquid LQ by the liquid supply port  35 , the size (volume) of the liquid immersion space LS formed between the liquid immersion member  4  and the substrate P is determined. The substrate P is exposed with the exposure light EL from the emission surface  23  via the liquid LQ between the emission surface  23  and the surface of the substrate P. 
     The gas supply port  36  is disposed on a predetermined portion of the liquid immersion member  4  so as to face the space S 1 . In the present embodiment, the gas supply port  36  is disposed on at least a part of the lower surface  30 . 
     The gas supply port  36  is disposed on the outer side of the liquid recovery port  40  in the radiation direction in relation to the optical axis AX. The gas supply port  36  is disposed on at least a part of the lower surface  30  around the optical path K (the optical axis AX). In the present embodiment, the gas supply port  36  is disposed at a position where it does not come into contact with the liquid LQ. That is, the gas supply port  36  is disposed on the outer side of the interface LG 1  in the radiation direction in relation to the optical axis AX. 
     In the present embodiment, the gas supply port  36  supplies the gas GD toward the surface of the substrate P facing the gas supply port  36 . In addition, the gas supply port  36  may supply the gas GD toward the inner side (toward the interface LG 1 ) in the radiation direction in relation to the optical axis AX. 
     In the present embodiment, the gas supply port  36  is disposed in at least a part of the circumference of the optical path K (the optical axis AX). In the present embodiment, the shape of the gas supply port  36  within the XY plane is ring-shaped (circular and annular). In the present embodiment, the gas supply port  36  is a slit opening that is formed so as to surround the optical path K of the exposure light EL. In addition, the shape of the gas supply port  36  within the XY plane may be rectangular or annular. 
     In the present embodiment, a concave portion  42  is formed on at least a part of the lower surface  30 . The concave portion  42  is recessed so as to be away from the surface of the substrate P facing the lower surface  30 . In the present embodiment, the gas supply port  36  is disposed on the inner surface of a concave portion that defines the concave portion  42 . 
     In the present embodiment, the shape of the concave portion  42  within the XY plane is ring-shaped (circular and annular). In addition, the shape of the concave portion  42  within the XY plane may be rectangular or annular. 
     The gas supply port  36  may be disposed in at least a part of the circumference of the optical path K (the optical axis AX). For example, a plurality of gas supply ports  36  may be disposed on the lower surface  30  around the optical path K at predetermined intervals. In this case, a plurality of concave portions  42  may be disposed on the lower surface  30  at predetermined intervals, and at least one gas supply port  36  may be disposed in a part or all of the plurality of concave portions  42 . 
     The plurality of gas supply ports  36  may be disposed to be separated in the radiation direction in relation to the optical axis AX. For example, the gas supply port  36  may include a first annular gas supply port disposed around the optical path K and a second gas supply port disposed on the outer side of the first gas supply port so as to be approximately concentric to the first gas supply port. In this case, both the first and second gas supply ports may be disposed on the inner surface of the concave portion  42 , and any one of the first and second gas supply ports may be disposed on the lower surface  30  on the outer side of the concave portion  42 , and the other may be disposed on the inner surface of the concave portion  42 . 
     The concave portion  42  may not be provided, and the gas supply port  36  may be disposed on the lower surface  30 . 
     The gas recovery port  38  is disposed in the liquid immersion member  4  so as to face the space S 1 . In the present embodiment, the gas recovery port  38  is disposed on at least a part of the lower surface  30 . 
     In the present embodiment, the gas recovery port  38  is disposed on the outer side of the gas supply port  36  in the radiation direction in relation to the optical axis AX. The gas recovery port  38  is disposed on at least a part of the lower surface  30  around the gas supply port  36 . The gas recovery port  38  is capable of recovering at least a part of the gas GD in the space S 1  around the interface LG 1 . 
     In the present embodiment, the shape of the gas recovery port  38  within the XY plane is ring-shaped (circular and annular). In the present embodiment, the gas recovery port  38  is a slit opening that is formed so as to surround the optical path K of the exposure light EL. In addition, the shape of the gas recovery port  38  within the XY plane may be rectangular or annular. 
     In the present embodiment, a concave portion  43  is formed on at least a part of the lower surface  30 . The concave portion  43  is recessed so as to be away from the surface of the substrate P facing the lower surface  30 . The concave portion  43  is disposed around the optical path K (the optical axis AX). The concave portion  43  is disposed on the outer side of the concave portion  42  in the radiation direction in relation to the optical axis AX. In the present embodiment, the gas recovery port  38  is disposed on the inner surface of the concave portion  43  that defines the concave portion  43 . 
     In the present embodiment, the shape of the concave portion  43  within the XY plane is ring-shaped (circular and annular). In addition, the shape of the concave portion  43  within the XY plane may be rectangular and annular. 
     The gas recovery port  38  may be disposed in at least a part of the circumference of the gas supply port  36 . For example, a plurality of gas recovery ports  38  may be disposed on the lower surface  30  around the optical path K (the optical axis AX) at predetermined intervals. In this case, a plurality of concave portions  43  may be disposed on the lower surface  30  around the optical path K at predetermined intervals, and at least one gas recovery port  38  may be disposed in each of the plurality of concave portions  43 . Moreover, the plurality of gas recovery ports  38  may be disposed so as to be separated in the radiation direction in relation to the optical axis AX. In this case, both a gas recovery port located closest to the optical path K (the optical axis AX) and a gas recovery port located farther from the optical axis AX than the first gas recovery port may be disposed on the inner surface of the concave portion  43 , and any one of them may be disposed on the inner surface of the concave portion  43 . 
     In the present embodiment, a humidifying system  44  is provided so as to make the humidity of the space S 1  supplied with the gas GD from the gas supply port  36  higher than the humidity of the inner space  8  controlled by the chamber device  5  (the environment control device  5 B). The humidifying system  44  humidifies the gas GD with the steam GW of the liquid LQ. 
     In the present embodiment, the humidifying system  44  includes an air supply port  45  for supplying the steam GW of the liquid LQ to the space S 1 . In the present embodiment, the air supply port  45  is disposed on the lower surface  30  of the liquid immersion member  4  so as to face the space S 1 . 
     In the present embodiment, the inner space  8  of the chamber device  5  is filled with clean air, and the air supply port  45  supplies air humidified by water vapor to the space S 1 . 
     In the present embodiment, the air supply port  45  is disposed in the vicinity of the gas supply port  36 . In the present embodiment, the air supply port  45  is disposed on the inner surface of the concave portion  42 . 
     In the present embodiment, the shape of the air supply port  45  within the XY plane is ring-shaped (circular and annular). In the present embodiment, the air supply port  45  is a slit opening that is formed so as to surround the optical path K of the exposure light EL. In addition, the shape of the air supply port  45  within the XY plane may be rectangular and annular. 
     A plurality of air supply ports  45  may be disposed so as to be separated in the radiation direction in relation to the optical axis AX. Moreover, the air supply port  45  may be disposed in at least a part of the circumference of the optical path K. For example, a plurality of air supply ports  45  may be disposed on the lower surface  30  around the optical path K at predetermined intervals. Moreover, the air supply port  45  may be disposed on the lower surface  30  on the outer side of the concave portion  42 . Furthermore, a part of the plurality of air supply ports  45  may be disposed on the concave portion  42 , and the remaining air supply ports may be disposed on the lower surface  30  on the outer side of the concave portion  42 . 
     The gas supply port  37  is disposed on a predetermined portion of the liquid immersion member  4  so as to face the space S 2 . In the present embodiment, the gas supply port  37  is disposed on at least a part of the inner side surface  32 A. 
     The gas supply port  37  is disposed above the emission surface  23 . The gas supply port  37  is disposed at a position where it does not come into contact with the liquid LQ. That is, the gas supply port  37  is disposed above the interface LG 2 . 
     In the present embodiment, the gas supply port  37  supplies the gas GD toward the outer side surface  31 A of the terminating optical element  22  facing the gas supply port  37 . In addition, the gas supply port  37  may supply the gas GD toward the lower side (toward the interface LG 2 ). 
     In the present embodiment, the gas supply port  37  is annular. In the present embodiment, the gas supply port  37  is a slit opening that is formed so as to surround the outer side surface  31 A. 
     The gas supply port  37  may be disposed around a part of the optical axis AX. For example, a plurality of gas supply ports  37  may be disposed on the inner side surface  32 A around the optical axis AX at predetermined intervals. 
     The gas recovery port  39  is disposed in the liquid immersion member  4  so as to face the space S 2 . In the present embodiment, the gas recovery port  39  is disposed on at least a part of the inner side surface  32 A. 
     The gas recovery port  39  is disposed above the gas supply port  37 . In the present embodiment, the gas recovery port  39  is annular. In the present embodiment, the gas recovery port  39  is a slit opening that is formed so as to surround the outer side surface  31 A. 
     The gas recovery port  39  may be disposed around a part of the optical path K. For example, a plurality of gas recovery ports  39  may be disposed on the inner side surface  32 A around the optical axis AX at predetermined intervals. 
     The gas supply port  37  and the gas recovery port  39  may be disposed on the upper surface  32 B. Moreover, the gas supply port  37  may be disposed on the inner side surface  32 A, and the gas recovery port  39  may be disposed on the upper surface  32 B. 
     As shown in  FIG. 2 , the liquid supply port  35  is connected to a liquid supply apparatus  46  through a supply flow channel. The supply flow channel includes an inner flow channel of the liquid immersion member  4  and a flow channel of a supply pipe that connects the inner flow channel and the liquid supply apparatus  46 . The liquid supply apparatus  46  supplies clean and temperature-adjusted liquid LQ to the liquid supply port  35 . 
     The liquid recovery port  40  is connected to a liquid recovery apparatus  47  through a recovery flow channel. In the present embodiment, the recovery flow channel includes an inner flow channel of the liquid immersion member  4  and a flow channel of a recovery pipe that connects the inner flow channel and the liquid recovery apparatus  47 . The liquid recovery apparatus  47  includes a vacuum system (a valve or the like that controls the connection state between a vacuum source and the liquid recovery port  40 ) and is capable of sucking and recovering the liquid LQ from the liquid recovery port  40 . 
     In the present embodiment, the control device  7  is capable of controlling the liquid recovery apparatus  47  to control a pressure difference between the upper surface side and the lower surface side of the porous member  41  so that only the liquid LQ passes from the lower surface-side space of the porous member  41  (the space between the lower surface of the porous member  41  and the surface of the substrate P) toward the upper surface-side space (the recovery flow channel). In the present embodiment, the lower surface-side space is open to the atmosphere and the pressure thereof is controlled by the chamber device  5 . The control device  7  controls the liquid recovery apparatus  47  so as to adjust the pressure of the upper surface side in accordance with the pressure of the lower surface side so that only the liquid LQ passes from the lower surface side of the porous member  41  toward the upper surface side. That is, the control device  7  adjusts the pressure of the upper surface-side space so that gas does not pass through the openings or pores of the porous member  41 . A technique of adjusting the pressure difference between one side and the other side of the porous member  41  so that only the liquid LQ passes from one side of the porous member  41  toward the other side is disclosed in the specification and the like of U.S. Pat. No. 7,292,313, for example. 
     In the present embodiment, “atmosphere” is gas surrounding the liquid immersion member  4 . In the present embodiment, the gas surrounding the liquid immersion member  4  is the gas in the inner space  8  which is formed by the chamber device  5 . In the present embodiment, the chamber device  5  fills the inner space  8  with clean air using the environment control device  5 B. Moreover, the chamber device  5  adjusts the pressure of the inner space  8  to approximately atmospheric pressure using the environment control device  5 B. Naturally, the pressure of the inner space  8  may be set to be higher than the atmospheric pressure. 
     In the present embodiment, the space between the side surface  31  of the projection optical system PL and the inner surface  32  of the liquid immersion member  4  is open to the atmosphere. Moreover, the space between the lower surface  30  of the liquid immersion member  4  and the surface of the substrate P is also open to the atmosphere. 
     The gas supply port  36  is connected to a gas supply apparatus  48  through a gas supply flow channel. The gas supply flow channel includes an inner flow channel of the liquid immersion member  4  and a flow channel of a gas supply pipe that connects the inner flow channel and the gas supply apparatus  48 . The gas supply apparatus  48  can supply clean and temperature-adjusted gas GD to the gas supply port  36 . 
     Similarly, the gas supply port  37  is connected to a gas supply apparatus  49  through a gas supply flow channel. 
     The air supply port  45  is connected to a humidifying apparatus  50  through a supply flow channel. The supply flow channel includes an inner flow channel of the liquid immersion member  4  and a flow channel of a supply pipe that connects the inner flow channel and the humidifying apparatus  50 . The humidifying apparatus  50  supplies the steam GW of the liquid LQ to the air supply port  45 . 
     The gas recovery port  38  is connected to a gas recovery apparatus  51  through a recovery flow channel. In the present embodiment, the recovery flow channel includes an inner flow channel of the liquid immersion member  4  and a flow channel of a recovery pipe that connects the inner flow channel and the gas recovery apparatus  51 . The gas recovery apparatus  51  includes a vacuum system and is capable of sucking and recovering gas in the space S 1  froth the gas recovery port  38 . 
     Similarly, the gas recovery port  39  is connected to a gas recovery apparatus  52  through a recovery flow channel. 
     Next, a method of exposing the substrate P using the exposure apparatus EX having the configuration described above will be described. 
     First, the control device  7  causes the emission surface  23  of the projection optical system PL and the lower surface  30  of the liquid immersion member  4  to face the surface of the substrate P (or the upper surface  26  of the substrate stage  2 ). 
     The control device  7  causes the liquid LQ to be delivered from the liquid supply apparatus  46  in a state where the emission surface  23  and the lower surface  30  face the surface of the substrate P. Moreover, the control device  7  operates the liquid recovery apparatus  47 . The liquid. LQ delivered from the liquid supply apparatus  46  is supplied to the liquid supply port  35 . The liquid supply port  35  supplies the liquid LQ to the space between the emission surface  23  and the upper surface  33  so that the optical path K between the emission surface  23  and the surface of the substrate P is filled with the liquid LQ. The liquid LQ supplied from the liquid supply port  35  to the space between the emission surface  23  and the upper surface  33  is supplied to the optical path K of the exposure light EL emitted from the emission surface  23 . In this way, the optical path K of the exposure light EL is filled with the liquid LQ. 
     Moreover, at least some of the liquid LQ supplied from the liquid supply port  35  is supplied to the space between the lower surface  30  and the surface of the substrate P through the opening  34  and is held between the lower surface  30  and the surface of the substrate P. In this way, the liquid immersion space LS is formed by the liquid LQ supplied from the liquid supply port  35  so that the optical path K of the exposure light EL, located between the emission surface  23  and the substrate P is filled with the liquid LQ. 
     At least some of the liquid LQ between the lower surface  30  and the surface of the substrate P is recovered through the liquid recovery port  40 . The liquid LQ recovered from the liquid recovery port  40  is recovered into the liquid recovery apparatus  47 . 
     Moreover, the control device  7  causes the gas GD to be delivered from the gas supply apparatuses  48  and  49 . Moreover, the control device  7  operates the gas recovery apparatuses  51  and  52 . Moreover, the control device  7  operates the humidifying apparatus  50 . 
     The gas GD delivered from the gas supply apparatus  48  is supplied to at least a part of the space S 1  around the liquid immersion space LS of the liquid LQ formed on the substrate P through the gas supply port  36 . Moreover, the steam GW delivered from the humidifying apparatus  50  is supplied to at least a part of the space S 1  through the air supply port  45 . Furthermore, the gas GD delivered from the gas supply apparatus  49  is supplied to at least a part of the space S 2  around the liquid immersion space LS through the gas supply port  37 . 
     The control device  7  controls the liquid supply apparatus  46 , the liquid recovery apparatus  47 , the gas supply apparatus  48 , the humidifying apparatus  50 , the gas recovery apparatus  51 , the gas supply apparatus  49 , and the gas recovery apparatus  52  so that the operation of supplying the liquid LQ by the liquid supply port  35 , the operation of recovering the liquid LQ by the liquid recovery port  40 , the operation of supplying the gas GD by the gas supply port  36 , the operation of supplying the steam GW by the air supply port  45 , the operation of recovering the gas GD and the steam GW by the gas recovery port  38 , the operation of supplying the gas GD by the gas supply port  37 , and the operation of recovering the gas GD by the gas recovery port  39  are executed concurrently. That is, the control device  7  supplies the gas GD and the steam GW to the space S 1  around the liquid immersion space LS and recovers the gas GD and the steam GW in the space S 1  in a state where the liquid immersion space LS is formed by the liquid LQ supplied from the liquid supply port  35 . Moreover, the control device  7  supplies the gas GD to the space S 2  around the liquid immersion space LS and recovers the gas GD in the space S 2  in a state where the liquid immersion space LS is formed. 
     The control device  7  starts the exposure of the substrate P in a state where the liquid immersion space LS is formed. The control device  7  causes the exposure light EL to be emitted from the illumination system IL so that the mask M is illuminated with the exposure light EL. The exposure light EL from the mask M is emitted from the emission surface  23  of the projection optical system PL. The control device  7  exposes the substrate P with the exposure light EL from the emission surface  23  via the liquid LQ between the emission surface  23  and the surface of the substrate P. In this way, the image of the pattern on the mask M is projected onto the substrate P, and the substrate P is exposed with the exposure light EL. During the exposure of the substrate P, the operation of supplying the liquid LQ by the liquid supply port  35 , the operation of recovering the liquid LQ by the liquid recovery port  40 , the operation of supplying the gas GD by the gas supply port  36 , the operation of supplying the steam GW by the air supply port  45 , the operation of recovering the gas GD and the steam GW by the gas recovery port  38 , the operation of supplying the gas GD by the gas supply port  37 , and the operation of recovering the gas GD by the gas recovery port  39  are executed concurrently. 
     Since the gas GD is supplied to the space S 1 , charging of the liquid LQ in the vicinity of the interface LG 1  is suppressed. Moreover, charging of the liquid immersion member  4  contacting the liquid LQ, charging of the substrate P, and charging of the substrate stage  2  (the plate member T) are suppressed. 
     In the present embodiment, since the concave portions  42  and  43  are provided, it is possible to increase the size of the space S 1  in which the gas GD is filled. Thus, the gas GD in the space S 1  can be smoothly dissolved in the liquid LQ, and charging can be suppressed. 
     Moreover, since the gas GD is supplied to the space S 2 , charging of the liquid LQ in the vicinity of the interface LG 2  is suppressed. Moreover, charging of the liquid immersion member  4  contacting the liquid LQ and charging of the terminating optical element  22  are suppressed. 
     Furthermore, since the gas GD in the space S 1  is recovered from the gas recovery port  38 , the gas GD is suppressed from flowing into a space (the atmosphere or the inner space  8 ) around the liquid immersion member  4 . Similarly the gas recovery port  39  suppresses the gas GD in the space S 2  from flowing into the space around the liquid immersion member  4 . 
     Moreover, in the present embodiment, the steam GW is supplied to the space S 1  in which the gas GD is supplied. By causing the gas GD and the liquid LQ to contact each other in a state where the humidity of the space S 1  around the liquid immersion space LS is high, the gas GD (the material that changes the specific resistance of the liquid LQ) becomes easily dissolved in the liquid LQ. Thus, by supplying the steam GW to the space S 1 , dissolution of the gas GD in the liquid LQ is accelerated, and charging of the liquid LQ can be suppressed more effectively. 
     Moreover, by increasing the humidity of the space S 1  around the liquid immersion space LS, it is possible to suppress vaporization of the liquid LQ in the liquid immersion space LS. Thus, it is possible to suppress the occurrence of a temperature change of the liquid LQ, the liquid immersion member  4 , and the substrate stage  2  (the plate member T) due to vaporization heat of the liquid LQ. 
     The gas supply apparatus  48  may supply a humidified gas GD to the gas supply port  36 . That is, the gas supply apparatus  48  may include a humidifying apparatus. In this case, the humidifying system  44  which includes the humidifying apparatus  50  and the air supply port  45  may not be provided. Moreover, the gas supply apparatus  49  may supply the humidified gas GD to the gas supply port  37 . 
     In the present embodiment, the control device  7  may adjust at least one of the supply amount per unit time of the gas GD supplied from the gas supply port  36  to the space S 1  and the supply amount per unit time of the gas GD supplied from the gas supply port  37  to the space S 2 . For example, a sensor capable of detecting the charge quantity of the liquid LQ is provided, and the control device  7  adjusts the supply amount of the gas GD based on the results of the detection by the sensor. For example, the control device  7  can adjust the supply amount of the gas GD based on the results of the detection by a capacitance sensor which is provided on at least a part of the liquid immersion member  4  and is capable of detecting the charge quantity of the liquid LQ. The specific resistance of the liquid LQ changes with the supply amount of the gas GD. For example, when the charge quantity of the liquid LQ is determined to be large based on the detection results from the sensor, the control device  7  increases the supply amount of the gas GD. On the other hand, when the charge quantity of the liquid LQ is determined to be small, the control device  7  decreases the supply amount of the gas GD. Moreover, the control device  7  may adjust at least one of the proportion (concentration) of the carbon dioxide included in the gas GD supplied from the gas supply port  36  and the proportion (concentration) of the carbon dioxide included in the gas GD supplied from the gas supply port  37 . In this case, adjustment can be performed based on the results obtained by the sensor described above. Moreover, the control device  7  may adjust the amount (flow rate) per unit time of the steam GW supplied from the air supply port  45  to the space S 1 . In this case, adjustment can be performed based on the results of the detection by the sensor. 
     When the liquid LQ supplied from the liquid supply port  35  is pure water (ultrapure water), the possibility of charging of the liquid LQ increases. Moreover, when the surface of a member contacting the liquid LQ such as the upper surface  26  of the substrate stage  2  (the plate member T) or the surface of the substrate P has insulating properties, the possibility of charging of the member increases. For example, when the upper surface  26  of the substrate stage  2  is formed of a liquid repellent material (fluorinated material or the like) having insulating properties, the possibility of charging increases. Moreover, when the surface of the substrate P is formed of an insulating top-coat film, the possibility of charging increases. Moreover, the exposure apparatus EX of the present embodiment is a scanning exposure apparatus, in which when the substrate P (the substrate stage  2 ) moves in a predetermined direction within the XY plane in a state where the liquid immersion space LS is formed, the possibility that at least one of the liquid LQ and the member (the substrate P, the substrate stage  2 , or the like) contacting the liquid LQ may be charged increases. 
     According to the present embodiment, since the gas GD including the material capable of changing the specific resistance of the liquid LQ is supplied t the spaces S 1  and S 2  around the liquid immersion space LS, it is possible to suppress charging of the liquid LQ and the member contacting the liquid LQ. That is, since the supplied gas GD changes the liquid LQ in the vicinity of the interfaces LG 1  and LG 2  into carbonated water, so that the specific resistance of the liquid LQ is changed, it is possible to suppress charging of the liquid LQ in the vicinity of the interfaces LG 1  and LG 2 . In particular, the present embodiment is effective when the liquid LQ in the vicinity of the interfaces LG 1  and LG 2  is likely to be charged. 
     In the present embodiment, the space S 1  around the interface LG 1  is filled with the gas GD, and the space S 2  around the interface LG 2  is filled with the gas GD. Thus, the spaces S 1  and S 2  filled with the gas GD suppress the liquid LQ in the liquid immersion space LS from coming into contact with the gas (air in the present embodiment) in the inner space  8  controlled by the chamber device  5 . 
     In the present embodiment, since the gas GD including the material capable of changing the specific resistance of the liquid LQ is supplied to the spaces S 1  and S 2  around the liquid immersion space LS formed by the liquid LQ which is supplied from the liquid supply port  35 , it is possible to suppress charging of the liquid LQ in the periphery of the liquid immersion space LS and the member contacting the liquid LQ while suppressing a change in the properties of the liquid LQ in the optical path K of the exposure light EL. Therefore, it is possible to expose the substrate P satisfactorily. 
     As described above, according to the present embodiment, it is possible to suppress charging of the liquid LQ in the liquid immersion space LS and charging of the member contacting the liquid LQ. Thus, it is possible to suppress the occurrence of exposure defects and to suppress the occurrence of defective devices. 
     For example, when at least one of the liquid LQ and the member is charged, there is a possibility that foreign materials (particles) are adsorbed to the liquid LQ or the member, and exposure defects occur. Examples of foreign materials include foreign materials generated from the substrate P (flakes of part of a photosensitive film, flakes of part of an top-coat film, flakes of part of an anti-reflection film, or the like), or foreign materials floating around the substrate stage  2 . 
     According to the present embodiment, since charging of the liquid LQ and the member contacting the liquid LQ is suppressed, it is possible to suppress foreign materials from being adsorbed to the liquid LQ and the member. Thus, it is possible to suppress the occurrence of exposure defects. 
     Second Embodiment 
     Next, the second embodiment will be described. In the following description, constituent elements which are the same as or similar to those of the above embodiment will be denoted by the same reference numerals, and description thereof will be simplified or omitted. 
       FIG. 4  is a view showing an example of a liquid immersion member  4 B according to the second embodiment. The second embodiment is a modified example of the first embodiment. The characteristic part of the second embodiment different from the first embodiment described above is that concave portions  53  and  54  are formed on at least a part of an inner side surface  32 A, a gas supply port  37 B for supplying the gas GD and an air supply port  55 B for supplying the steam GW are disposed on the inner surface of a concave portion  53  that defines the concave portion  53 , and a gas recovery port  39 B for recovering the gas GD and the steam GW is disposed on the inner surface of a concave portion  54  that defines the concave portion  54 . 
     In  FIG. 4 , the concave portion  53  is recessed so as to be away from an outer side surface  31 A facing the inner side surface  32 A. The concave portion  53  is disposed around the outer side surface  31 A. The concave portion  54  is disposed above the concave portion  53 . The concave portion  54  is recessed so as to be away from the outer side surface  31 A facing the inner side surface  32 A. The concave portion  54  is disposed around the outer side surface  31 A. 
     The gas supply port  37 B is disposed on the inner surface of the concave portion  53 . The gas supply port  37 B supplies the gas GD to the space S 2  between the outer side surface  31 A and the inner side surface  32 A. The air supply port  55 B supplies the steam GW of the liquid LQ to the space S 2  and makes the humidity of the space S 2  supplied with the gas GD higher than the humidity of the inner space  8 . 
     In the present embodiment, since the concave portions  53  and  54  are formed, it is possible to increase the size of the space S 2  in which the gas GD is filled. Thus, the gas GD in the space S 2  can be smoothly dissolved in the liquid LQ, and charging can be suppressed. Moreover, since the steam GW is supplied to the space S 2 , dissolution of the gas GD in the liquid LQ is accelerated, and charging of the liquid LQ can be suppressed more effectively. Furthermore, since vaporization of the liquid LQ in the vicinity of the interface LG 2  of the liquid LQ is suppressed, it is possible to suppress a change in the temperature of the liquid LQ, the terminating optical element  22 , and the liquid immersion member  4 B. 
     In the second embodiment, although the gas supply port  37 B and the air supply port  55 B are disposed in the concave portion  53 , one of them may be disposed in the concave portion  53 , and the other may be disposed on the inner side surface  32 A on the outer side of the concave portion  53 . 
     Moreover, the concave portion  53  may not be provided, and the gas supply port  37 B and the air supply port  55 B may be disposed on the inner side surface  32 A. Moreover, the concave portion  54  may not be provided, and the gas recovery port  39 B may be disposed on the inner side surface  32 A. 
     Furthermore, in the second embodiment, at least one of the gas supply port  37 B, the gas recovery port  39 B, and the air supply port  55 B may be provided on the upper surface  32 B of the liquid immersion member  4 B. 
     Third Embodiment 
     Next, the third embodiment will be described. In the following description, constituent elements which are the same as or similar to those f the above embodiments will be denoted by the same reference numerals, and description thereof will be simplified or omitted. 
       FIG. 5  is a view showing an example of a liquid immersion member  4 C according to the third embodiment. The third embodiment is a modified example of the first embodiment. The characteristic part of the third embodiment different from the first embodiment described above is that a gas supply port  36 C, an air supply port  45 C, and a gas recovery port  38 C are disposed in at least a part of the circumference of the optical path K of the exposure light EL and on a holding member  56  disposed on the outer side of the liquid immersion member  4 C in the radiation direction in relation to the optical axis AX. 
     In the present embodiment, the holding member  56  is an annular member disposed around the liquid immersion member  4 C. The holding member  56  includes a lower surface  57  which is configured to face the surface of the substrate P. In the present embodiment, at least some of the gas GD supplied from the gas supply port  36 C is held between the lower surface  57  of the holding member  56  and the surface of the substrate P. 
     In the present embodiment, a liquid supply port  35 C for supplying the liquid LQ in order to fill the optical path K of the exposure light EL with the liquid LQ, a liquid recovery port  40 C (a porous member  41 C) for recovering the liquid LQ, a gas supply port  37 C for supplying the gas GD to the space S 2 , and a gas recovery port  39 C for recovering the gas GD in the space S 2  are disposed in the liquid immersion member  4 C. 
     In the present embodiment, a gas supply port  36 C for supplying the gas GD to the space S 1 , an air supply port  45 C for supplying the steam GW to the space S 1 , and a gas recovery port  38 C for recovering the gas GD and the steam GW in the space S 1  are disposed on the lower surface  57  of the holding member  56 . The gas supply port  36 C and the air supply port  45 C are disposed on the inner surface of a concave portion  42 C formed on the lower surface  57 , and the gas recovery port  38 C is disposed on the inner surface of a concave portion  43 C formed on the lower surface  57 . In the present embodiment, the space S 1  is a space between at least a part of the lower surface  30 C of the liquid immersion member  4 C and the lower surface  57  of the holding member  56 , and the surface of the substrate P. 
     In the present embodiment, is possible to suppress charging of the liquid LQ and the like and to suppress the occurrence of exposure defects. 
     In the present embodiment, the gas supply port  36 C and the air supply port  45 C may be disposed in the liquid immersion member  4 C, and the gas recovery port  38 C may be disposed on the holding member  56 . That is, some of the gas supply port  36 C, the air supply port  45 C, and the gas recovery port  38 C may be disposed on the holding member  56 , and the remaining ports may be disposed in the liquid immersion member  4 C. Moreover, some of the gas supply port  36 C, the air supply port  45 C, and the gas recovery port  38 C may be disposed on still another member. 
     Moreover, in the third embodiment, one of the gas supply port  36 C and the air supply port  45 C may be disposed in the concave portion  42 C, and the other may be disposed on the lower surface  57  of the holding member  56 . The concave portion  42 C may not be provided, and both the gas supply port  36 C and the air supply port  45 C may be provided on the lower surface  57 . Moreover, in the third embodiment, the concave portion  43 C may not be provided, and the gas recovery port  38 C may be provided on the lower surface  57 . Furthermore, in the third embodiment, the humidified gas GD may be supplied from the gas supply port  36 C, and the air supply port  45 C may be omitted. In the third embodiment, the steam of the liquid LQ may be supplied to the space S 2 , and the humidified gas GD may be supplied from the gas supply port  37 C. 
     In the first to third embodiments described above, although a case where the steam GW humidifies the gas GD by the steam of the liquid LQ has been described as an example, the gas GD may be humidified by the steam of liquid different from the liquid LQ. 
     Moreover, in the first to third embodiments described above, although the gas GD supplied to the space S 1  from the gas supply port is the same as the gas GD supplied to the space S 2  from the gas supply port, they may be different from each other. For example, the gas GD supplied to the space S 1  may include carbon dioxide as the material that changes the specific resistance of the liquid LQ, and the gas GD supplied to the space S 2  may include hydrogen as the material that changes the specific resistance of the liquid LQ 1 . Alternatively, the concentration (proportion) of the material that changes the specific resistance of the liquid LQ may be different between that in the gas GD supplied to the space S 1  and that in the gas GD supplied to the space S 2 . 
     Furthermore, in the first to third embodiments described above, the gas including the material that changes the specific resistance of the liquid LQ may be supplied to any one of the spaces S 1  and S 2 . Moreover, in the first to third embodiments described above, although at least a part of the space S 1  is humidified by supplying the steam GW from the air supply port and/or supplying the humidified gas GD from the gas supply port, the space S 1  may not be humidified. Furthermore, in the first to third embodiments described above, at least one of the gas recovery port for recovering the gas from the space S 1  and the gas recovery port for recovering the gas from the space S 2  may be omitted. 
     Fourth Embodiment 
     Next, the fourth embodiment will be described. In the following description, constituent elements which are the same as or similar to those of the above embodiments will be denoted by the same reference numerals, and description thereof will be simplified or omitted. 
       FIG. 6  is a view showing an example of a liquid immersion member  4 D according to the fourth embodiment. In  FIG. 6 , the liquid immersion member  4 D includes a first supply port  35 D for supplying a first liquid LQ 1  in order to fill the optical path K of the exposure light EL emitted from the emission surface  23  with the first liquid LQ 1  having a first specific resistance and a second supply port  36 D for supplying a second liquid LQ 2  having a specific resistance different from the first liquid LQ 1  to at least a part of a space S 11  around a liquid immersion space LS 1  formed by the first liquid LQ 1 . In the present embodiment, the second liquid LQ 2  has a specific resistance lower than the first liquid LQ 1 . 
     Similarly to the liquid immersion member  4  of the first embodiment described above, the liquid immersion member  4 D according to the present embodiment is disposed in at least a part of the circumference of the optical path K. A part of the liquid immersion space LS 1  is formed between the substrate P facing the lower surface  30 D of the liquid immersion member  4 D and the lower surface  30 D of the liquid immersion member  4 D. 
     The first supply port  35 D supplies the first liquid LQ 1  to the space between the emission surface  23  and the upper surface  33 . In the present embodiment, the first liquid LQ 1  is water (pure water). 
     The second supply port  36 D is disposed on the lower surface  30 D of the liquid immersion member  4 D. The second supply port  36 D supplies the second liquid LQ 2  to the space S 11 . In the present embodiment, the second liquid LQ 2  includes the first liquid. LQ 1 . That is, the component of the second liquid LQ 2  is the first liquid LQ 1  (water). 
     In the present embodiment, the second liquid LQ 2  is formed by dissolving (adding) a material that decreases the specific resistance of the first liquid LQ 1  in the first liquid LQ 1 . In the present embodiment, the material is carbon dioxide. That is, the second liquid LQ 2  is carbonated water which is formed by dissolving carbon dioxide in the first liquid LQ 1  (water). 
     The second liquid LQ 2  may include ozone or hydrogen. That is, the second liquid LQ 2  may be ozone water in which ozone is dissolved in water and may be hydrogen water in which hydrogen is dissolved in water. The ozone water or the hydrogen water can decrease the specific resistance of the first liquid LQ 1 . 
     Moreover, the liquid immersion member  4 D includes a first recovery port  40 D that is disposed on the lower surface  30 D so as to recover at least some of the first liquid LQ 1  on the substrate P. A porous member  41 D is disposed in the first recovery port  40 D. The first recovery port  40 D of the liquid immersion member  4 D has approximately the same configuration as the liquid recovery port  40  of the liquid immersion member  4  of the first embodiment described above, and detailed description thereof will be omitted. 
     The second supply port  36 D is disposed on the outer side of the first recovery port  40 D in the radiation direction in relation to the optical axis AX. In the present embodiment, the shape of the second supply port  36 D within the XY plane is annular. The second supply port  36 D is disposed so as to surround the first recovery port  40 D. In addition, a plurality of second supply ports  36 D may be disposed on the lower surface  30 D around the optical path K at predetermined intervals. 
     Moreover, the liquid immersion member  4 D includes a second recovery port  58 D that is disposed on the lower surface  30 D so as to recover at least some of the second liquid LQ 2  on the substrate P. The second recovery port  58 D is disposed on the outer side of the second supply port  36 D in the radiation direction in relation to the optical axis AX. A porous member  59 D is disposed in the second recovery port  58 D. Similarly to the first recovery port  40 D, the second recovery port  58 D recovers only liquid through the openings or pores of the porous member  59  but does not recover gas. 
     Moreover, the liquid immersion member  4 D includes a gas supply port  37 D which is disposed on the inner side surface  32 A so as to be capable of supplying gas GD including a material capable of changing the specific resistance of the first liquid LQ 1  to the space S 2  between the terminating optical element  22  and the liquid immersion member  4 D and a gas recovery port  39 D capable of recovering the gas GD in the space S 2 . The gas supply port  37 D and the gas recovery port  39 D of the liquid immersion member  4 D have approximately the same configurations as the gas supply port  37  and the gas recovery port  39 D of the liquid immersion member  4  of the first embodiment described above, and detailed description thereof will be omitted. 
     Next, a method of exposing the substrate P using the exposure apparatus EX having the configuration described above will be described. 
     The control device  7  performs the operation of supplying the first liquid LQ 1  by the first supply port  35 D and the operation of recovering liquid by the first recovery port  40 D in a state where the emission surface  23  and the lower surface  30 D face the surface of the substrate P. The first supply port  35 D supplies the first liquid LQ 1  to the optical path K of the exposure light EL. At least some of the first liquid LQ 1  between the lower surface  30 D and the surface of the substrate P is recovered through the first recovery port  40 D. A liquid immersion space LS 1  is formed by the first liquid LQ 1  supplied from the first supply port  35 D so that the optical path K of the exposure light EL between the emission surface  23  and the surface of the substrate P is filled with the first liquid LQ 1 . 
     Moreover, the control device  7  performs the operation of supplying the gas GD to the space S 2  by the gas supply port  37 D and the operation of recovering the gas GD in the space S 2  by the gas recovery port  39 D. In this way, the space S 2  is filled with the gas GD, and the gas GD comes into contact with the interface LG 2  of the first liquid LQ 1 . 
     Moreover, the control device  7  performs the operation of supplying the second liquid LQ 2  to the space S 11  by the second supply port  36 D and performs the operation of recovering the second liquid LQ 2  in the space S 11  by the second recovery port  58 D. At least some of the second liquid LQ 2  supplied to the space S 11  through the second supply port  36 D is recovered through the first recovery port  40 D. Moreover, at least some of the second liquid LQ 2  supplied to the space S 11  through the second supply port  36 D is recovered through the second recovery port  58 D. That is, in the present embodiment, the first recovery port  40 D recovers the first and second liquid LQ 1  and LQ 2  on the substrate P, and the second recovery port  58 D mainly recovers the second liquid LQ 2  on the substrate P. 
     In this way, the space S 11  is filled with the second liquid LQ 2 , and the second liquid LQ 2  supplied to the space S 11  through the second supply port  36 D comes into contact with the interface LG 1  of the first liquid LQ 1  in the liquid immersion space LS 1 . 
     The control device  7  starts exposure of the substrate P in a state where the liquid immersion space LS 1  is formed. The control device  7  exposes the substrate P with the exposure light EL from the emission surface  23  via the first liquid LQ 1  between the emission surface  23  and the surface of the substrate P. 
     During exposure of the substrate P, the operation of supplying the first liquid LQ 1  by the first supply port  35 D, the operation of supplying the second liquid LQ 2  by the second supply port  36 D, the operation of recovering the first and second liquid LQ 1  and LQ 2  by the first recovery port  40 D, the operation of recovering the second liquid LQ 2  by the second recovery port  58 D, the operation of supplying the gas GD by the gas supply port  37 D, and the operation of recovering the gas GD by the gas recovery port  39 D are executed concurrently. 
     In the present embodiment, the space S 1  around the liquid immersion space LS 1  formed by the first liquid LQ 1  is filled with the second liquid LQ 2  having a low specific resistance, and the space S 11  filled with the second liquid LQ 2  suppress the first liquid LQ 1  in the liquid immersion space LS 1  from coming into contact with the gas (air in the present embodiment) in the inner space  8  controlled by the chamber device  5 . 
     In the present embodiment, since the second liquid LQ 2  which has a lower specific resistance than the first liquid LQ 1  and which is mixed with the first liquid LQ 1  in the vicinity of the interface LG 1  and is capable of decreasing the specific resistance of the first liquid LQ 1  in the vicinity of the interface LG 1  is supplied to the space S 11 , charging of the first liquid LQ 1  is suppressed. Moreover, charging of the liquid immersion member  4  contacting the first liquid LQ 1 , charging of the substrate P, and charging of the substrate stage  2  (the plate member T) are suppressed. 
     Fifth Embodiment 
     Next, the fifth embodiment will be described. In the following description, constituent elements which are the same as or similar to those of the above embodiments will be denoted by the same reference numerals, and description thereof will be simplified or omitted. 
       FIG. 7  is a view showing an example of a liquid immersion member  4 E according to the fifth embodiment. The liquid immersion member  4 E according to the fifth embodiment is a modified example of the liquid immersion member  4 D according to the fourth embodiment. The characteristic part of the liquid immersion member  4 E according to the fifth embodiment different from the liquid immersion member  4 D according to the fourth embodiment is that a second supply port  36 E for supplying the second liquid LQ 2  is disposed on the inner side of a first recovery port  40 E in the radiation direction in relation to the optical axis AX. Moreover, in the liquid immersion member  4 E of the present embodiment, the second recovery port ( 58 D) is not provided. 
     In the present embodiment, the second supply port  36 E is disposed on the lower surface  30 E of the liquid immersion member  4 E around the optical path K. That is, the shape of the second supply port  36 E is annular. In addition, a plurality of second supply ports  36 E may be disposed on the lower surface  30 E around the optical path K at predetermined intervals. 
     Moreover, the liquid immersion member  4 E includes a gas supply port  37 E for supplying the gas GD to the space S 2  and a gas recovery port  39 E for recovering the gas GD in the space S 2 . The gas supply port  37 E and the gas recovery port  39 E of the liquid immersion member  4 E have approximately the same configurations as the gas supply port  37  and the gas recovery port  39 D of the liquid immersion member  4  of the first embodiment described above, and detailed description thereof will be omitted. 
     In the present embodiment, the optical path K is formed by the first liquid LQ 1 , and the periphery of a liquid immersion space LS 2  including an interface LG 11  between the liquid immersion member  4 E and the substrate P is formed by the first liquid. LQ 1  from the first supply port  35 E and the second liquid LQ 2  from the second supply port  36 E. The first recovery port  40 E recovers both the first liquid LQ 1  and the second liquid LQ 2  through a porous member  41 E. 
     In the present embodiment, since the second liquid LQ 2  having a lower specific resistance than the first liquid LQ 1  is supplied in the vicinity of the interface LG 11 , it is possible to effectively suppress charging of the liquid in the liquid immersion space LS in the vicinity of the interface LG 11 . 
     In the present embodiment, a second recovery port disposed to be separated from the first recovery port  40 E may be provided on the lower surface  30 E of the liquid immersion member  4 E on the outer side of the first recovery port  40 E in the radiation direction in relation to the optical axis AX. 
     Moreover, in the present embodiment, an air supply port for supplying the steam of the second liquid LQ 2  may be provided on the outer side of the first recovery port  40 E in the radiation direction in relation to the optical axis AX, and similarly to the first to third embodiments described above, a space having higher humidity than the inner space  8  may be formed in at least a part of the circumference of the liquid immersion space LS 2 . 
     Sixth Embodiment 
     Next, the sixth embodiment will be described. In the following description, constituent elements which are the same as or similar to those of the above embodiments will be denoted by the same reference numerals, and description thereof will be simplified or omitted. 
       FIG. 8  is a view showing an example of a liquid immersion member  4 F according to the sixth embodiment. The sixth embodiment is a modified example of the fourth embodiment. The characteristic part of the sixth embodiment different from the fourth embodiment is that a second supply port  36 F and a second recovery port  58 F (a porous member  59 F) are disposed in at least a part of the circumference of the optical path K of the exposure light EL and on a holding member  56 F disposed on the outer side of the liquid immersion member  4 F in the radiation direction relation to the optical axis AX. 
     In the present embodiment, the holding member  56 F is an annular member disposed around the liquid immersion member  4 F. The holding member  56 F includes a lower surface  57 F which is configured to face the surface of the substrate P. In the present embodiment, at least some of the second liquid LQ 2  is held between the lower surface  57 F of the holding member  56 F and the surface of the substrate P. 
     In the present embodiment, a first supply port  35 F for supplying the first liquid LQ 1  to the optical path K, a first recovery port  40 F in which the porous member  41 F is disposed and which recovers the liquid on the substrate P, a gas supply port  37 F for supplying the gas GD to the space S 2 , and a gas recovery port  39 F for recovering the gas GD in the space S 2  are disposed in the liquid immersion member  4 F. 
     In the present embodiment, a second supply port  36 F for supplying the second liquid LQ 2  to the space S 11  and a second recovery port  58 F for recovering at least some of the second liquid LQ 2  are disposed on the lower surface  57 F of the holding member  56 F. The second recovery port  58 F recovers the second liquid LQ 2  through a porous member  59 F. The second recovery port  58 F is disposed on the outer side of the second supply port  36 F in the radiation direction in relation to the optical axis AX. The second recovery port  58 F mainly recovers the second liquid LQ 2  from the second supply port  36 F, and the first recovery port  40 F recovers the first liquid LQ 1  from the first supply port  35 F and the second liquid LQ 2  from the second supply port  36 F. 
     In the present embodiment, it is possible to suppress charging of the first liquid LQ 1  and the like and to suppress the occurrence of exposure defects. 
     In the present embodiment, the second supply port  36 F may be disposed on the holding member  56 F, and the second recovery port  58 F may be disposed on a member different from the liquid immersion member  4 F and the holding member  56 F. 
     Seventh Embodiment 
     Next, the seventh embodiment will be described. In the following description, constituent elements which are the same as or similar to those of the above embodiments will be denoted by the same reference numerals, and description thereof will be simplified or omitted. 
       FIG. 9  is a view showing an example of a liquid immersion member  4 G according to the seventh embodiment. The seventh embodiment is a modified example of the sixth embodiment. 
     As shown in  FIG. 9 , a second supply port  36 G for supplying the second liquid LQ 2  to the space S 11  is provided on the lower surface  30 G of the liquid immersion member  4 G. Moreover, the liquid immersion member  4 G includes a first supply port  35 G for supplying the first liquid LQ 1  to the optical path K, a gas supply port  37 G for supplying the gas GD to the space S 2 , a gas recovery port  39 G for recovering the gas GD in the space S 2 , and a first recovery port  40 G for recovering the liquid on the substrate P. 
     In the present embodiment, a second recovery port  58 G for recovering at least some of the second liquid LQ 2  is provided on the lower surface  57 G of the holding member  56 G. 
     In the present embodiment, it is possible to suppress charging of the first liquid LQ 1  and the like and to suppress the occurrence of exposure defects. 
     In the fourth to seventh embodiments described above, although a case where the second liquid LQ 2  is formed by dissolving the material that decreases the specific resistance of the first liquid LQ 1  in the first liquid LQ 1  has been described as an example, the second liquid LQ 2  may be formed by dissolving the material in a liquid different from the first liquid LQ 1 . That is, the main component of the first liquid LQ 1  may be different from the main component of the second liquid LQ 2 . 
     Moreover, in the fourth to seventh embodiments described above, the material that decreases the specific resistance of the first liquid LQ 1  included in the second liquid LQ 2  may be different from the material that decreases the specific resistance of the first liquid LQ 1  included in the gas GD supplied to the space S 2 . 
     Moreover, in the fourth to seventh embodiments described above, the gas recovery port ( 39 D,  39 E,  39 F, or  39 G) for recovering the gas from the space S 2  may be provided on the upper surface  32  of the liquid immersion member ( 4 D,  4 E,  4 F, or  4 G), and the gas recovery port ( 39 D,  39 E,  39 F, or  39 G) may not be provided. 
     Moreover, in the fourth to seventh embodiments described above, the steam of the first liquid LQ 1  may be supplied to the space S 2 , and the gas GD humidified by the steam of the first liquid LQ 1  may be supplied to the space S 2 . 
     Moreover, in the fourth to seventh embodiments described above, the gas supply port ( 37 D,  37 E,  37 F, or  37 G) for supplying the gas GD to the space S 2  and the gas recovery port ( 39 D,  39 E,  39 F, or  39 G) for recovering the gas from the space S 2  may be omitted. 
     Moreover, in the fourth, sixth and seventh embodiments described above, an air supply port for supplying the steam of the second liquid LQ 2  may be provided on the outer side of the second recovery port ( 58 D,  58 F, or  58 G) in the radiation direction in relation to the optical axis AX, and similarly to the first to third embodiments described above, a space of which the humidity is higher than the inner space  8  may be formed in at least a part of the circumference of the space S 11 . 
     Moreover, in the fourth, sixth, and seventh embodiments described above, although the difference between the pressure of the upper surface-side space of the porous member ( 59 D,  59 F, or  59 G) and the pressure of the lower surface-side space is adjusted so that the second recovery port ( 58 D,  58 F, or  58 G) recovers only liquid, the second recovery port ( 58 D,  58 F, or  58 G) may recover liquid together with gas. In this case, the porous member ( 59 D,  59 F, or  59 G) may be omitted. 
     Moreover, in the fourth, sixth, and seventh embodiments described above, the second recovery port (the porous member) may be disposed on the lower side than the first recovery port (the porous member). 
     Moreover, in the first to seventh embodiments described above, although the first recovery port ( 40  or the like) recovers only liquid, the first recovery port may recover liquid together with gas. In this case, the porous member ( 41  or the like) of the first recovery port ( 40  or the like) may be omitted. 
     Moreover, in the first to seventh embodiments described above, the liquid immersion member ( 4  or the like) may be movable relative to the terminating optical element  22  in parallel to at least one of the X, Y, and Z axes and may be rotatable about the X, Y, and Z axes. 
     Moreover, in the first to seventh embodiments described above, the plate portion  41  of the liquid immersion member may be omitted. For example, the lower surface ( 30  or the like) of the liquid immersion member may be provided in at least a part of the circumference of the emission surface  23 . In this case, the lower surface ( 30  or the like) of the liquid immersion member may be disposed at the same height as the emission surface  23  or on the upper side (+Z side) than the emission surface  23 . 
     Moreover, in the first to seventh embodiments described above, although the optical path on the emission side (image plane side) of the terminating optical element  22  of the projection optical system PL is filled with the liquid LQ (the first liquid LQ 1 ), a projection optical system in which the optical path on the incidence side (object plane side) of the terminating optical element  22  is also filled with liquid may be employed as disclosed in the pamphlet of PCT International Publication No. 2004/019128, for example. The liquid filled in the incidence-side optical path of the terminating optical element  22  may be the same kind of liquid as the liquid LQ (the first liquid LQ 1 ) and may be a different kind of liquid from the liquid LQ (the first liquid LQ 1 ). 
     Although the liquid LQ (the first liquid LQ 1 ) of the respective embodiments described above is water, it may be liquid other than water. For example, hydrofluoroether (HFE), perfluorinated polyether (PFPE), fomblin oil, or the like can be used as the liquid LQ (the first liquid LQ 1 ). Moreover, various liquids, for example a supercritical liquid, can be used as the liquid LQ. 
     Furthermore, the substrate P of the respective embodiments described above may be not only a semiconductor wafer for manufacturing semiconductor devices but also a glass substrate for display devices, a ceramic wafer for thin-film magnetic heads, or the raw plate (synthetic quartz or a silicon wafer) of a mask or a reticle that is used by an exposure apparatus. 
     As for the exposure apparatus EX, a step-and-scan type scanning exposure apparatus (a scanning stepper) that scans and exposes the pattern of the mask M by synchronously moving the mask M and the substrate P, and a step-and-repeat type projection exposure apparatus (a stepper) that performs exposure of the pattern of the mask M in a batch with the mask M and the substrate P in a stationary state and then sequentially moves the substrate P in a stepwise manner can be used. 
     Furthermore, the step-and-repeat type exposure may be performed in a batch such that after a reduced image of a first pattern is transferred to the substrate P using the projection optical system in a state where the first pattern and the substrate P are substantially stationary, a reduced image of a second pattern is transferred to the substrate P so as to be partially superimposed on the first pattern using the projection optical system in a state where the second pattern and the substrate P are are substantially stationary (a stitch type batch exposure apparatus). In addition, a step-and-stitch type exposure apparatus in which at least two patterns are transferred to the substrate P in a partially superimposed manner, and the substrate P is sequentially moved can be used as the stitch type exposure apparatus. 
     Moreover, as disclosed in U.S. Pat. No. 6,611,316, for example, the present invention can also be applied to an exposure apparatus that combines the patterns of two masks on a substrate through a projection optical system and double exposes, substantially simultaneously, a single shot region on the substrate using a single scanning exposure. Furthermore, the present invention can also be applied to a proximity type exposure apparatus, a mirror projection aligner, or the like. 
     Moreover, the present invention can also be adapted to a twin stage type exposure apparatus that includes a plurality of substrate stages, as disclosed in the specifications of U.S. Pat. Nos. 6,341,007, 6,208,407, and 6,262,796, for example. 
     In addition, the present invention can also be applied to an exposure apparatus that includes a substrate stage which holds a substrate and a measurement stage on which a reference member having a reference mark formed thereon and/or various photoelectric sensors are mounted, and which does not hold an exposure target substrate, as disclosed in the specification of U.S. Pat. No. 6,897,963 and the specification of US Patent Application Publication No. 2007/0127006, for example. Moreover, the present invention can also be applied to an exposure apparatus that includes a plurality of substrate stages and a plurality of measurement stages. 
     The type of exposure apparatus EX is not limited to an exposure apparatus for manufacturing semiconductor devices that exposes the pattern of a semiconductor device on the substrate P, but can be widely applied to exposure apparatuses used for manufacturing liquid crystal display devices or displays and exposure apparatuses used for manufacturing thin-film magnetic heads, image capturing devices (CCDs), micromachines (MEMS), DNA chips, or reticles and masks, for example. 
     Moreover, in the respective embodiments described above, an ArF excimer laser may be used as a light source apparatus that generates ArF excimer laser light as the exposure light EL. However, as disclosed in U.S. Pat. No. 7,023,610, for example, a harmonic generation device which includes a solid-state laser light source such as a DFB semiconductor laser or a fiber laser, an optical amplifier part including a fiber amplifier and the like, and a wavelength converter, and which outputs pulsed light with a wavelength of 193 nm may be used. Furthermore, in the above embodiments, although the illumination regions and projection regions described above have a rectangular shape, they may have a different shape, for example, a circular arc shape. 
     Furthermore, in the respective embodiments described above, a transmitting mask in which a predetermined shielding pattern (or a phase pattern or a dimming pattern) is formed on a transmissive substrate has been used. However, instead of this mask, as disclosed in the specification of U.S. Pat. No. 6,778,257, for example, a variable form mask (also referred to as an electronic mask, an active mask, or an image generator) that forms a transmission pattern, a reflection pattern, or a light emitting pattern based on electronic data of the pattern to be exposed may be used. The variable form mask includes a digital micro-mirror device (DMD), which is one kind of non-emission type image display device (spatial light modulator), for example. In addition, instead of a variable form mask that includes a non-emission type image display device, a pattern forming apparatus that includes a self-emission image display device may be provided. Examples of the self-emission type image display device include a cathode ray tube (CRT), an inorganic EL display, an organic EL display (OLED: organic light emitting diode), an LED display, an LD display, a field emission display (FED), and a plasma display (PDP: plasma display panel). 
     In the respective embodiments described above, although the exposure apparatus that includes the projection optical system PL has been described as an example, the present invention can be applied to an exposure apparatus and an exposure method which do not use the projection optical system PL. As above, even when the projection optical system PL is not used, the exposure light is irradiated onto the substrate through optical members such as lenses, and a liquid immersion space is formed in a predetermined space between these optical members and the substrate. 
     Furthermore, as disclosed in the pamphlet of PCT International Publication No. 2001/035168, for example, the present invention can be also applied to an exposure apparatus (a lithography system) that exposes the substrate P with a line-and-space pattern by forming interference fringes on the substrate P. 
     As described above, the exposure apparatus EX of the present embodiment is manufactured by assembling various subsystems including the respective constituent elements mentioned in the claims of the present application so that predetermined mechanical, electrical, and optical accuracies are maintained. To ensure these various accuracies, adjustments are performed before and after this assembly, including an adjustment for achieving optical accuracy for various optical systems, an adjustment for achieving mechanical accuracy for various mechanical systems, and an adjustment for achieving electrical accuracy for various electrical systems. The process of assembling various subsystems into the exposure apparatus includes, for example, the mechanical interconnection of various subsystems, the wiring and connection of the circuits, and the piping and connection of the atmospheric pressure circuit. Naturally, prior to performing the process of assembling various subsystems into the exposure apparatus, the processes of assembling individual subsystems are performed. When the process of assembling various subsystems into the exposure apparatus is completed, comprehensive adjustments are performed, whereby various accuracies of the exposure apparatus as a whole are secured. Furthermore, it is preferable to manufacture the exposure apparatus in a clean room where the temperature, the cleanliness level, and the like are controlled. 
     As shown in  FIG. 10 , a microdevice such as a semiconductor device is manufactured through: a step  201  of designing the functions and performance of the microdevice; a step  202  of fabricating a mask (a reticle) based on this designing step; a step  203  of manufacturing a substrate which is the base material of the device; a substrate processing step  204  including exposing the substrate with exposure light using the pattern of the mask in accordance with the embodiments described above and developing the exposed substrate; a device assembling step  205  (including a processing process such as a dicing process, a bonding process, and a packaging process); an inspecting step  206 ; and the like. 
     Furthermore, the requirements of the respective embodiments may be appropriately combined with each other. Moreover, some constituent elements may not be used. As far as is permitted by the law; the disclosures in all of the Patent Application Publications and US Patents elated to exposure apparatuses and the like cited in the above respective embodiments and modified examples, are incorporated herein by reference.